Geology topics

Yongchun Tang

Publications and source records attributed to Yongchun Tang.

6 recordsLinked to original sources

USGS2019

Kinetics of elemental sulfur reduction by petroleum hydrocarbons and the implications for hydrocarbon thermal chemical alteration

Although sulfur-containing compounds are known to play a significant role in the diagenic and catagenic processes that generate oil and gas, relatively little is known about the kinetics of reactions between elemental S and petroleum hydrocarbons. To investigate this subject, a series of closed-system pyrolysis experiments using paraffin, a low-sulfur oil, and a high-sulfur oil with and without elemental S were conducted, and first-order chemical kinetics were fit to the experimental results. The average value for the activation energy required to reduce elemental S to H 2 S and to thermochemically alter higher molecular weight hydrocarbons to methane was calculated to be 193 kJ mol -1 (46 kcal mol -1 ). The results of this study demonstrate that under typical geologic conditions the rate of reduction of elemental S to H 2 S by petroleum hydrocarbons is quite rapid. The maximum time for substantial amounts of elemental S to persist in contact with petroleum hydrocarbons is estimated to be no more than a few million years in cool reservoirs (e.g., <80 °C), and in hotter reservoirs (e.g., >120 °C) the half-life of elemental S may be as short as hundreds of years. Additionally, the presence of elemental S substantially lowers the onset temperature of hydrocarbon thermal chemical alteration (TCA). The activation energy for TCA of a low-sulfur oil to generate methane is estimated to be lowered by 92 kJ mol -1 (22 kcal mol -1 ) due to the presence of elemental sulfur. Consequently, the presence of elemental S in petroleum reservoirs is expected to lower the thermal stability of oil and decrease the maximum depth at which oil occurs within a basin (thermal deadline). The observed acceleration of hydrocarbon TCA is possibly due to organic sulfur compounds (e.g., thiols and sulfides) that form through the reaction of H 2 S or polysulfides with hydrocarbons and subsequently thermally degrade leading to the formation of sulfur radicals that in turn enhance TCA reactions.

Geochimica et Cosmochimica Acta↗

USGS2016

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n -hexadecane ( n -C 16 ) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H 2 S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H 2 S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4&permil; for H 2 S and as much as 22.2&permil; for BT. The fractionations decrease as the H 2 S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H 2 S and sulfate (&sim;17&permil;). Experiments involving sparingly soluble CaSO 4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H 2 S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO 4 is replaced with fully soluble Na 2 SO 4 , sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO 4 dissolution can lead to the apparent lack of fractionation between H 2 S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ 34 S values obtained from bulk phases such as H 2 S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Geochimica et Cosmochimica Acta↗

USGS2014

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C 2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C 2–5 hydrocarbons becoming more enriched in 13 C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ 13 C 2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Geochimica et Cosmochimica Acta↗

USGS2008

The role of labile sulfur compounds in thermal chemical sulfate reduction

The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n -octane and CaSO 4 in the presence of reduced sulfur (e.g. H 2 S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H 2 S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n -octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H 2 S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H 2 S. Second, we considered the generation of olefines in association with the elimination of H 2 S during thermal degradation of thiols because olefines are much more reactive than n -alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S–O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H 2 S accumulation in petroleum reservoirs.

Geochimica et Cosmochimica Acta↗

USGS2008

Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H 2 S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO 4 in the presence of variable H 2 S partial pressures at three different pH conditions. The experimental results showed that the in - situ pH of the aqueous solution (herein, in - situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in - situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H 2 S occurred under acidic conditions (at pH ∼3–3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H 2 S concentrations. To investigate whether the reaction of H 2 S (aq) and HSO 4 - "> HSO4- occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO 4 and variable H 2 S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO 4 reduction was not measurable in the absence of paraffin even with high H 2 S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H 2 S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H 2 S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82 , 1911–1916). Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H 2 S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H 2 S pressure. Thus, we propose that the LSC produced from H 2 S reaction with HC are most likely the reactive intermediates for H 2 S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.

Geochimica et Cosmochimica Acta↗

USGS2008

Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO 4 2- are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO 4 2- is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions ( HSO 4 - ) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of " HSO 4 - relative to SO 4 2- . However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO 4 - is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO 4 2- , aqueous calcium sulfate ([CaSO 4 ] (aq) ), and aqueous magnesium sulfate ([MgSO 4 ] (aq) ). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions ( HSO 4 - ) and/or magnesium sulfate contact ion-pairs ([MgSO 4 ] CIP ) rather than ‘free’ sulfate ions ( SO 4 2- ) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.

Geochimica et Cosmochimica Acta↗