Guidelines For Kinetic Input and Calibration of Petroleum System Models PDF

PetroMod & Petroleum Systems Technology Days
Technology Days
April 17-19, 2018
Aachen, Germany
Practical Guidelines for Kinetic Input and

Calibration of Petroleum System Models
Ken Peters
Potential Energy
Geochemistry Advisor, Schlumberger Ea Product
Adjunct Professor, Stanford BPSM Reactant
Reaction Progress
Outline of the Presentation
• Introduction to the Arrhenius equation and optimization

• Repeatability, depositional environment, kerogen type,
and kinetic response
• Single vs. multiple heating ramp pyrolysis for kinetics
• Global kinetics of vitrinite maturation and its use in
model calibration
• Conclusions and references
1 PetroMod Technology Days

Summary of Some Key Points
• Kerogen type (HI) is not linked to kinetic response!

• Depositional environment does not define kerogen type!
• Default kinetics may differ for the same kerogen type in
different basins. Use default kinetics with caution.
• Kerogen kinetics vary laterally/vertically in source rock.
• Both Ea and A are required to define kinetic response.
• Easy%Ro is less accurate than Basin%Ro or Easy%RoDL

Reaction Rate Depends on Temperature and Pre-Exponential
Arrhenius Equation

Many Factors Influence Rate Constant
• Temperature is the primary control

• Pressure
✓ Role in kerogen conversion is controversial
✓ Most publications indicate only small effects*
• Pore fluid composition
✓ Potassium in brine controls smectite-to-illite rate
• Reactant composition
✓ Fission track annealing depends on chlorine-fluorine in
apatite
✓ Sulfur and oxygen increase kerogen cracking rate
*Petroleum was generated at the same temperature (~120oC) but different depths in the Los
Angeles and Ventura basins (~2.4 and 3.8 km depth, respectively; Philippi, 1965). Because
pressure is directly related to depth, T rather than P exerts the main control on petroleum
generation.
Some Kinetic Models in PetroMod
• Kerogen conversion to hydrocarbons

• Vitrinite reflectance (Easy%Ro)
• Liquid hydrocarbon cracking to gas
• Smectite to illite transformation
• Apatite fission track annealing
• Biomarker isomerization/aromatization
• Opal A-opal CT-quartz phase transition

Various Approaches for Petroleum Generation Kinetics
• Default kinetics based on kerogen type as

defined by Rock-Eval hydrogen index (Waples,
1992; Pepper, 2003)
• Global kinetics based on field and laboratory
data for collections of source rocks from five
generic organofacies (Pepper and Corvi, 1995)
• Asphaltene kinetics (di Primio et al., 2000)
• Measured kinetics for immature equivalents of
source rock in the study area (Ungerer, 1990;
Dieckmann, 2005; Peters et al., 2015)
Pyrolysis Systems for Kinetics: Pyromat II™, SR Analyzer™
Pyromat II™
SR Analyzer™

Pyromat II® Optimizes Position of Sample and Thermocouple
Polarization
Electrode
Pyromat II®
Coinjector
Electrode
Temperature
Programmed
Oven
Thermocouple
High Temperature
Flame Ionization
10 cm Detector
Open Position
Helium Flow
Designed and Built by Lab Instruments & LLNL
Quartz Crucible
3-10 mg Rock or Kerogen
Closed Position
1 cm
To FID
Dynaseal O-ring Seal Thermocouple Quartz Wool

Inserted

“Discrete Activation Energy Models”: One Frequency Factor
k = Ae-Ea/RT
k = Arrhenius rate constant (kerogen to oil and gas )
A = frequency factor (e.g., vibrational frequency of bonds broken)
Ea = activation energy, R = gas constant, T = temperature
Laboratory Pyrolysis Optimization Geologic Conditions

1.0
Transformation Ratio
Calculated A=1x 1014 sec-1
Detector Signal
Experimental 50°C/min 0.8 3oC/my

Fraction
30°C/min 0.6
50% TR
5°C/min 10°C/min
0.4
3°C/min
0.2
1°C/min
0
300 350 400 450 500 550 600 41 43 45 47 49 51 53 55 57 59 61 63 65 50 100 150 200
Temperature (°C) Ea (kcal/mol) Temperature (oC)

Technology Days
April 17-19, 2018
Aachen, Germany
Repeatability, Depositional Environment,

Kerogen Type, and Kinetic Response
Ken Peters
Geochemistry Advisor, Schlumberger
Adjunct Professor, Stanford BPSM Fraction
EEa, kcal/mol
,
a
kcal/mo
le
Purpose - Use Open-System Programmed Pyrolysis to Find:
• Kinetic response for a worldwide collection of

Type II source rocks
• Kinetic response for a collection of Type I and
II samples within one source rock

10 Replicate Analyses Test Repeatable Pyrolysis Method
1.0
0.8
Green River Shale Samples
25oC/min in SR Analyzer
Signal
0.6
0.4
0.2
250 300 350 400 450 500 550 600 650

Data courtesy of Dan Jarvie
Temperature (oC) (Humble Instruments & Services)

Excellent Repeatability for 10 Green River Shale Analyses
1.0
Fractional Conversion
0.9
0.8 Green River Shale

0.7
1oC/my Burial 80
70
60
0.6
Fraction
50 A = 9.34E+13
2.3 o C
40
0.5
30
20
0.4
10
0
0.3 39 41 43 45 47 49 51 53 55 57 59 61 63 65
E a (kcal/mol)
0.2
0.1
70 90 110 130 150 170 190

Data courtesy of Dan Jarvie
Temperature (oC) (Humble Instruments & Services)

Examine Kinetics for a Global Collection of Type II Kerogens
140
S2 (mg HC/g rock) 120

Type I Type II
100
80
60
29 Worldwide
40
Source Rocks
20
0
0 10 20 30 40
TOC (wt.%)
Peters et al. (2006)
*HI = Rock-Eval hydrogen index = 100 x S2/TOC
Generation Timing Varies for Worldwide Type II Kerogens
1.0
0.9
Fractional Conversion
0.8
Type II Samples
0.7 1oC/my Burial
0.6
0.5 30oC
0.4
0.3
0.2 Pepper & Corvi (1995)

Behar et al. (1997)
0.1 Dieckmann et al. (2000)
50 70 90 110 130 150 170 190

Temperature (oC)
Examine Kinetics for Samples Within One Source Rock
Calvert
Orton
90 Quest
S2 (mg HC/g TOC)
Rixon
80
Saxon
70
60 Type I
50 52 Jurassic Oxford
40 Clay Samples, U.K.
30
Type II
20
10
0
0 2 4 6 8 10 12 14
TOC (wt.%) Peters et al. (2006)

Are Kinetics Uniform Within One Source Rock? No!
0.9
0.8 Oxford Clay Samples

1oC/my Burial
0.7
0.6
0.5 23oC
0.4
0.3
0.2
0.1
70 90 110 130 150 170 190

17 PetroMod Technology Days Temperature (oC)
Depositional Setting ≠ Kerogen Type ≠ Kinetics!
• Two ‘Leaps of Faith’: Kerogen type from depositional

environment and kinetics from kerogen type…..
Setting Type ~TOC ~H/C ~HI Kinetics
Lacustrine I >3% 1.6 600-900 “Type I”
Marine II >2% 1.3 300-600 “Type II”
Terrigenous III variable 0.9 100-300 “Type III”
DON’T DO IT!
Predict Kerogen Type (Not Kinetics) from Depositional Setting
Depositional Kerogen
Tectonic Setting Lithofacies
Environment Type
Marine Source Rocks
Restricted Basin Anoxic with clay Marine shale II
Anoxic, saline
Restricted Basin Carbonate IIS
with/without clay
Epicontinental Seaway Anoxic Shale, carbonate II
Shale, carbonate,
Upwelling Shelf Area Anoxic or suboxic II, IIS
chert, phosphorite
Open Ocean Oxic or suboxic Prodelta shale III
Nonmarine Source Rocks
Coastal Swamp Anoxic Coal III
Paralic Basin Oxic or suboxic Prodelta shale III
Open Lacustrine Anoxic, freshwater Oil shale I
Restricted Lacustrine Anoxic, saline Oil shale IIS
Marginal Lacustrine, Fluvial Oxic or suboxic Siltstone, shale II/III
Biomarker Guide, p. 86

Lower Cretaceous Facies Map: Songliao Basin, China
200 km
Beijing
China
Fluvial Facies Type III

Shallow Lake Type II
Facies
Deep Lake Type I
Facies
Oil Field After Wanli et al. (1985)

Use Pepper & Corvi (1995) Default Kinetics as a Last Resort
Oil Generation Gas Generation

Conclusions: Kerogen Type and Kinetic Response
• Source rocks having similar kerogen based on Rock-

Eval pyrolysis can show very different kinetics.
✓ Kerogen type as defined by hydrogen index is not
systematically linked to kinetic response.
✓ Default kinetics for type I or II kerogen can
introduce unacceptable errors into numerical
calculations.
• Measured kinetics may not adequately account for
source-rock organofacies variations.

References for Kerogen Type and Kinetic Response
• Dieckmann V., 2005. Modeling petroleum formation from heterogeneous

source rocks: the influence of frequency factors on activation energy
distribution and geological prediction: Marine and Petroleum Geology 22,
375-390.
• Nielsen S.B., 1992. Uncertainties in kerogen kinetic parameters and
consequences for hydrocarbon modeling: Journal of Applied Geophysics
29, 69-70.
• Pepper A.S., P.J. Corvi, 1995. Simple kinetic models of petroleum
formation. Part I: Oil and gas generation from kerogen: Marine and
Petroleum Geology 12, 291-319.
• Peters K.E., C.C. Walters, P.J. Mankiewicz, 2006. Evaluation of kinetic
uncertainty in numerical models of petroleum generation: AAPG Bulletin
90, 1-19.
• Peters K.E., A.K. Burnham, C.C. Walters, 2015. Petroleum generation
kinetics: Single- versus multiple heating-ramp open-system pyrolysis:
AAPG Bulletin 99, 591-616.

Technology Days
April 17-19, 2018
Aachen, Germany
Petroleum Generation Kinetics: Single-

Versus Multiple-Heating Ramp Pyrolysis
1.0
Ken Peters
90% TR
0.8
Geochemistry Advisor, Schlumberger 0.6
50% TR
Adjunct Professor, Stanford BPSM

0.4
3oC/my
0.2
10% TR
0
50 100 150 200
Temperature (oC)
Recent Papers Recommend “Single-Ramp Kinetics”
• Single-ramp* kinetics (Waples et al., 2002, 2010), Waples

and Nowaczewski (2013) use a fixed, universal A.
• Single-ramp is faster and cheaper than multiple-ramp
kinetics and can be used on archived pyrolysis data.
• Multiple-ramp kinetics optimize both Ea and A: Pyromat II®
ramps = 1, 3, 5, 10, 30, and 50oC/min
*Ramp = heating rate
Example of a Commercial Offering
https://siriusxgc.com/training/

Purpose – Compare Single- and Multiple-Ramp Kinetics
• Compare reliability of various combinations of open-
system pyrolysis ramps to determine the kinetics of
petroleum generation for 52 global source rocks.
• Is single-ramp kinetics using a fixed A (1 x 1014 sec-1)
more reliable than multiple-ramp kinetics where both Ea
and A are optimized?
Geologic Conditions
Laboratory Pyrolysis Optimization 1.0
0.8
90% TR
0.6
Kinetics05® 0.4
50% TR
Software 3oC/my
0.2
10% TR
0
50 100 150 200
Pyromat II® Micropyrolysis Temperature (oC)

Assessment of Single-Ramp Kinetics Involves Three Factors
1) Are there real differences in frequency factors (A) for

petroleum generation from kerogen in source rocks?
2) Are the differences in A large enough to significantly
impact extrapolation of temperatures to geologic
conditions (e.g., at different transformation ratios)?
3) What experimental conditions are required to answer
questions 1 and 2?
A = 1 x 1014/sec
Fraction
Ea (kcal/mol)

Arrhenius Equation Expressed Relative to Reference Values
k = Ae-Ea/RT
k1 = A1e-E /RT 1 k2 = A2e-E /RT
2
Pick T so that k1 = k2
A1e-E /RT= A2e-E /RT
1 2
Ln A1/A2 = (E1 – E2)/RT
Log A – Log Aref = (Ea – Eref)/2.303RT

Compensation Law: Lab Predictions Deviate at Geologic Heating Rates
2
Log A – Log Aref Loci of solutions with
equal residual error TR50 = 152oC
1
0 TR50 = 132oC Eref = 50 kcal/mol

Aref = 1 x 1014 sec-1
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
29
Modified from Burnham (1992)
PetroMod Technology Days

Ea- Eref, kcal/mol
1 Kcal/mol Error in Ea is Compensated by 2-Fold Change in A
2
1
Log 2 = 0.3
0 TR50 = 132oC Eref = 50 kcal/mol

Aref = 1 x 1014 sec-1
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
30

Ea- Eref, kcal/mol
Errors in Predicted Geologic Temperature Can be Substantial
2
1 Log 4 = 0.6
Log 2 = 0.3
0 TR50 = 132oC
3oC/my
-1
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
31

Ea- Eref, kcal/mol
1 Kcal/mol Error in Ea is Compensated by 2-Fold Change in A
2
1
0 TR50 = 132oC
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
32

Ea- Eref, kcal/mol
Fixed A Introduces Error in Geologic T Extrapolation (~20oC)
1-2-3 Rule: 1 kcal/mol error doubles A and yields

~3oC error in geologic extrapolation of temperature
Range A for 52 kerogens = 1012 to 1016 sec-1

Assume a fixed A of 1 x 1014 sec-1
1014/1012 = 100
Log2100 = 6.65 (i.e., A doubles 6.65 times)
6.65 x 3oC/my ~ 20oC error

16 Single-Ramp Replicates Give ‘Best’ Ea of ±0.28 Kcal/mole
Geologic Extrapolation
Bellagio Road outcrop (Type II) Assuming 3oC/my
Afixed = 1 x 1014 sec-1
Mean Ea, Temp oC Temp oC Temp oC
Tmax, oC
kcal/mole at 10% TR at 50% TR at 90% TR
Average 449.3 53.54 112.0 137.3 163.7
Minimum 447.8 52.97 105.2 135.8 160.4
Maximum 452.1 53.87 115.0 138.4 168.2
Std. Dev. 1.3 0.28 2.3 0.8 2.2
TR = transformation ratio (extent of conversion of kerogen to petroleum)

Fixed vs. Optimized A: Offset of Ea by Compensation Law
2.0
Log A (Single Run – Multi Run) Type
Type
I
II
1.5 y = 0.3067x + 0.0459
Type IIS
Type II/III R² = 0.9943
1.0 Type III
0.5 Log 2 = 0.3
0.0
52 Global
-0.5 Source Rocks
-1.0
-1.5
-4 -3 -2 -1 0 1 2 3 4 5
Ea Mean (Single run – Multi Run)
Single- and Multi-Ramp Models Yield Different Temperatures
Temp. (°C) at 50% TR (Single Ramp)

170
165 Type I
Type II
160
Type IIS
155 Type II/III
Type III
150
145
140
135 3oC/my
130
125
120
120 130 140 150 160 170
Temp. (°C) at 50% TR (Multiple Ramp)

Heating-Rate Ratio (Rr) = Maximum / Minimum Ramp
• Pyromat II® Ramps = 1, 3, 5, 10, 30, and 50oC/min

• Therefore, Rr of 1 is a single-ramp experiment (fixed A).
• Rr of 50 consists of all 50/1 multi-ramp experiments
(optimized A):
1,50
1,3,50
1,5,50
1,10,50 oC/min
1,3,5,50
1,5,10,50
1,10,30,50
1,3,5,10,30,50
Single- vs. Multi-Ramp: Wide vs. Narrow Deviation in Ea
10
Kimmeridge Clay
6 Monterey Shale
Average Ea (kcal/mol)
Deviation from
2
3σ
-2
-6
Multiple-Ramp
-10
Single-Ramp 0 10 20 30 40 50 60
38 PetroMod Technology Days Heating-Rate Ratio (Rr)
Variation in Ea Becomes Small for Heating-Rate Ratios >16
10
Kimmeridge Clay
6 Monterey Shale
Average Ea (kcal/mol)
Deviation from
2
3σ
-2
-6
Multiple-Ramp
-10
Single-Ramp 0 10 20 30 40 50 60
39 PetroMod Technology Days Heating-Rate Ratio (Rr) Peters et al. (2015)
Differing A and Ea are Real and Not Measurement Artifacts
56
Activation Energy (kcal/mol)
Kimmeridge
54 (all heating rates)
52
Monterey Rr >16
(all heating rates) e.g., 1,3,30;
1,3,5,30;
50 1,3,5,10,30;
1,3,5,10,30,50
48
1 x 1012 1 x 1013 1 x 1014 1 x 1015

Frequency Factor (sec-1)
More Ramps Focus Predicted Temperature and Transformation Ratio
150 125
145
140 Kimmeridge 10% 120
115
Monterey 10%
135 110
130 105
125 100
1,3,5,10,30,50 1,3,5,10,30,50
Temperature (oC)
120 95
115 90 10,50 10,30,50
10,50 10,30,50
110 85
1 2 3 4 5 6 1 2 3 4 5 6
150
165 50% 140 50%
155 130
120 1,3,5,10,30,50
145 10,30,50
1,3,5,10,30,50 110
135 100
10,50 10,30,50
30,50
125 90
1 2 3 4 5 6 1 2 3 4 5 6
175
190
170
180
90% 165
90%
170 160
155
160 1,3,5,10,30,50
150 1,3,5,10,30,50
150 10,50 10,30,50 145
10,50 10,30,50
140 140
1 2 3 4 5 6 1 2 3 4 5 6
Single Ramp
= Multiple Ramp,
41
Fixed A
PetroMod TechnologyOptimized
Days Ea and A Number of Ramps = 50oC/min Ramp
Multiple Ramps, Optimized Ea and A Yield More Reliable Predictions
150 125
145
140 Kimmeridge 10% 120
115
Monterey 10%
135 110
130 105
125 100
1,3,5,10,30,50 1,3,5,10,30,50
120
Temperature (oC)
95
115 90 10,50 10,30,50
10,50 10,30,50
110 85
1 2 3 4 5 6 1 2 3 4 5 6
150
165 50% 140 50%
155 130
120 1,3,5,10,30,50
145 10,30,50
1,3,5,10,30,50 110
135 100
10,50 10,30,50
30,50
125 90
1 2 3 4 5 6 1 2 3 4 5 6
175
190
170
180
90% 165
90%
170 160
155
160 1,3,5,10,30,50
150 1,3,5,10,30,50
150 10,50 10,30,50 145
10,50 10,30,50
140 140
1 2 3 4 5 6 1 2 3 4 5 6
Single Ramp
= Multiple Ramp,
42
Fixed A
PetroMod TechnologyOptimized
Days Ea and A Number of Ramps = 50oC/min Ramp
Conclusions (I)
• Single-ramp pyrolysis can yield kinetic results that are

inconsistent with those from multiple-ramp experiments.
• Frequency factors (A) for 52 global source rocks are
statistically distinct within measurement uncertainty and
vary over four orders of magnitude (1012 to 1016 sec-1).
• Assuming a universal value for A erroneously presumes
that temperature measurements do not have sufficient
accuracy for reliable kinetics.
• Adoption of fixed A of 1 x 1014 sec-1 can result in error in
geologic temperature extrapolation of up to ~20oC.

Conclusions (II)
• Pyrolysis ramps of 30-50oC/min can be too fast for good

kinetic fit because of thermal lag; minimize sample and
thermocouple size, optimize thermocouple orientation.
• Heating rate x sample weight (Pyromat II) <100mgoC/min.
• 20- to 30-fold variation in heating rate using at least three
ramps is recommended (e.g., 1, 5, 25oC/min or 1, 3,10,
25oC/min) with replicates at highest and lowest rates.
• Neither single- nor multiple- ramp discrete Ea distribution
models are reliable for kerogens with narrow Ea ranges
where nucleation-growth models are needed.

References for Single- vs. Multiple-Ramp Kinetics
• Braun R.L. et al., 1991. Pyrolysis kinetics for lacustrine and marine source rocks by
programmed micropyrolysis: Energy & Fuels, v. 5, p. 192-204.
• Burnham A.K., 2014. Obtaining reliable phenomenological chemical kinetic models for
real-world applications: Thermochimica Acta 597, 35-40.
• Peters K.E., A.K. Burnham, C.C. Walters, 2015. Petroleum generation kinetics: Single-
versus multiple heating-ramp open-system pyrolysis. AAPG Bulletin 99, 591-616.
• Peters K.E., A.K. Burnham, C.C. Walters, 2016. Petroleum generation kinetics: Single
versus multiple heating-ramp open-system pyrolysis: Reply: AAPG Bulletin 100, 690-694.
• Waples D.W., V.S. Nowaczewski, 2013. Source-rock kinetics, accessed January 26, 2016
https://siriusdummy.files.wordpress.com/2013/11/perspective-on-sr-kinetics-ss.pdf.
• Waples D.W., A. Vera, J. Pacheco, 2002. A new method for kinetic analysis of source rocks:
development and application as a thermal and organic facies indicator in the Tithonian of
the Gulf of Campeche, Mexico: Abstracts, 8th Latin American Congress on Organic
Geochemistry, Cartagena, p. 296-298.
• Waples D.W. et al., 2010. A new method for obtaining personalized kinetics from archived
Rock-Eval data applied to the Bakken Formation, Williston Basin. Abstract, AAPG Annual
Convention, Calgary, accessed February 11, 2016,
https://www.searchanddiscovery.com/pdfz/abstracts/pdf/2010/intl/abstracts/ndx_waples02.
pdf.html.
Technology Days
April 17-19, 2018
Aachen, Germany
Global Kinetics of Vitrinite Maturation

and Its Use in Model Calibration
Ken Peters
Geochemistry Advisor, Schlumberger
Adjunct Professor, Stanford BPSM
Aromatization Liberates Hydrogen and Increases Ro
Huminite or
Anthracite
Vitrinite
6H

Vitrinite Reflectance (Ro) Histograms: 20-100 Measurements
Ordered Ro Values
5
Ro = 0.74 ± 0.05% for One Rock Sample
Frequency
4 0.63 0.64 0.64 0.65 0.66 0.66

0.67 0.67 0.68 0.68 0.69 0.69
0.69 0.70 0.70 0.70 0.71 0.71
3
0.71 0.72 0.72 0.72 0.72 0.73
0.73 0.73 0.73 0.74 0.74 0.74
2 0.74 0.74 0.75 0.75 0.75 0.76
0.76 0.76 0.76 0.77 0.77 0.77
1 0.78 0.78 0.78 0.78 0.79 0.79
0.80 0.80 0.81 0.83 0.84 0.84
0.85
Number of Measurements = 55
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.2 1.3
Average Reflectance = 0.74%
Vitrinite Reflectance (Ro, %) Standard Deviation = 0.05%
10 µm Polished surface of vitrinite is

‘low-gray’ in reflected light

Catagenetic Loss of Volatiles Changes Kerogen Composition
Van Krevelen Diagram
McCarthy et al. (2011) After Van Krevelen (1961)

4.0 Volatiles
H2O Loss
CO2 Loss
Atomic H/C
3.0 CH4 Loss
Atomic H/C
1.5
2.0
Vitrinite
1.0
1.0
0.5
0 0.1 0.2 0.3 0 0.5 1.0 1.5 2.0
Atomic O/C Atomic O/C

Most Model Calibrations Use Vitrinite Reflectance
• Vitrimat (Burnham et al., 1989, GCA 53: 2649-

2657) – first compositional kinetic model of
vitrinite reflectance
• Easy%Ro (Sweeney and Burnham, 1990,
AAPG Bulletin 74: 1559-1570) – simplified and
faster due to elimination of compositional
information

Easy%Ro: Model Calibrated to H/C Correlation of Vitrimat
VITRIMAT elemental
balance equations and
reflectance correlations
Burnham et al. (2016)

Easy%Ro is Used to Calculate Vitrinite Reflectance
• Global vitrinite maturation is described by:

8
Reaction, %
A = 1.0 x 1013 sec-1
Amount of
0
0 40 50 60 70
Activation Energy, kcal/mol

• Reflectance is related to total conversion by:
%Ro = exp(-1.6 + 3.7 * fractional conversion)

EasyRo Does Not Calibrate Ro Below the Dogleg at 4000 m
Aurora-1
Well A Aurora-1
Well A
Easy%RoDL Easy%RoDL
Basin%Ro Basin%Ro
Easy%Ro Easy%Ro
Dogleg

Basin%Ro Better Replicates the Dogleg and Deeper Ro Data
Aurora-1
Well A Aurora-1
Well A
Easy%RoDL Easy%RoDL
Basin%Ro Basin%Ro
Easy%Ro Easy%Ro
Dogleg

EasyRo is Less Reliable Than Basin%Ro and Basin%RoDL
Aurora-1
Well A Aurora-1
Well A
Easy%RoDL Easy%RoDL
Basin%Ro Basin%Ro
Easy%Ro Easy%Ro
Optimized A, sec-1
Easy%RoDL: 2.0 x 1014
Basin%Ro: 9.696 x 1012
Easy%Ro: 1.0 x 1013
Dogleg

Kinetic Models Predict Different Ro Trends with Temperature
5
Basin%Ro
Vitrinite Reflectance, %Ro
Easy%Ro
4
Vitrimat H/C %Ro
3 Basin%Ro rises
faster at high maturity
Sediments heated at 2.8 C/my
2
Agreement at ~2% R o
1
Sharper ‘dogleg’ in oil
generation window
0
0 50 100 150 200 250 300
Temperature, oC
Burnham et al. (2016)

Influence of Pressure on Ro are Small or Inconsistent
• Huang (‘96): large differences for open vs. closed pyrolysis, but little
difference from 0.5-2.0 kbar
• Landais et al. (‘94): little effect between 0.5 and 4 kbar
• Uguna (‘12): pressure slightly inhibited Ro in range 0.2-0.9 kbar
• Della Torre (‘97), Le Bayon et al. (‘11): inhibition/acceleration
depending on pressure and Ro range
Le Bayon et al., 2011
Relevant geological
pressures are <2 kbar!

Synopsis: Some Discussion Points
• Kerogen type is not linked to kinetic response!

• Depositional environment does not define kerogen type!
• Kerogen kinetics vary laterally/vertically in source rock.
• Both Ea and A are required to define kinetic response.
• Measured kinetics are generally better than defaults, but
require representative thermally immature equivalents.
• Role of pressure is controversial but probably minor.
• Kinetic uncertainty is described by the 1-2-3 rule.
• Easy%Ro less accurate than Basin%Ro and Easy%RoDL

References for Global Vitrinite Reflectance Kinetics
• Braun R.L., A.K. Burnham, 1994. KINETICS: A computer program to analyze chemical reaction data: Lawrence Livermore
National Laboratory, UCRL-ID-21588, Rev 2, 14 p.
• Burnham, A.K., 2017. Global Chemical Kinetics of Fossil Fuels–How to Model Maturation and Pyrolysis, Springer, 315 p.
• Burnham, A.K., K.E. Peters, O. Schenk, 2016. Evolution of vitrinite reflectance models, Presentation to Linked-In
Petroleum Systems Analysts, https://www.youtube.com/watch?v=rOYNujm80uU.
• Hantschel T., A.I. Kauerauf, 2009. Fundamentals of Basin and Petroleum Systems Modeling: Springer, 476 p.
• Nielsen S.B., O.R. Clausen, E. McGregor, 2015. Basin%Ro: A vitrinite reflectance model derived from basin and
laboratory data: Basin Research, 1-22.
• Pepper A.S., P.J. Corvi, 1995. Simple kinetic models of petroleum formation. Part I: Oil and gas generation from kerogen:
Marine and Petroleum Geology 12, 291-319.
• Schenk, O., K.J. Bird, L.B. Magoon, K.E. Peters, 2012. Petroleum system modeling of Northern Alaska. In K.E. Peters, D.
Curry, M. Kacewicz (eds.) Basin Modeling: New Horizons in Research and Applications. AAPG Hedberg 4, 317-338.
• Schenk, O., K.E. Peters, A.K. Burnham, 2017. Evaluation of alternatives to Easy%Ro for calibration of basin and
petroleum system models. Extended abstract, EAGE, Paris, France.
• Suggate R.P., 1998. Relations between depth of burial, vitrinite reflectance and geothermal gradient. Journal of
Petroleum Geology 21, 5-32.
• Sweeney J.J., A.K. Burnham, 1990. Evaluation of a simple model of vitrinite reflectance based on chemical kinetics.
AAPG Bulletin 74, 1559-1570.

About the Speaker: Ken Peters
• 40 years: Chevron, Mobil, ExxonMobil, USGS, Schlumberger, UC Berkeley, Stanford
• ~165 peer reviewed papers in geology, geochemistry, and basin modeling
• The Biomarker Guide (1993, 2005); Getting Started in Basin and Petroleum System
Modeling (2009); Basin Modeling: New Horizons in Research and Applications (2012)
• Adjunct Professor, Stanford University (BPSM Industrial Affiliates Program)
• Schlumberger NExT Instructor, EAGE Instructor
• Honorary Teaching Fellow (U. of Aberdeen); Visiting Professor (Jacobs U., Bremen)
• Chair Gordon Research Conference on Organic Geochemistry (1998)
• Chair AAPG Research Committee (2007-2010)
• Fellow in The Geochemical Society, AAPG Charles Taylor Fellow;
AAPG Distinguished Lecturer (2009 and 2010)
• Associate Editor for AAPG Bulletin, Journal of Petroleum Geology,
and Organic Geochemistry
• Alfred E. Treibs Medalist (2009); AAPG Honorary Member Award
(2013); EAGE Alfred Wegener Award (2016); AAPG Heritage of the
Petroleum Geologist Honoree (2017)
• Experience in most basins worldwide

Guidelines For Kinetic Input and Calibration of Petroleum System Models PDF

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PetroMod & Petroleum Systems Technology Days

Practical Guidelines for Kinetic Input and

Adjunct Professor, Stanford BPSM Reactant

• Introduction to the Arrhenius equation and optimization

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• Kerogen type (HI) is not linked to kinetic response!

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• Temperature is the primary control

• Kerogen conversion to hydrocarbons

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• Default kinetics based on kerogen type as

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Dynaseal O-ring Seal Thermocouple Quartz Wool

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Laboratory Pyrolysis Optimization Geologic Conditions

Experimental 50°C/min 0.8 3oC/my

Temperature (°C) Ea (kcal/mol) Temperature (oC)

Repeatability, Depositional Environment,

• Kinetic response for a worldwide collection of

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250 300 350 400 450 500 550 600 650

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0.8 Green River Shale

70 90 110 130 150 170 190

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S2 (mg HC/g rock) 120

0.2 Pepper & Corvi (1995)

50 70 90 110 130 150 170 190

TOC (wt.%) Peters et al. (2006)

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0.8 Oxford Clay Samples

70 90 110 130 150 170 190

• Two ‘Leaps of Faith’: Kerogen type from depositional

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Fluvial Facies Type III

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Oil Generation Gas Generation

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• Source rocks having similar kerogen based on Rock-

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• Dieckmann V., 2005. Modeling petroleum formation from heterogeneous

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Petroleum Generation Kinetics: Single-

Geochemistry Advisor, Schlumberger 0.6

Adjunct Professor, Stanford BPSM

• Single-ramp* kinetics (Waples et al., 2002, 2010), Waples

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Pyromat II® Micropyrolysis Temperature (oC)

1) Are there real differences in frequency factors (A) for

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Ln A1/A2 = (E1 – E2)/RT

Log A – Log Aref = (Ea – Eref)/2.303RT

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0 TR50 = 132oC Eref = 50 kcal/mol

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0 TR50 = 132oC Eref = 50 kcal/mol

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1-2-3 Rule: 1 kcal/mol error doubles A and yields

Range A for 52 kerogens = 1012 to 1016 sec-1

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