Guidelines For Kinetic Input and Calibration of Petroleum System Models PDF
Guidelines For Kinetic Input and Calibration of Petroleum System Models PDF
Guidelines For Kinetic Input and Calibration of Petroleum System Models PDF
Technology Days
April 17-19, 2018
Aachen, Germany
Ken Peters
Potential Energy
Geochemistry Advisor, Schlumberger Ea Product
Reaction Progress
Outline of the Presentation
Arrhenius Equation
Pyromat II™
SR Analyzer™
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
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
Transformation Ratio
Calculated A=1x 1014 sec-1
Detector Signal
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
Technology Days
April 17-19, 2018
Aachen, Germany
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:
1.0
0.8
Green River Shale Samples
25oC/min in SR Analyzer
Signal
0.6
0.4
0.2
1.0
Fractional Conversion
0.9
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
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
14 PetroMod Technology Days
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
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
0.9
Transformation Ratio
0.6
0.5 23oC
0.4
0.3
0.2
0.1
DON’T DO IT!
18 PetroMod Technology Days
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
200 km
Beijing
China
Technology Days
April 17-19, 2018
Aachen, Germany
1.0
Ken Peters
Transformation Ratio
90% TR
0.8
50% TR
Temperature (oC)
Recent Papers Recommend “Single-Ramp Kinetics”
https://siriusxgc.com/training/
Transformation Ratio
0.8
90% TR
0.6
Kinetics05® 0.4
50% TR
Software 3oC/my
0.2
10% TR
0
50 100 150 200
Fraction
Ea (kcal/mol)
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
2
Log A – Log Aref Loci of solutions with
equal residual error TR50 = 152oC
1
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
29
Modified from Burnham (1992)
2
Log A – Log Aref Loci of solutions with
equal residual error TR50 = 152oC
1
Log 2 = 0.3
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
30
Modified from Burnham (1992)
2
Log A – Log Aref Loci of solutions with
equal residual error TR50 = 152oC
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
Modified from Burnham (1992)
2
Log A – Log Aref Loci of solutions with
equal residual error TR50 = 152oC
1
0 TR50 = 132oC
-1 3oC/my
TR50 = 109oC
-2
8 -6 -4 -2 0 2 4 6 8 10
32
Modified from Burnham (1992)
1014/1012 = 100
Log2100 = 6.65 (i.e., A doubles 6.65 times)
6.65 x 3oC/my ~ 20oC error
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)
0.0
52 Global
-0.5 Source Rocks
-1.0
-1.5
-4 -3 -2 -1 0 1 2 3 4 5
Peters et al. (2015)
35 PetroMod Technology Days
Ea Mean (Single run – Multi Run)
Single- and Multi-Ramp Models Yield Different Temperatures
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
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
Peters et al. (2015)
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
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)
Technology Days
April 17-19, 2018
Aachen, Germany
Ken Peters
Geochemistry Advisor, Schlumberger
Adjunct Professor, Stanford BPSM
Aromatization Liberates Hydrogen and Increases Ro
Huminite or
Anthracite
Vitrinite
6H
Biomarker Guide, p. 91
Ordered Ro Values
5
Ro = 0.74 ± 0.05% for One Rock Sample
Frequency
Biomarker Guide, p. 90
Atomic H/C
3.0 CH4 Loss
Atomic H/C
1.5
2.0
Vitrinite
1.0
1.0
0.5
VITRIMAT elemental
balance equations and
reflectance correlations
0
0 40 50 60 70
Aurora-1
Well A Aurora-1
Well A
Easy%RoDL Easy%RoDL
Basin%Ro Basin%Ro
Easy%Ro Easy%Ro
Dogleg
Aurora-1
Well A Aurora-1
Well A
Easy%RoDL Easy%RoDL
Basin%Ro Basin%Ro
Easy%Ro Easy%Ro
Dogleg
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
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)
Relevant geological
pressures are <2 kbar!