Design and performance study of hybrid photocatalytic reactor-PVDF/MWCNT nanocomposite membrane system for treatment of petroleum refinery wastewater

CATEGORY: WASTEWATER TREATMENT 
Design and performance study of hybrid photocatalytic reactor-PVDF/MWCNT nanocomposite membrane system for treatment of petroleum refinery wastewater

Type	Journal Article
Author	A. Moslehyani
Author	A. F. Ismail
URL	http://www.sciencedirect.com/science/article/pii/S0011916415000727
Series	Hybrid Systems for Desalination
Volume	363
Pages	99-111
Publication	Desalination
Date	May 1, 2015
Abstract	Focuses on the design and performance of a hybrid system consisting of a photocatalytic reactor and a membrane permeation cell. Researchers installed an ultraviolet lamp in the photocatalytic reactor to decompose the organic pollutants in the presence of 200 ppm titanium-dioxide (TiO2). They identified individual hydrocarbon pollutants using gas chromatography–mass spectrometry (GC–MS) analysis of wastewater samples. Polyvinylidene fluoride (PVDF)/multi-walled carbon nanotube (MWCNT) nanocomposite membranes were fabricated to enhance the rejection, flux and fouling resistance for full filtration of pollutants from photocatalytic reactor such as decomposed refinery wastewater and TiO2 photocatalyst. The nanocomposite membranes were characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TiO2 cross-over during permeation was detected by using an atomic adsorption spectrometer, which proved that TiO2 rejection was more than 99% for oxidized MWCNT nanocomposite membranes. Researchers found tThe nanocomposite membrane with 1.0 wt.% of oxidized MWCNTs incorporated in PVDF matrix to be the best nanocomposite membrane among all of the fabricated membranes for the filtration purposes, due to the over 99% rejection and excellent anti-fouling property.

Thermogravimetric monitoring of crude oil and its cuts in an oil refinery

CATEGORY: THERMOGRAVIMETRIC MODELING 
Thermogravimetric monitoring of crude oil and its cuts in an oil refinery

Type	Journal Article
Author	Agustin Garcia Barneto
Author	Jose Ariza Carmona
URL	http://dx.doi.org/10.1021/ef5028795
Publication	Energy & Fuels
Date	March 17, 2015
Abstract	The thermal degradation profile for any type of oil-based sample under thermogravimetric analysis (TGA) conditions displays three distinct stages: vaporization from room temperature to 340/350 ºC, cracking from 340/350 ºC to 480/500 ºC and char oxidation from 500 ºC to 570 ºC. The former two stages occur in both inert (nitrogen) and oxidative (air) environments. The latter occurs only in the presence of oxygen. Deconvoluting thermogravimetric data makes it possible to estimate the composition of oil derivatives, enabling expeditious acquisition of useful information from a refining process. Accordingly, researchers modelled thermal degradation of crude oil and its main refining cuts using the smallest possible number of representative pseudo-components. In order to ensure accurate fitting of thermogravimetric results, they interprested mass losses in terms of autocatalytic kinetics. Fitting to an nth-order kinetics was useful below 350 ºC, but not above this temperature owing to cracking with fast mass losses in the vicinity of certain temperatures. The modelling scheme for thermogravimetric results afforded the following conclusions: (a) atmospheric gas-oil typically contains 10% residual kerosene fraction; (b) atmospheric residue still contains 35?45% distillable compounds; (c) the main component of visbreaking feed (nearly 66%) degrades at a similar temperature as asphaltenes; (d) visbreaking residue is similar to feed at high temperatures but contains light components similar to naphtha or gas-oil which vaporize at low temperatures; (e) simulating crude oil allowed us to estimate the potential production of distillates. Such useful information can be used by process engineers to assess the performance of equipment such as distillation columns or visbreaking units, and also to estimate the quality of some streams such as atmospheric gas-oil or visbreaking feed.

Propane Dehydrogenation Catalyzed by ZSM-5 Zeolites. A Mechanistic Study Based on the Selective Energy Transfer (SET) Theory

CATEGORY: PROPANE 
Propane Dehydrogenation Catalyzed by ZSM-5 Zeolites. A Mechanistic Study Based on the Selective Energy Transfer (SET) Theory

Type	Journal Article
Author	Ragnar Larsson
URL	Free Full Text Source:  http://www.mdpi.com/1420-3049/20/2/2529
Volume	20
Issue	2
Pages	2529-2535
Publication	Molecules
Date	2015-02-02
Abstract	Experimentally determined activation energies of propane dehydrogenation catalyzed by ZSM-5 zeolites have been used to test the SET theory. The basis of this theory is that the catalyst system transfers vibrational energy via a resonance process to a specific vibration mode of the reacting molecule. Being excited up to a certain number of vibrational quanta the molecule is brought to reaction. By analyzing the above-mentioned activation energies we found the wave number of this “specific mode” to be 1065 cm−1. This is very close to the rocking vibration of propane (1053 cm−1). Authors suggest that the propane molecule reacts when excited so that the CH3 group has been forced towards a flat structure with a carbon atom hybridization that is more sp2 than sp3. Consequently there is no way for three H-atoms to bind to the carbon and one of them must leave. This is the starting point of the reaction. The isokinetic temperature of the system was found as Tiso = 727 ± 4 K. From the SET formula for Tiso when both energy-donating (ω) and energy-accepting (ν) vibrations have the same frequency, viz., Tiso = Nhcν/2R, we obtain ν = ω = 1011 ± 6 cm−1. This agrees rather well with the CH3 rocking mode (1053 cm−1) and also with asymmetric “TO4” stretching vibrations of the zeolite structure (ω).

Effect of sulfate addition on the performance of Co/Al2O3 catalysts in catalytic dehydrogenation of propane

CATEGORY: PROPANE 
Effect of sulfate addition on the performance of Co/Al2O3 catalysts in catalytic dehydrogenation of propane

Type	Journal Article
Author	Ya-nan Sun
Author	Ya-nan Gao
URL	http://www.sciencedirect.com/science/article/pii/S1566736714004774
Volume	60
Pages	42-45
Publication	Catalysis Communications
Date	February 5, 2015
Abstract	Reports results of an investigation of the effect of sulfate species in propane dehydrogenation over Co/Al2O3 catalysts. While the interaction between SO42− and cobalt species leads to better dispersed cobalt oxide and restrains the reduction to metallic Co species, inhibiting cracking reaction, the initial C–H bond activation and scission are facilitated on the electron-deficient cobalt and sulfate sites, resulting in dramatically improved dehydrogenation performance. XPS, MS and XRD results reveal that the reduction of sulfate species to SO2 and consequently the loss of active cobalt species contribute to the irreversible deactivation of catalyst.

Characterization of oily sludge from a refinery and biodegradability assessment using various hydrocarbon degrading strains and reconstituted consortia

CATEGORY: OILY SLUDGE 
Characterization of oily sludge from a refinery and biodegradability assessment using various hydrocarbon degrading strains and reconstituted consortia

Type	Journal Article
Author	Jublee Jasmine
Author	Suparna Mukherji
URL	http://www.sciencedirect.com/science/article/pii/S0301479714004976
Volume	149
Pages	118-125
Publication	Journal of Environmental Management
Date	February 1, 2015
Abstract	Oily sludge obtained from a refinery in India contained 10–11% oil associated with fine particulates. Along with Fe, Ca and Mg various toxic elements were associated with the sludge solids. The oil contained 41–56% asphaltenes and the maltenes comprised of 49 ± 4%, 42 ± 2% and 4 ± 2%, aliphatic, aromatic and polar fractions, respectively. Biodegradation studies with the maltene fraction of oil provided as sole substrate revealed higher degradation by various 3-5 membered reconstituted consortia compared to pure bacterial strains and up to 42 ± 8% degradation could be achieved over 30 days. Over the same period, in contrast, up to 71.5 ± 2% oil degradation could be achieved using dried oily sludge as sole substrate. Significant biodegradation in the un-inoculated controls indicated the presence of indigenous microorganisms in oily sludge. However, researchers noted large variability in oil degradation in the un-inoculated controls. Greater biodegradation of the maltene fraction led to significant enrichment of asphaltenes in residual oil associated with the sludge.

Understanding octane number evolution for enabling alternative low RON refinery streams and octane boosters as transportation fuels

CATEGORY: OCTANE 
Understanding octane number evolution for enabling alternative low RON refinery streams and octane boosters as transportation fuels

Type	Journal Article
Author	Nikola Rankovic
Author	Guillaume Bourhis
Author	Rueil-Malmaison, France, Aramco Fuel Research Center
URL	http://www.sciencedirect.com/science/article/pii/S0016236115001453
Volume	150
Pages	41-47
Publication	Fuel
Date	June 15, 2015
Abstract	Spark ignition (SI) engine performance is limited by knock phenomena, which are linked to fuel resistance to auto-ignition, quantified by its octane number. While high octane numbers are crucial for efficient high load operating points, they are less necessary at low load. Consequently, if the octane number of the fuel could be tuned as any other engine setting parameter, the engine efficiency and CO2 emissions could be improved, leading to an Octane on Demand concept, using, for instance, a dual fuel strategy. This requires understanding the behavior of dual fuel combustions with lower/higher octane fuels, and more particularly the evolution of RON when blending high RON fuels with low RON ones. Developing an Octane on Demand concept requires the choice of appropriate octane enhancers and understand their blending behavior. Accordingly, researchers measured  RON for a CFR engine using a broad range of mixtures of low-octane base fuels with various boosters capable of increasing the antiknock resistance of the blends. The chemical composition of booster streams was chosen to assess the potential of using alternative refinery products for improving fuel resistant auto-ignition properties when added to a whole-range naphtha and RON 91 gasoline. The study covers five octane boosters: ethanol, reformate, di-isobutylene, 2-butanol, and a mixture of butanols. Experimental results revealed a non-linear behavior of RON values with respect to volumetric incorporation rates of octane boosters. In the cases when the booster is an alcohol (C2 or C4), linear by-mole blending rules can be applied with an acceptable prediction error. For boosters rich in olefins and aromatics, molar blending was less accurate. Ethanol exhibited the strongest boosting effect among all the octane boosters on the one hand. On the other hand, the octane enhancing effect is stronger for the base fuel of lower starting RON value. Experimental results of the current study represent a comprehensive database for tailoring fuel RON properties aimed to explore combustion behavior of low-octane fuels enhanced through an addition of an external booster.

Microwave irradiated nickel nanoparticles on Vulcan XC-72R carbon black for methanol oxidation reaction in KOH solution

CATEGORY: METHANOL OXIDATION 
Microwave irradiated nickel nanoparticles on Vulcan XC-72R carbon black for methanol oxidation reaction in KOH solution

Type	Journal Article
Author	R. M. Abdel Hameed
Author	Rabab M. El-Sherif
Author	Cairo University, Giza, Egypt Chemistry Department, Faculty of Science
URL	http://www.sciencedirect.com/science/article/pii/S0926337314003968
Volume	162
Pages	217-226
Publication	Applied Catalysis B: Environmental
Date	January 2015
Abstract	Researchers fabricated Ni/C electrocatalysts using chemical deposition of nickel nanoparticles on Vulcan XC-72R carbon black using microwave irradiation technique. They varied the time of microwave irradiation during the reduction step and nickel weight percentage. They observed this to affect the morphology of formed Ni/C powder as shown by TEM analysis. Increasing nickel weight percentage resulted in the formation of more aggregated deposits. The electrocatalytic activity of various Ni/C samples towards methanol oxidation reaction in KOH solution was examined by applying cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopic techniques. Ni/C electrocatalyst containing 30 wt.% Ni [Ni/C-30] exhibited 5.2 times higher electrocatalytic activity than that with 10 wt.% Ni [Ni/C-10]. Heating Ni/C powder into microwave oven using the pulse mode of 30 s on/10 s off formed the most stable electrocatalyst for prolonged oxidation reaction. Electrochemical impedance measurements revealed that Ni/C-30 electrocatalyst has the lowest impedance value of 0.022 kΩ cm2, while the highest one is for Ni/C-10 [0.331 kΩ cm2] in (0.4 M methanol + 0.5 M KOH) solution at 500 mV. It confirmed that Ni/C-30 has the highest electrocatalytic activity towards methanol oxidation reaction.

Separation of aromatic solvents from oil refinery reformates by a newly designed ionic liquid using gas chromatography with flame ionization detection

CATEGORY: LIQUID-LIQUID EXTRACTION 
Separation of aromatic solvents from oil refinery reformates by a newly designed ionic liquid using gas chromatography with flame ionization detection

Type	Journal Article
Author	Indra Bahadur
Author	Mbongeni Mabaso
URL	http://onlinelibrary.wiley.com/doi/10.1002/jssc.201400990/abstract
Volume	38
Issue	6
Pages	951-957
Publication	Journal of Separation Science
Date	March 1, 2015
Abstract	Reports a study to determine whether the novel ionic liquid, N,N-dimethyl-2-oxopyrrolidonium iodide is a suitable solvent for the separation of aromatic components benzene, toluene, ethylbenzene, and xylenes from petroleum mixtures (reformates) in liquid–liquid extraction. Researchers developed a method to extract all components of a mixture, containing four aromatic components simultaneously. A novel ionic liquid and a previously used liquid were compared for their extraction abilities. The ionic liquids were N,N-dimethyl-2-oxopyrrolidinium iodide and 1-ethyl-3-methyl imidazolium ethyl sulfate. Researchers measured the concentrations of each benzene, toluene, ethylbenzene, and xylenes component in the extract and raffinate phases using gas chromatography with flame ionization detection as volume percent to determine the extraction ability of the ionic liquids. Results obtained for both the reformate samples and model mixtures indicated that the new ionic liquid was effective as an extracting solvent for the recovery of aromatic components from reformates. In addition, analysis results using gas chromatography with flame ionization detection for the reformate samples were as good as the results obtained by a local oil refinery. The extraction results also show that the developed method is suitable for the separation and analysis of aromatic components in reformates.

Recent Advances in Osmium-Catalyzed Hydrogenation and Dehydrogenation Reactions

CATEGORY: HYDROGENATION 
Recent Advances in Osmium-Catalyzed Hydrogenation and Dehydrogenation Reactions

Type	Journal Article
Author	Giorgio Chelucci
Author	Salvatore Baldino
URL	http://dx.doi.org/10.1021/ar5003818
Volume	48
Issue	2
Pages	363-379
Publication	Accounts of Chemical Research
Date	February 17, 2015
Abstract	A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. There is also great interest in multitasking catalysts that can efficiently promote various organic transformations by careful switching of such reaction parameters as temperature, solvent, and cocatalyst. Osmium complexes have exhibited the ability to efficiently catalyze various types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, interest has focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proven to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. In contrast, osmium catalysts have received much less attention, because they are considered less active on account of their slower ligand exchange kinetics. Authors highlight developments achieved over the past few years on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon/oxygen and carbon/nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. Authors demonstrate that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Results give an idea of the potential of Os complexes for the design of new highly productive and robust catalysts for the synthesis of chiral and nonchiral alcohols and amines as well as ketones from alcohols.

Hydroalkylation Process (ExxonMobil)

CATEGORY: HYDROALKYLATION 
Hydroalkylation Process (ExxonMobil)

Type	Patent
Inventor	Christopher L. Becker
Inventor	James R. Lattner
URL	Free Full Text Source:  http://www.google.com/patents/US20150005531
Assignee	Exxonmobil Chemical Patents Inc.
Patent Number	US20150005531 A1
Issue Date	Jan 1, 2015
Abstract	In a process for producing phenol, benzene is hydroalkylated with hydrogen in the presence of a catalyst under conditions effective to produce a hydroalkylation reaction product comprising cyclohexylbenzene and cyclohexane. At least a portion of the cyclohexane from said hydroalkylation reaction product is then dehydrogenated to produce a dehydrogenation effluent comprising benzene, toluene and hydrogen. At least a portion of the dehydrogenation effluent is washed with a benzene-containing stream to transfer at least a portion of the toluene from the dehydrogenation effluent to the benzene-containing stream.

Method of injecting fuel into a gasifier via pressurization (ExxonMobil)

CATEGORY: GASIFICATION 
Method of injecting fuel into a gasifier via pressurization (ExxonMobil)

Type	Patent
Inventor	Michael F. Raterman
URL	Free Full Text Source:  http://www.google.com/patents/US8951315
Assignee	Exxonmobil Research And Engineering Company
Patent Number	US8951315 B2
Issue Date	Feb 10, 2015
Abstract	The present invention relates to an improved gasifier injection system. In particular, the present invention provides an improved apparatus and operating scheme to improve the control flow of solid particulates in a multi-burner gasifier. The system also provides for integrated flow control and emergency shutoff in the case of abnormal operating conditions or unexpected backflow of the process burners. This improved design simplifies the mechanical systems required for large multi-burner gasifiers thus providing a more reliable and compact gasifier feed system. In preferred embodiments, the gasifier hydrocarbon feed is substantially in a solid particulate state and is preferably comprised of coal, petrochemical coke, and/or solid biomass.