Experimental study of the reaction of methane with petroleum hydrocarbons in geological conditions

In order to assess the possible role of methane in petroleum formation, we studied the reaction of methane with liquid hydrocarbons representing the three main classes of compounds dominant in crude oil. The experimental reaction conditions simulated those of a geological setting for petroleum formations, at 1000 atm and 150–250°C in the presence of montmorillonite, a natural clay catalyst. Since we expected very slow reaction rates and thus low yields, we used ¹⁴C labeled methane to trace the reaction products. We report here the detection of ethylbenzene and ethyltoluene formed by the interaction of methane with benzene and toluene, respectively. Instead of methylation of benzene, predominantly C₂ addition occurred, although very small amounts of products corresponding to C₁ addition were also detected. We propose that catalytic dissociation of methane occurred, forming ethylene which participated in a Friedel-Crafts type alkylation process of the aromatic ring on the catalyst surface. In addition to ring alkylation, side reactions such as polymerization of unsaturates (ethylene, acetylene) appeared to have occurred on the catalyst surface. The nature of these polymers is yet to be determined.     

Markers for secondary reactions of migrated crude oil on carbonaceous surfaces

A high abundance of ethyl substituted aromatic hydrocarbons (HCs) relative to their methyl counterparts is an unusual feature of some crude oils. Enhanced stability of ethyl aromatic HCs in the presence of tetralin was observed when individual ethylated compounds were heated with activated carbon in sealed tubes over a range of 170–340 °C. In addition, conversion of the common distribution of alkyl aromatic HCs to an unusual distribution, containing a higher relative abundance of ethyl compounds, was demonstrated by way of closed system heating of the aromatic fraction of a crude oil in the presence of activated carbon. The conditions for this unusual process require the presence of hydrogen donor components, which selectively limit the reaction and depletion of ethylated compounds relative to methylated compounds. The phenomenon has been shown to occur for substituted benzenes, naphthalenes, phenanthrenes and biphenyls. Enhanced abundance of ethyl aromatic HCs relative to their methylated counterparts is therefore proposed as an indicator for secondary reactions of migrated crude oil that has undergone thermal alteration after contact with carbonaceous surfaces in sediments. Application of these principles to selected crude oils and sediment extracts from the Carnarvon and Cooper/Eromanga Basins (Australia) indicates that significant secondary reaction of migrated crude oil has occurred.     

Acid catalysis of alkyl hydrogen exchange and configurational isomerisation reactions: acyclic isoprenoid acids

Acid-catalysed alkyl hydrogen exchange and configurational isomerisation has been studied in a series of acyclic isoprenoid acids when they were heated at 160°C in the presence of a montmorillonite. Hydrogen exchange occurred between the adsorbed water of the clay surface and the a position of the isoprenoid acids. In cases where this position was chiral, exchange was accompanied by configurational isomerisation. Configurational isomerisation occurred more slowly in experiments conducted without a clay matrix in the presence of water. These results have been rationalized in terms of a reaction mechanism involving protonation of the carbonyl oxygen causing enolization and consequent hydrogen exchange at the a position of the acids. This mechanism was used to account for the relatively fast rate of isomerisation of C-2 chiral centres in sedimentary acyclic isoprenoid acids during maturation.     

有机粘土化学研究进展与展望

有机粘土化学是研究粘土矿物与有机化合物之间相互作用的一门学科,其内容包括粘土矿物对有机化合物的吸附作用,粘土矿物对有机化合物转化的催化作用以及有机化合物对粘土矿物的合成与风化的影响。着重阐述了近20年来有机粘土化学的研究进展,并就这一学科领域的研究作了展望。     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

Investigation of the deuteration of crystalline layer forms of silica and alumina in liquid D2O

The mechanism of hydrogen-deuterium isotopic exchange was studied in crystalline layer forms of silica (hydrous and cation-substituted SiO₂-X₂ and SiO₂-Y varieties) and alumina (hydrargillite and boehmite) in contact with liquid D₂O at temperatures of 20–200°C and saturated vapor pressure. Extensive exchange was observed between adsorbed H₂O and D₂O molecules via the self-diffusion mechanism in all silica varieties and boehmite at a temperature of 20°C. Deuterium substitution for hydrogen in structural OH groups was observed at 20°C only in the H-form of SiO₂-Y (0.7%) and boehmite (1.2 or 17% with molecular deuteration). When the temperature of the hydrothermal treatment of samples was raised up to 200°C, the degree of structural deuterium exchange increased up to 12% (35% with molecular deuteration) in the former case and up to 34% in the latter case. In the former case, the process of isotopic exchange occurred by the nucleophile substitution S_Ni near surface silicon atoms, and in the latter case, the electrophile substitution E_Ni in surface OH groups.     

Characterization of hydrocarbon-bearing fluid inclusion in sandstones of Jaisalmer basin, Rajasthan: A preliminary approach

The quartz grains from the sandstone of Jaisalmer, Pariwar and Goru Formations of the Jaisalmer basin, Rajasthan, India, exhibits a variety of primary and secondary fluid inclusions. Most of them are hydrocarbon bearing fluid inclusions. Laser Raman studies indicate that the primary fluid inclusions were mostly having aliphatic hydrocarbons with lower degree of maturity, while the secondary fluid inclusions were generally with aliphatic as well as aromatic hydrocarbons with higher degree of maturity. This inference was consistent with their fluorescence characteristics. The homogenization temperatures of primary monophase CH₄ rich fluid inclusions varied from ?80°C to ?100°C, whereas the primary biphase fluid inclusions (CH₄-CO₂) homogenized between +80°C and +150°C. The secondary petroleum rich monophase fluid inclusions were having homogenization temperature between ?80°C to ?90°C, whereas the secondary biphase fluid inclusions homogenized between +130°C and +180°C. Most of the secondary biphase fluid inclusions were having the mixtures of H₂O-CO₂-NaCl, and were identified on the basis clathrate formation and they got homogenized between +140°C and + 250 °C. The three past events of migration of petroleum inferred in the host rock which were marked by the presence of characteristic secondary fluid inclusions. They were identified on the basis of cross-cutting relationships of different trails of fluid inclusions in the quartz. The cement generation in the basin might have been occurred in two stages as per the fluid inclusion petrography.     

Thermal catalytic transformation of pentacyclic triterpenoids: Alteration of geochemical fossils during coalification

To elucidate the possible natural evolutionary pathways for the transformation of pentacyclic triterpenoids, three terpenoid samples, Δ²-allobetulene, tetranormethylallobetulheptaene and fernenes were heated independently at 150°C for 7 weeks with montmorillonite clay. Common products from these reactions consisted of di, tri-, tetra-, and pentacyclic hydroaromatic and aromatic hydrocarbons, which are commonly found in higher rank coals. C-ring cleaved (8,14-seco) aromatic terpenoid derivatives were also found in the thermal catalytic reaction products of Δ²-allobetulene. Such compounds could be important intermediates in the formation of bicyclic hydrocarbons from pentacyclic triterpenoids.     

The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ¹⁸O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ¹⁸O value of +3.5%., which corresponds to equilibration at 295°–360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al³⁺ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.     

Determination of the hydrogen isotopic composition of bone collagen and correction for hydrogen exchange

The hydrogen isotopic measurement (δD) of the non-exchangeable hydrogens in herbivore bone collagen has potential for paleoclimate research. We have developed the methodology for extracting the hydrogen from collagen for isotopic analysis and for correcting the δD results for hydrogen exchange. Preparations of whole bone powders, demineralized bone, or gelatin extracts from fresh bone samples all give reliable δD results and have isotopic results, yields, and proportions of exchangeable hydrogens consistent with that expected for collagen. Gelatin extraction for removal of contaminants remains a valuable option for the study of fossil bone samples.Vacuum preheating under good vacuum at 150°C for two days for whole bone powders and at 100°C for one day for gelatins is an important step to remove all adsorbed water before samples are oxidized for isotopic analysis. Of the remaining hydrogens released following oxidation, 20.5% in whole bone powders and 23.1% in gelatin extracts exchange with laboratory atmospheric water vapor within 48 hours. The δD results can be corrected for this exchange and for minor effects of sample preparation by using a calibration bone standard to determine the δD value of laboratory water vapor.     

The diagenesis of carbohydrates by hydrogen sulfide

Carbohydrates react with hydrogen sulfide under low temperature (100° to 200°C) yielding a variety of organosulfur compounds including thiophenes, thiols, sulfides and sulfones. A polymer is also produced, whose elemental composition is within the range of natural coals. When reductive dehydration is carried out in the presence of hydrocarbon, organosulfur compounds are formed in the carbon number range of the hydrocarbon used. In these processes, an active hydrogen transfer catalyst is produced which facilitates the passage of hydrogen between normal paraffins and saccharide units, distributing sulfur between these two families primarily in the form of thiophene rings. The simplicity of these systems—H₂S, carbohydrates, H₂O, hydrocarbon—and the facility of the chemistry would suggest that the carbohydrates and hydrogen sulfide may be important agents in the diagenetic processes leading to petroleum and coal. Carbohydrate reduction by hydrogen sulfide may constitute an important route through which certain organosulfur compounds found in petroleum and coal entered these materials in early diagenesis.     

Formation of solid bituminous matter in pegmatites: Constraints from experimentally formed organic matter on microporous silicate minerals

The formation of solid bituminous matter (SBM) on surfaces of microporous silicates was experimentally studied at pressure and temperature conditions typical of late-stage magmatic and hydrothermal processes. Aliquots of microporous silicate minerals (zorite and kuzmenkoite-Mn, Lovozero Alkaline Massif, Kola Peninsula, Russia) were exposed to solid or liquid organic carbon sources (natural brown coal and liquid 1-hexene for synthesis purposes) in a 0.1 M NaCl-solution for 7 days, at constant pressure (50 MPa), and at three individual temperatures (200, 275, and 300 °C). No thermal decomposition of the solid organic sources happened at 200 °C and only a thin film of brown coal derivatives on the silicates’ surfaces and no formation of SBM were observed at 275 °C and 300 °C. But solid bituminous matter on the surfaces of both microporous silicates were detected in experiments with liquid 1-hexene as organic carbon source and at temperatures of 275 °C and 300 °C with a more pronounced formation of SBM at 300 °C compared to 275 °C. The aromatic and aliphatic hydrocarbons, as well as alcoholic compounds of the experimentally produced SBM are similar, if not even partly identical, with natural SBM occurrences of the Khibiny and Lovozero Massifs, Kola Peninsula, Russia, and from the Viitaniemi granitic pegmatite, Finland, as shown by FT-IR and ¹H NMR spectroscopy. This strengthens the hypothesis of formation of natural solid bituminous matter by catalytic reactions between microporous Ti-, Nb- and Zr-silicates and hydrocarbons at postmagmatic hydrothermal conditions.     

The influence of humic materials on the flotation of coal

The effect of humic material on the flotation response of coal has been examined. The results show that while hydrogen ions do not adversely affect the flotation of coal particles, they interact with humic material adsorbed on the surface of the clay particles and render their surfaces oleophilic. This behaviour enables the clay particles to adsorb collector in preference to the coal particles and thus inhibit coal flotation.     

Closed system Fischer-Tropsch synthesis over meteoritic iron,iron ore and nickel-iron alloy

Meteoritic iron, iron ore and nickel-iron alloy (either alone or in some cases mixed with alumina, carbonaceous chondrite, potassium carbonate or sodium carbonate) were used to catalyze the reaction of deuterium and carbon monoxide in a closed reaction vessel. The mole ratio of deuterium to carbon monoxide ranged from 1/2:1 to 10:1, the reaction temperature from 195 to 370°C, and the reaction time from 6 to 480 hr. Analysis of the reaction products showed that normal alkanes and alkenes (C₁₁-C₂₅), their monomethyl substituted isomers and aromatic hydrocarbons (e.g. naphthalene, acenaphthene, fluorene, phenanthrene and the methyl derivatives of these hydrocarbons) were synthesized. In addition to the aforementioned hydrocarbons, one reaction product was shown to contain perdeutero normal fatty acids (10:0–16:0).     

Proteins as a possible source material of low molecular weight petroleum hydrocarbons

Low temperature cracking experiments of a representative protein, at temperatures not far above the observed temperature range of 130–160°C of mature California oil source rocks, indicate the formation of all gaseous and of some gasoline range hydrocarbons of petroleum. Based on protein derivatives only it is estimated that a maximum of at least 3–8% by weight of the total organic matter of oil source sediments may be converted into such hydrocarbons. This is in addition to hydrocarbons originating from lipids.     

Laboratory simulation of meteoritic noble gases. II. Sorption of xenon on carbon: Etching and heating experiments

Sixteen amorphous carbon (lampblack) samples that had been exposed to Xe¹²⁷ and pumped for >9 hrs to remove the most labile gas were examined by etching with HNO₃, for comparison with the release pattern of meteoritic xenon. Samples originally exposed at 100–200°C lost 90% of their Xe very readily, when the surface had been etched to a mean depth of only ~0.2 Å. This suggests that the Xe is adsorbed mainly at rare sites that are unusually reactive to HNO₃. The adsorbed Xe survived several months' storage in vacuum, but on exposure to air, part of it was lost within a few hours, while the remainder persisted without measurable exchange. Samples exposed at 800–1000°C had a similar adsorbed component, as well as a second, tightly bound component extending to a mean depth of up to 30 Å; this component had apparently diffused into the carbon during exposure. The (microscopic) diffusion coefficient for graphitic crystallites is 5 × 10^?20 cm²/sec at 1000°C.PVDC carbon lost its adsorbed Xe at about the same rate as lampblack on exposure to air or HNO₃, though it differs from lampblack in being non-graphitizable and more porous. It had only a small diffused component, however.The most tightly bound part of the Xe adsorbed on lampblack resembles planetary Xe in most characteristics: surface siting, etchability, persistence in vacuum, and lack of exchange with atmospheric Xe. The Xe concentrations—if interpreted as equilibrium distribution coefficients—are some 10⁶× too small to account for meteoritic Xe, but it appears that equilibrium had not been reached by any of the samples, even after 1 day's exposure to Xe. If the uptake of Xe is controlled by rate rather than equilibrium, then the high noble gas concentrations in meteorites may simply reflect the much longer uptake times in the solar nebula. It seems likely that the trapping mechanisms discussed here can also explain two other features: elemental fractionations of noble gases, and the close correlation between planetary Xe and CCFXe.     

Use of Tunisian raw clay to remove dye from aqueous solution

This paper presents the first attempt to investigate the potential of Tunisian palygorskite-rich clay (Pal-clay) on the effectiveness of a textile dye “Direct orange 34” (DO34) removal. Important parameters which affect adsorption, such as initial solution pH, contact time, adsorbent mass, initial dye concentration, and temperature, were investigated. The raw Pal-clay was characterized using X-ray diffractometer (XRD), X-ray fluorescence (XRF), Fourier transform infrared spectroscopy (FTIR), cation exchange capacity (CEC), specific surface area (SSA) analysis, and point of zero charge (PZC) determination. The results showed that the Pal-clay has a high selectivity for DO34 and had maximum removal efficiency reaching up to about 91 %. The highest adsorption capacity was obtained at 25 °C and pH of 2. The dye uptake process fitted well to the pseudo-second-order kinetic expression and was best described by the Langmuir and Freundlich isotherms. Intra-particle diffusion studies showed that the adsorption mechanism was not exclusively controlled by the diffusion step and was more likely to be governed by external mass transfer. Thermodynamic parameters such as change in free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also calculated. The parameters revealed that the adsorption of dye by the raw clay is spontaneous and exothermic. The results indicate that the Pal-clay has a moderate adsorption capacity towards anionic dye.     

A first step towards identification of tannin-derived black carbon: Conventional pyrolysis (Py–GC–MS) and thermally assisted hydrolysis and methylation (THM–GC–MS) of charred condensed tannins

Tannins account for a significant proportion of plant biomass and are likely to contribute to the residues formed by incomplete biomass combustion (black carbon, BC). Nonetheless, the molecular properties of thermally modified tannins have not been investigated in laboratory charring experiments. We applied conventional analytical pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) and thermally assisted hydrolysis and methylation (THM–GC–MS) to investigate the effects of heat treatment with a muffle furnace on the properties of condensed tannins (CT) from Corsican pine (Pinus nigra) needles. Py–GC–MS showed a decrease in the relative abundance of the 1,2,3-trihydroxybenzenes (pyrogallols) at ⩾300 °C and of the dihydroxybenzenes (mainly catechols) at ⩾350 °C due to dehydroxylation of the CT B ring. Further dehydroxylation led to formation of monohydroxybenzenes (phenols), which showed a strong enrichment between 350 and 400 °C and, at higher temperatures, to a series of monocyclic and polycyclic aromatics [benzene, alkyl benzenes and polycondensed aromatic hydrocarbons (PAHs)]. Degradation of the A ring could not be recognized via Py–GC–MS, probably because of the poor chromatographic behavior of 1,3,5-trihydroxybenzenes (phloroglucinols). The progressive dehydroxylation and eventual polycondensation of the CT B ring was corroborated using THM–GC–MS. In addition, with THM–GC–MS the thermal rearrangement of CT A rings at 300 °C and higher was inferred from the relative abundance of 1,3,5-trimethoxybenzenes (methylated phloroglucinol derivatives). These compounds were observed at moderate/high temperature (up to 450 °C) and can not be produced from THM of lignin, suggesting that they may be markers of CT in natural BC samples.     

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.     

The hydrogen isotope fractionation between kaolinite and water

Hydrogen isotope fractionation factors between kaolinite and water were determined at temperatures between 200° and 352°C. Five-gram samples of kaolinite were heated in contact with 8-mg samples of water in sealed glass reaction tubes. Under these conditions the approach to equilibrium with time will be reflected primarily in the change of the δ D in the water. Also the δ D of the hydrogen in the kaolinite will be relatively constant, subject to minor corrections. About seventy sealed vessels were heated for various times at various temperatures. During four months of heating, ～ 25% of kaolinite hydrogen exchanged with the water at 200°C, whereas 100% exchanged at 352°C. The α-values were estimated assuming equilibrium between exchanged kaolinite and water. The 10³lnα-values are estimated to be ?20, ?15, ?6 and +7 for 352°, 300°, 250° and 200°C, respectively, which are in approximate agreement with reported values previously determined at 400°C using conventional methods as well as those estimated from kaolinite in hydrothermally active systems. The curve representing the relationship between the hydrogen isotope fractionation factor for the kaolinite-water system and temperatures between 400° and 25°C is not monotonic but rather has a maximum at 200°C.