An experimental and modeling study of vacuum residue upgrading in supercritical water

Arabian Heavy crude oil was fractionated into distillate and vacuum residue fractions. The vacuum residue fraction was treated with supercritical water (SCW) at 450°C in a batch reactor for 15–90 min. The main products were gas, coke, and upgraded vacuum residue; the upgraded residue consisted of gasoline, diesel, and vacuum gas oil range components. The molecular composition of gas and upgraded vacuum residue was analyzed using gas chromatography (GC, GC × GC). SCW treatment converted higher carbon number aliphatics (≥C₂₁) and long‐chain (≥C₅) alkyl aromatic compounds into C₁?C₂₀ aliphatics, C₁?C₁₀ alkylaromatics, and multiringed species. The concentrations of gasoline and diesel range compounds were greater in the upgraded product, compared to the feed. A first‐order, five lump reaction network was developed to fit the yields of gas, coke, diesel, and gasoline range components obtained from SCW upgrading of vacuum residue. Distillation of crude oil followed by SCW treatment of the heavy fraction approximately doubled the yield of chemicals, gasoline, and diesel, while forming significantly less coke than conventional upgrading methods. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1732–1743, 2018     

Hydrogen transfer and activation of propane and methane on ZSM5-based catalysts

Hydrogen exchange between undeuterated and perdeuterated light alkanes (CD₄-C₃H₈, C₃D₈-C₃H₈) occurs on H-ZSM5 and on Ga- and Zn-exchanged H-ZSM5 at 773 K. Alkane conversion to aromatics occurs much more slowly because it is limited by rate of disposal of H-atoms formed in C-H scission steps and not by C-H bond activation. Kinetic coupling of these C-H activation steps with hydrogen transfer to acceptor sites (Ga ⁿ⁺, Zn ^m+) and ultimately to stoichiometric hydrogen acceptors (H⁺, CO₂,O₂, CO) often increases alkane activation rates and the selectivity to unsaturated products. Reactions of¹³ CH₄/C₃H₈ mixtures at 773 K lead only to unlabelled alkane, alkene, and aromatic products, even though exchange between CD₄ and C₃H₈ occurs at these reaction conditions. This suggests that the non-oxidative conversion of CH₄ to higher hydrocarbons on solid acids is limited by elementary steps that occur after the initial activation of C-H bonds.     

Designing maleic anhydride-α-olifin copolymeric combs as wax crystal growth nucleators

Modification of the wax crystal habit is of great practical interest during transportation and processing of crude oil at low temperature. Various pour point depressant (PPD) additives can facilitate this modification by different mechanisms. Comb shaped polymer additives are known to depress the pour point of crude oil by providing different nucleation sites for the precipitation of wax. This paper describes performance based design, synthesis, characterization and evaluation of comb shaped polymeric diesters. Copolymers of maleic anhydride with different unsaturated C₂₂ esters were synthesized and copolymers then reacted with two unsaturated fatty alcohols. All products were characterized by Fourier Transform Infra Red (FTIR) spectroscopy and Gel Permeation Chromatography (GPC). Rheological properties of crude (with and without additive) were studied by Advance Rheometer AR-500. In this study the additive based on oleic acid was evaluated as good PPD and rheology modifier.     

Study of a newly isolated thermophilic bacterium capable of Kuhemond heavy crude oil and dibenzothiophene biodesulfurization following 4S pathway at 60 °C

BACKGROUND: To meet stringent emission standards stipulated by regulatory agencies, the oil industry is required to bring down the sulfur content in fuels. As some compounds cannot be desulfurized by existing desulfurizing processes (such as hydrodesulfurization, HDS) biodesulfurization has become an interesting topic for researchers. Most of the isolated biodesulfurizing microorganisms are capable of desulfurization of refined products whose predominant sulfur species are dibenzothiophenes so biocatalyst development is still needed to desulfurize the spectrum of sulfur‐bearing compounds present in whole crude. RESULTS: The first desulfurizing bacterium active at 60 °C has been isolated, which reduces DBT concentration from 2 mmol L^?1 to 0.1 mmol L^?1 after 95 h, following the 4S pathway. Its DBT desulfurization pattern was represented by the Michaelis‐Menten equation. Various parameters such as V_max, K_m, µ_m, K_s and maximum specific DBT desulfurization rate were calculated which are 0.092 mmol L^?1 h^?1, 3.554 mmol L^?1, 0.157 h^?1, 3.722 mmol L^?1 and 0.192 mmol L^?1 DBT g^?1 DCW (dry cell weight) h^?1, respectively. It can desulfurize 50% of the sulfur content of Kuhemond heavy crude oil (KHC oil) with an initial sulfur content of 7.6%wt in 6 days. Its maximum specific desulfurization rate for KHC oil is equivalent to 0.005 g sulfur g^?1 DCW h^?1. The bacterium was isolated during a heavy crude oil biodesulfurization project initiated by PEDEC, a subsidiary of National Iranian Oil Company. CONCLUSION: The KHC oil sulfur removal efficiency of the bacterium is approximately five times that of BBRC‐9016 bacterium. It removes sulfur selectively without using sulfur‐containing compounds as its carbon source. By applying various media during its isolation, the probability of screening the correct microorganism is increased. Copyright © 2008 Society of Chemical Industry     

Curing temperature effect on smokeless fuel briquettes prepared with molasses and H3PO4

Chars from the co-carbonisation of a low-rank coal and olive stones have been used to prepare environmental acceptable smokeless fuel briquettes. The blend was a mixture of char, molasses and H₃PO₄. This acid was added to favour the polymerisation of the binder. The effect of the curing temperature on the physico-chemical features of the briquettes was studied by Fourier Transform Infrared Spectroscopy and Temperature Programmed Decomposition followed by Mass Spectrometry. The presence of H₃PO₄ as well as the curing process at 200 °C of temperature, contribute to the formation of carboxylic acids which lead to the production of briquettes with adequate mechanical properties.     

Highly Efficient Oxidative Desulfurization of Fuels by Lewis Acidic Ionic Liquids Based on Iron Chloride

Acidic ionic liquids (ILs) have been employed as extractant and catalyst in the oxidative desulfurization (ODS) process of fuels in recent years. Several Lewis acidic ionic liquids [C₆³MPy]Cl/nFeCl₃ (molar fraction n = 0.5, 1, 2, 3) and [C₆MIM]Cl/FeCl₃ were prepared and used to remove the aromatic sulfur compounds dibenzothiophene and benzothiophene from fuels. In the ODS process, the used ILs acted as both extractant and catalyst with 30 wt % hydrogen peroxide aqueous solution as oxidant. The effects of Lewis acidity of ILs, IL's cation structure, molar ratio of O/S, reaction temperature, and different sulfur compounds on the sulfur removal of model oil were investigated. The results indicated that the sulfur removal for dibenzothiophene was affected by Lewis acidity of ILs and nearly reached 100 % by [C₆³MPy]Cl/FeCl₃ at conditions of 298 K, IL/oil mass ratio of 1/3, O/S molar ratio of 4/1, in 20 min. The sulfur removal of real gasoline reached 99.7 % after seven ODS runs in the [C₆³MPy]Cl/FeCl₃‐H₂O₂ system.     

Fullerenic structures derived from oil asphaltenes

The handling and properties of heavy oils are becoming an increasingly important problem. Even though petroleum is the widest used source of fuels and it has been studied for decades, its complex nature is still an enigma in several ways. A reasonable approach to a definition of a crude oil is a colloidal fluid formed by several dispersed phases from gases (light hydrocarbons) to solids (heavy paraffins and asphaltenes). Through all these years of research, applications have been found for almost all classes of components in crude oil except for some of the solid phases such as asphaltenes. Very heavy petroleum is a non-newtonian liquid with a viscosity of ≈10⁶ Poise, and an average molecular weight of 600 amu. The solids that are toluene soluble but heptane insoluble are called asphaltenes and are the most aromatic fraction with the highest molecular weight of unconverted petroleum. In the present work, we applied high resolution transmission electron microscopy (HREM) and energy dispersive spectrometry (EDS) in the study of asphaltenes. It was found that when the asphaltenes are well separated from the resins the sample consists of a carbon structure containing S, V, Si, related to fullerenic carbon. During observation in the microscope it was possible to see the formation of fullerenes such as onions and C₂₄₀ @ C₆₀ structures. The fact that they decomposed under further irradiation suggests that they are metastable structures. Since the heteroatoms are still present they are likely to cause instability to the structure. Not only does our result indicate the possibility of obtaining fullerenes from crude oil but it also suggests the asphaltene molecule, when it is resin free, might be a precursor of fullerenic structures.     

Catalytic steam cracking of heavy crude oil with molybdenum and nickel nanodispersed catalysts

The catalytic steam cracking (CSC) of heavy crude oil with high amount of sulfur (4.3 wt %) and high-boiling fractions (>500°C) is studied using Mo and Ni nanodispersed catalysts under static conditions (in an autoclave) at 425°C. Experiments on thermal cracking, steam cracking, and catalytic cracking without water are performed to compare and identify the features of CSC. The relationship between the composition and properties of liquid and gaseous products and process conditions, the type of catalyst, and water is studied. Using Ni catalyst in CSC raises the H: C ratio (1.69) in liquid products, compared to other types of cracking, but also increases the yield of coke and gaseous products, so the yield of liquid products falls. When Mo catalyst is used in CSC, low-viscosity semi-synthetic oil with a higher H: C ratio (1.70) and the lowest amount of sulfur in liquid products (2.8 wt %) is produced. XRF and HRTEM studies of the catalyst-containing solid residue (coke) show that under CSC conditions, nickel is present in the form of well-crystallized nanoparticles of Ni₉S₈ 15–40 nm in size, while molybdenum exists in two phases: MoO₂ and MoS₂, the ratio between which depends on the conditions of the transformation of heavy crude oil. The findings indicate that CSC is a promising process for improving heavy crude oil.     

Oxidative dimerization of CH4/CD4 mixtures: Evidence for methyl intermediate

Isotope tracer experiments prove the role of methyl in the oxidative coupling of methane and disprove a recently proposed mechanism involving methylene. The ethane product from oxidative coupling of CH₄/CD₄ mixtures over a Li/MgO catalyst consists of C₂H₆, C₂D₆ and CH₃CD₃ thus proving that ethane is formed by combination of methyl intermediates. The co-reaction of labelled CH₄ (D and¹³C) with C₂H₄ produces propylene labelled predominantly at the methyl (3) position, thus proving C₃ formation by terminal addition of methyl to ethylene rather than via a cyclic intermediate as has been proposed.     

The study on composition changes of heavy oils during steam stimulation processes

Using the heavy oils obtained from Liaohe oilfields in China, we have conducted the aquathermolysis reaction in laboratory at 240 °C. The results showed that Liaohe heavy oils have been undergoing visbreaking in the process of steam-drive and steam stimulation. After reaction with steam, the viscosity of the heavy oil was reduced by 28-42% and the amount of the saturated and aromatic hydrocarbons increased, while resin and asphaltene decreased. The gas partition chromatography showed that the accumulated amount of carbon numbers increased, after reaction, the accumulated amount of carbon numbers less than C₂₀ are 38.79-53.92%, and before reaction they are 13.30-20.92%. The results provided the basic data for heavy oil recovery by in situ catalytic method in production of heavy oil in oilfields.     

A TDS study of D adsorption on terraces and terrace edges of graphite (0 0 0 1) surfaces

Adsorption of thermal (2000 K) D atoms on (0 0 0 1) surfaces of various highly oriented pyrolytic graphite (HOPG) and natural graphite substrates was studied under ultra high vacuum (UHV) conditions with thermal desorption spectroscopy (TDS). D chemisorption on terrace and terrace edge sites of graphite (0 0 0 1) surfaces was identified. Recombinative desorption of D adsorbed on terraces was observed between 400 and 600 K. The analysis of TD spectra from various graphite surfaces reveals the existence of three desorption states intrinsic to graphite (0 0 0 1), and proposed as being due to adsorbate structures composed of one (monomer) and two neighbouring (dimer) chemisorbed D atoms, and aggregates thereof (mixed). The dimer structure is supposed to exhibit higher stability than the monomer. Reaction of D with terrace edges leads to the formation of CD, CD₂ and CD₃-groups at edge C atoms. These groups decompose during heating between 790 and 1300 K via release of gaseous D₂ and CD_x, C₂D_x and C₃D_x-hydrocarbons.     

Catalytic Dehydration of Alcohols. Kinetic Isotope Effect for the Dehydration of t-Butanol

The kinetic isotope effects (KIE) for the conversion of an equimolar mixture of C₄D₉OH and C₄H₉OH and for the KIE for the intermolecular elimination of water from (CD₃)₂CH₃COH for an alumina-catalyzed reaction were the same, 2.1–2.3. These results eliminate a carbocation intermediate for the dehydration of even a tertiary alcohol. Thus, for an alumina catalyst alcohol dehydration occurs by a concerted elimination mechanism. H/D exchange occurs to different extents prior to or during elimination for zirconia, thoria and magnesia catalysts; however, the data are consistent with a concerted elimination mechanism in combination with H/D exchange.     

Extractive Desulfurization of Fuel Oils with Dicyano(nitroso)methanide-based Ionic Liquids

The inability of traditional hydrodesulfurization (HDS) to effectively remove aromatic sulfur compounds such as thiophene (TS) and dibenzothiophene (DBT) has called for alternative methods to be studied, among which extractive desulfurization using ionic liquids (ILs) has attracted increasing interest. In this work, we prepared a new IL, 1-butyl-3-methylimidazolium dicyano(nitroso)methanide ([C₄mim][dcnm]), and investigated its extractive desulfurization for both model oils and real FCC gasoline, where model diesel fuel was composed of n-hexane and droplets of DBT and model gasoline was composed of n-hexane, toluene and droplets of TS. Other three [dcnm]-based ILs, 1-ethyl-3-methylimidazolium dicyano(nitroso)methanide ([C₂min][dcnm]), N-ethyl-N-methylpyrrolidinium dicyano(nitroso)methanide ([C₂mpyr][dcnm]), and N-butyl-N-methylpyrrolidinium dicyano(nitroso)methanide ([C₄mpyr][dcnm]), were also comparatively investigated. These [dcnm]-based ILs have low viscosity which favors the mass transfer and reduces the extractive equilibrium time, also are fluorine-free which avoids the corrosion by hydrogen fluoride from anion decomposition that occurs generally in fluorine-containing ILs. The desulfurization ability follows the order [C₄min][dcnm] > [C₄mpyr][dcnm] > [C₂min][dcnm] > [C₂mpyr][dcnm]. Typically, [C₄min][dcnm] is capable of removing 66% DBT and 53% TS from their respective model oils after one cycle (initial 500 ppm S, 25°C, 15 min, mass ratio of IL:oil 1:1), and < 10 ppm S-content can be obtained after 4 cycles. It was observed interestingly that the S-content in real FCC gasoline can be reduced from initial 250 ppm to < 30 ppm after 6 cycles using [C₄min][dcnm] as extractive reagent, which is better than some previous results for real feedstocks. Mutual solubility, extractive temperature, IL:oil mass ratio, multiple extraction, initial S-content, and regeneration were also studied. These dcnm-based ILs are competitive extractive reagents compared with some other ILs to remove those aromatic S-compounds from fuel oils.     

Deep extractive desulfurization of oil over 12-molibdophosphoric acid encapsulated in metal-organic frameworks

A desulfurization process for model oil and real oil was investigated based on the chemical oxidation of mixed sulfur containing compounds in the presence of nitrogen compounds (indole and quinoline) using hydrogen peroxide as oxidizing agent and dodecamolibdophosphoric acid (H₃PMo₁₂O₄₀) encapsulated in a kind of metal-organic framework (HKUST-1) as PMo@HKUST-1. The effect of isopropanol, ethanol and acetonitrile as extractive solvent and 1-ring (toluene, xylene and mesitylene) and 2-ring (naphthalene) aromatic hydrocarbons in desulfurization of model oil was studied. The desulfurization of sulfur-containing compounds was accelerated in the presence of aromatic hydrocarbons. In fact, a higher desulfurization efficiency of the heterogeneous catalyst could be achieved with system containing a polar solvent in contact with an aromatic hydrocarbon. Quinoline had no effect on oxidative desulfurization (ODS) reaction, whereas indole had a slightly negative effect. Presence of aromatic compounds had slightly positive effect on ODS reaction.     

The pyrolysis of individual plastics and a plastic mixture in a fixed bed reactor

Six thermoplastics, which represent more than two-thirds of all polymer production in western Europe, were pyrolysed in a static batch reactor in a nitrogen atmosphere. These were high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), polypropylene (PP), polyethylene terephthalate (PET) and polyvinyl chloride (PVC). The heating rate used was 25°C min⁻¹ to a final temperature of 700°C. These six plastics were then mixed together to simulate the plastic fraction of municipal solid waste found in Europe. The effect of mixing on the product yield and composition was examined. The results showed that the polymers studied did not react independently, but some interaction between samples was observed. The product yield for the mixture of plastics at 700°C was 9·63% gas, 75·11% oil, 2·87% char and 2·31% HCl. The gases identified were H₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, C₄H₈, C₄H₁₀, CO₂ and CO. The composition of oils were determined using Fourier Transform infra-red spectrometry and size exclusion chromatography. Analysis showed the presence mainly of aliphatic compounds with small amounts of aromatic compounds. ©1997 SCI     

Production of Saponin Biosurfactant from <Emphasis Type="Italic">Glycyrrhiza glabra</Emphasis> as an Agent for Upgrading Heavy Crude Oil

Saponins are the main group of phytogenic biosurfactants extracted from plants. One of the significant applications of these compounds is upgrading and viscosity reduction of heavy crude oil water in oil (W/O) emulsions. In this research, use of saponin extracted from Glycyrrhiza glabra was investigated for viscosity reduction of heavy crude oil and upgrading its API properties. The extracted saponin was characterized using Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Phase behavior analysis demonstrated a reduction in initial viscosity and improved API gravity of the heavy oil from 2350 mPa·s and 19 to 900 mPa·s and 27, respectively. In addition, the emulsification index (E ₂₄) was found to be 98 % at a saponin concentration of 8 % w/v. It was observed that the emulsions were stable in the pH range of 5.5–13, temperature from 30 to 80 °C and salinity up to 6 % w/v of NaCl solution. Average diameter of W/O droplets evaluated by dynamic light scattering (DLS) were in the range of 10–15 µm. The results obtained from the present research revealed that the extracted saponin improved the physical characteristics of heavy crude oil. We propose the use of saponin as a potential alternative to conventional emulsifiers for upgrading heavy crude oil in petroleum industry.     

Catalyst modification and process design considerations for the oxidation of low concentrations of hydrogen sulfide in natural gas

Low concentrations of hydrogen sulfide (H₂S) in natural gas can be selectively oxidized over an activated carbon catalyst to elemental sulfur, water and a small fraction of sulfur dioxide (SO₂). Efforts to improve catalyst performance and product sulfur quality have been made by a) modification of the catalyst composition b) removal of the heavy hydrocarbons from the feed and c) choice of reaction conditions. The use of a guard bed to absorb heavy hydrocarbons and operation at elevated pressures show positive results. A preliminary flow diagram incorporating these findings has been prepared for a small commercial unit capable of processing sour natural gas containing 1.0% H₂S.     

Ultraviolet Absorption Spectrum of Toluene-D8

The near ultraviolet absorption spectrum of toluene-d₈ has been recorded with the help of a E₁ large quartz spectrograph. The (O,O) band has been identified at 37672 cm^?1. The spectrum has been analysed with the help of the excited state fundamentals 282, 378, 431, 454, 508, 700, 926, 1150 and 1432 cm^?1. These frequencies have been correlated with the corresponding frequencies of the normal molecule. The ration R = ν(C₆H₅CH₃)/ν(C₆D₅CD₃) has been calculated for each excited state mode of vibration and compared with the corresponding value of R found for the ground state vibrations.     

Application of geochemical parameters for classification of crude oils from Egypt into source-related types

Seven crude oils representing the different petroleum-bearing basins in the Western Desert were characterized by a variety of biomarker and nonbiomarker parameters. For comparison, one crude oil from the Gulf of Suez region has also been studied. The oils have been analyzed for geochemical biomarkers using GC and GC-MS techniques. The results reveal significant differences within the oils that suggest five oil types. Type 1 oils from the Gulf of Suez show C₂₉/C₃₀ 17α(H) hopane ratio >1, high C₃₅ homohopane index, and the presence of considerable amounts of gammacerane indicating a marine saline carbonate or evaporite source rock and highly reducing (low Eh) conditions. Type 2 oils from Matruh basin and type 3 oils from Shushan basin are very similar and show relatively high Pr/Ph ratios, low sulfur and metal contents, paucity of C₃₀ steranes and the presence of high relative abundance of 17α(H) diahopane (C₃₀*) suggesting that they probably originated from source rocks containing a significant proportion of higher plant material. Another related feature of these oils is the absence of 18α(H)-oleanane which suggests a source age older than Cretaceous. Type 4 oils from Abu-Elgharadig basin show terpane distribution dominated by C₂₄ tricyclic, absence of C₃₀*-diahopane and medium diasterane/sterane ratios which reflect generation from marine siliciclastic source rocks. Type 5 oils from Alamein basin possess source biomarkers indicating a mixed contribution of terrestrial and marine sources. The presence of measurable amounts of oleanane in this type of oils suggests source rocks deposited in deltaic or near shore environment in Post-Cretaceous basin.     

Composition of the heteroorganic compounds of oil shale in Cambrian rocks from the east of the Siberian Platform

The molecular composition of the S-, O-, and N-containing heterocyclic aromatic compounds of bitumen separated from the rocks of the Cambrian oil shale formation was studied. Among the sulfur compounds, dibenzothiophene, its alkyl and naphthene derivatives, naphthobenzothiophenes, and their alkyl homologs were identified. Among the oxygen compounds, unbranched dibenzo- and naphthobenzofuran and their C₁–C₄ and C₁–C₂ alkyl homologs, respectively, were detected. Acridinones, benzoacridinones, and their alkyl homologs were present among the nitrogen compounds.