The role of metal sulfates in thermochemical sulfate reduction (TSR) of hydrocarbons: Insight from the yields and stable carbon isotopes of gas products

Lü, Hong; Greenwood, Paul F.; Chen, Tengshui; Liu, Jinzhong; Peng, Ping’an

doi:10.1016/j.orggeochem.2011.03.011

Cited by 32 publications

(39 citation statements)

References 25 publications

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“…The reactants were loaded into 50 mm Â 4.2 mm Â 0.22 lm i.d. Au-tube reactors of high ductility and distilled water (40.0 lL) was added to each treatment to aid dissolution (Zhang et al, 2008a;Lu et al, 2010Lu et al, , 2011. The tubes were flushed with Ar to remove air and the open end of the Au-tube was crimped and welded closed whilst the tube bottom was submerged in a cold bath of Ar and water to prevent sample volatilization.…”

Section: Gold-tube Pyrolysismentioning

confidence: 99%

“…Each Au-tube surface was cleaned with dichloromethane and loaded separately into a piercing unit connected to a custom-made glass vacuum line (Pan et al, 2006;Lu et al, 2010Lu et al, , 2011. The tubes were pierced under vacuum.…”

Section: Gas Analysismentioning

confidence: 99%

“…The hydrophile nature of solid anhydrite could increase the likelihood of TSR (Heydari and Moore, 1989). The presence of MgSO 4 can significantly reduce the temperatures at which TSR occurs (Gillaizeau and Tang, 2001;Zhang et al, 2007Zhang et al, , 2008aLu et al, 2011), the high reactivity of this sulfate being attributed to HSO À 4 formation under acidic conditions reducing the activation energy between MgSO 4 and hydrocarbon reactants (Zhang et al, 2008b) and so destabilisation the SO 4 by the formation of contact ion-pairs (Ma et al, 2008 The most common TSR product is H 2 S, which has high solubility. Hydrogen sulfide produced in the initial stages of TSR may actually contribute to subsequent acceleration of the TSR process (Orr, 1982;Krouse, 1990, 1993;Goldhaber and Orr, 1995) by reacting (Eq.…”

Section: Introductionmentioning

confidence: 99%

“…Reaction processes were studied by monitoring the yields and stable isotopic values of gas and liquid hydrocarbon products. A similar analytical procedure was recently used to compare the TSR of 3 separate metal sulfates (MgSO 4 , CaSO 4 , Na 2 SO 4 ) under isothermal pyrolysis conditions (420°C; Lu et al, 2011). The focus of the present research was the reaction mechanisms and potential interplay of TSR and S production of H 2 S.…”

Section: Introductionmentioning

confidence: 99%

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The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

Lü

Greenwood

Chen

et al. 2012

Applied Geochemistry

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Section: Gold-tube Pyrolysismentioning

confidence: 99%

Section: Gas Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

Lü

Greenwood

Chen

et al. 2012

Applied Geochemistry

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“…All tubes were accurately weighed before and after pyrolysis to confirm the structural integrity of the pyrolyzed tubes. 11 2.3. Non-isothermal Temperature Program.…”

Section: Introductionmentioning

confidence: 99%

Impact of Inorganically Bound Sulfur on Late Shale Gas Generation

et al. 2014

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Nonisothermal, confined pyrolysis was applied to a mature shale sample from the Ordovician Salgan Formation in Tarim Basin, northwest China. Experiments were conducted using gold-tubes with added water at a very slow heating rate (2°C/h) and end temperatures between 336 and 600°C. To investigate the influence of inorganically bound sulfur on the generation of gases and to consider the geological occurrence of sulfur-containing minerals, such as prevalent pyrite in shales, the experiments were carried out with and without admixtures of MgSO 4 , CaSO 4 , and pyrite. High amounts of methane along with lower amounts of wet gases were formed from highly mature shale without minerals added, demonstrating a huge late gas generation potential at post peak-oil window maturities. In the experiments with added sulfates and pyrite, all organic gases were consumed in varying proportions, resulting in different chemical and stable carbon isotopic compositions. Pyrite treatment affects wet gas (C 2 −C 5 ) evolution directly, but it affects methane (C 1 ) evolution indirectly. In contrast, sulfate treatments affect C 1 −C 5 evolution directly. The cumulative yield ratio of CO 2 /H 2 S indicates that pyrite impacts on the hydrocarbon gas generation through low valence sulfur such as S 0 or others, which are associated with H 2 S generation. In the pyrite series, the smooth increase in ethane yield at temperatures exceeding 504°C, together with a concomitant stable carbon isotope reversal, demonstrates a new origin for ethane at high temperatures. The isotopic reversal may come from reactions between water and solid kerogen/coke/pyrobitumen. Isotopic reversal of ethane occurs only in the control and pyrite series but not in the sulfate treatments. This provides evidence that anoxic conditions are required. Thus, one can expect to encounter isotopic reversals in high maturity, unconventional gas shale environments in the presence of pyrite.

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Experimental evidence for formation water promoting crude oil cracking to gas

et al. 2012

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Crude oil cracking to gas is the key to determining the exploration potential and strategy for deep hydrocarbon resources. Identifying the factors that affect the threshold and potential of crude oil cracking to gas as well as other possible influencing factors will provide the scientific basis for deep hydrocarbon exploration. A comparison of pyrolysis simulation experiments of crude oil, hydrous crude oil, and various water media under a constant temperature (350°C) and pressure (50 MPa) shows that water plays a large role in crude oil cracking to gas. (1) When water is added, the gas yields increase significantly, including those of alkane gases and non-hydrocarbon gases: the yield of alkane gases increases 1.8-3 times; the yields of H 2 and CO 2 also increase significantly. This means that water takes part in the process of crude oil cracking to gas, and supplies hydrogen. Therefore, the presence of water will dramatically enhance the potential of crude oil cracking to gas. (2) Mg 2+ ions in the formation water promote the crude oil + water reaction to some extent and increase the total yield of alkane gases and the yields of both H 2 and CO 2 ; more interestingly, the i-C 4 /n-C 4 and i-C 5 /n-C 5 ratios increase significantly. This indicates that Mg 2+ ions in formation water act as a catalyst, and a disproportionation reaction is involved in the crude oil + water reaction. This study helps us to understand the factors influencing crude oil cracked gas and to evaluate the hydrocarbon resources in deep sedimentary basins.

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The role of metal sulfates in thermochemical sulfate reduction (TSR) of hydrocarbons: Insight from the yields and stable carbon isotopes of gas products

Cited by 32 publications

References 25 publications

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

Impact of Inorganically Bound Sulfur on Late Shale Gas Generation

Experimental evidence for formation water promoting crude oil cracking to gas

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