Experimental heating and kinetic models of source rocks: comparison of different methods

Ritter, U; Myhr, May Britt; Vinge, Torun; Aareskjold, Kaare

doi:10.1016/0146-6380(94)00108-d

Cited by 20 publications

(5 citation statements)

References 7 publications

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“…The pyrolysis products obtained in this way contain olefinic species rarely present in crude oils − and the evolution of the pyrolysis products with increasing maturity is far different from that expected under geologic conditions ,, with product yields being highly dependent on heating rates (decrease of the oil yield with decreasing heating rate). − Analyses of the residual kerogens following open pyrolysis also showed differences manifested in the results of elemental analyses, petroleum potential, T max (as determined by Rock Eval pyrolysis), and ratios determined by IR which often show evolutionary pathways that deviate from the natural trends (Figure ). ,,,− To improve the quality of the simulation, low heating rates are required, but this in turn leads to lower product yields. Poor results obtained in terms of simulation of natural processes can be attributed to the nature of the reacting medium developed in such a pyrolysis system.…”

Section: Thermal Characterization Of Organic Matter and Artificial Ma...mentioning

confidence: 93%

“…61 There are also discrepancies in product yields and their evolution with maturation, 59,61 , 62 with product yields being highly dependent on heating rates (decrease of the oil yield with decreasing heating rate). [63][64][65][66] Analyses of the residual kerogens following open pyrolysis also showed differences manifested in the results of elemental analyses, petroleum potential, T max (as determined by Rock Eval pyrolysis), and ratios determined by IR which often show evolutionary pathways that deviate from the natural trends (Figure 9). 57,58,61,[67][68][69] To improve the quality of the simulation, low heating rates are required, but this in turn leads to lower product yields.…”

Section: Thermal Characterization Of Organic Matter and Artificial Ma...mentioning

confidence: 99%

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Petroleum Geochemistry: Concepts, Applications, and Results

Philp

Mansuy

1997

Energy Fuels

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Petroleum geochemistry has played an important role in many areas of exploration and production for fossil fuels. Many of the more recent developments can be seen to have developed in parallel with developments in analytical chemistry such as gas chromatography and gas chromatography-mass spectrometry. For the past two decades such analytical techniques have been used to search for trace amounts of compounds known as biomarkers present in oils and source rock extracts which can be used to provide valuable information on the origin and history of the oil. In the past two or three years much more effort has been placed on the development and utilization of such techniques as an aid to solving reservoir and production problems. In this paper it is proposed to provide an overview of major developments that have occurred in a number of areas of geochemistry in recent years. This will include developments in reservoir geochemistry such as the use of high-resolution gas chromatography for reservoir continuity studies and high-temperature gas chromatography for characterization of wax deposits. A brief overview of recent developments in biomarker geochemistry will be provided in the section on exploration geochemistry along wth a discussion on the use of various pyrolysis techniques for the purposes of artificial maturation or characterization of the insoluble organic matter in source rocks or asphaltenes in oils. While this paper is not intended for the specialist in geochemistry, it is designed to provide the interested reader with a broad overview of the areas of geochemistry where the significant developments have occurred and continue to occur. As our analytical capabilities increase so do our abilities to obtain a far more detailed and comprehensive picture on the origin of fossil fuels than could ever have been imagined a mere two decades ago.

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Section: Thermal Characterization Of Organic Matter and Artificial Ma...mentioning

confidence: 93%

Section: Thermal Characterization Of Organic Matter and Artificial Ma...mentioning

confidence: 99%

Petroleum Geochemistry: Concepts, Applications, and Results

Philp

Mansuy

1997

Energy Fuels

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“…These methods include closed-system isothermal pyrolysis, such as hydrous pyrolysis (e.g., Lewan et al, 1979;Lewan and Ruble, 2002), microscale sealed vessel pyrolysis (e.g., Horsfield et al, 1989), or gold tube reactors (e.g., Behar et al, 1992). Debate continues as to the reliability of kinetics determined using open-versus closed-system pyrolysis (e.g., Schenk and Horsfield, 1993;Ritter et al, 1995;Barth et al, 1996;Lewan and Ruble, 2002). This paper does not address that issue, but instead focuses on open-system pyrolysis and distributed activation energy models for organic matter decomposition to petroleum, because most source-rock kinetic parameters are obtained using these methods.…”

Section: Introductionmentioning

confidence: 99%

Petroleum generation kinetics: Single versus multiple heating-ramp open-system pyrolysis

Peters

Burnham²,

Walters

2015

Bulletin

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A B S T R A C TSome recent publications promote one-run, open-system pyrolysis experiments using a single heating rate (ramp) and fixed frequency factor to determine the petroleum generation kinetics of source-rock samples because, compared to multiple-ramp experiments, the method is faster, less expensive, and presumably yields similar results. Some one-ramp pyrolysis experiments yield kinetic results similar to those from multiple-ramp experiments. However, our data for 52 worldwide source rocks containing types I, II, IIS, II/III, and III kerogen illustrate that one-ramp kinetics introduce the potential for significant error that can be avoided by using high-quality kinetic measurements and multiple-ramp experiments in which the frequency factor is optimized by the kinetic software rather than fixed at some universal value. The data show that kinetic modeling based on a discrete activation energy distribution and three different pyrolysis temperature ramps closely approximates that determined from additional runs, provided the three ramps span an appropriate range of heating rates. For some source rocks containing well-preserved kerogen and having narrow activation energy distributions, both single-and multiple-ramp discrete models are insufficient, and nucleation-growth models are necessary. Instrument design, thermocouple size or orientation, and sample weight likely influence the acceptable upper limit of pyrolysis heating rate. Caution is needed for ramps of 30-50°C/min, which can cause temperature errors due to impaired heat transfer between the oven, sample, and thermocouple. Compound volatility may inhibit pyrolyzate yield at the lowest heating rates, depending on the effectiveness of the gas sweep. We recommend at least three pyrolysis ramps that span at least a 20-fold variation of comparatively lower rates, such as 1, 5, and 25°C/min. The product of heating rate and

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“…An early study performed with gold tube pyrolysis of kerogen Type-III did not show an impact of water on bulk parameters like Rock-Eval or elementary analysis (Monthioux et al, 1985). Data presented by Ritter et al (1995) support this observation. In contrast, Behar et al (2003) reported that the vitrinite reflectance values for anhydrous experiments were on average 0.2 % R0 lower in comparison to hydrous experiments.…”

Section: Yields Of Hydrocarbons (Oil and Gas)mentioning

confidence: 67%

Experimental Simulation Of Hydrocarbon Expulsion

Schwark¹,

Stockhausen²,

Galimberti³

et al. 2014

International Petroleum Technology Conference

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Investigating generation, expulsion and primary migration usually suffers from inadequate methodologies, failing in the provision of natural conditions, prevailing during the genesis of oil and gas. Destructive sample preparation, inappropriate pressure regimes and pyrolysis in closed mode and/or in the absence of water caused results not representative for natural processes. To overcome these limitations, a newly designed apparatus was developed and built, capable to perform pyrolysis experiments with intact rock samples under pressure regimes, prevailing during catagenesis. In detail, lithostatic (or overburden-) pressures and hydrostatic (or pore-) pressures, corresponding to 3000 m depth and beyond, can be simulated by this apparatus, the "Expulsinator" device. Additionally, the experiments are conducted as hydrous, semi-open pyrolysis, allowing the time-based sampling of the expelled products. Thus, generation/expulsion profiles are generated for each investigated source-rock. Comparison of generation and expulsion efficiency of the Expulsinator with established pyrolysis methodologies (MSSV, HyPy, Rock Eval and closed small vessel pyrolysis (CSVP)) reveals striking differences: Expulsinator experiments yielded more bitumen and released lower gas amounts than classic pyrolysis. This is caused by secondary alteration of products in case of classic pyrolysis, e.g. oil to gas cracking at higher temperatures and polymerization to pyrobitumen. The open setup of the Expulsinator experiments prevents successfully secondary alteration, increasing the liquid product yields and lowering the gas formation. This is mirrored in TOC conversion rates as well: Expulsinator conversion exceeds 81 %, whereas those of hydrous CSVP remains at 65 %. Further, interactions between kerogen, bitumen, pyrobitumen and pyrite are reduced in case of Expulsinator experiments. In contrast, CSVP experiments residues show enrichment of nitrogen and oxygen and depletion of sulphur, indicating intense interaction between the mentioned components. Investigating the impact of catagenesis onto the yields and composition of expelled products was carried out by a stepwise experimental setup, simulating burial depths of ~2000 m, ~2500 m and 3000 m, implementing overburden pressures from 600 bar to 900 bar and hydrostatic pressures from 200 bar to 300 bar. Each experiment step shows a distinct expulsion maximum of liquid hydrocarbons, reaching the total maximum at 3000 m. Confrontation of Expulsinator results with comparative CSVP and MSSV experiments reveal expulsion and primary migration effects onto the n-alkane distribution in dependence of maturation and subsidence. An n-alkane increase towards larger molecular size with ongoing expulsion is associated with molecular size controlled retention effects. The expulsion progress is mirrored in trends of isoprenoid-ratios (pristane vs. phytane) and isoprenoidn-alkaneratios (pristane vs. n-C17), caused mainly by generation controlled effects. However, both ratios qualify as expulsion indicator, taking ...

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Experimental heating and kinetic models of source rocks: comparison of different methods

Cited by 20 publications

References 7 publications

Petroleum Geochemistry: Concepts, Applications, and Results

Petroleum Geochemistry: Concepts, Applications, and Results

Petroleum generation kinetics: Single versus multiple heating-ramp open-system pyrolysis

Experimental Simulation Of Hydrocarbon Expulsion

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