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SLT Middle East
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2
SLT Middle East 2008
‘New Applications in Petroleum Geochemistry’
Dr. Peter Nederlof
Biography
• Peter Nederlof is Shell’s principal technical expert for geochemistry and responsible for a global skill-pool of some 60 petroleum geochemists. Peter has a Ph.D. in Chemistry from the University of Amsterdam and did a postdoctoral fellowship in Natural Product Chemistry at Stanford University in California. Peter joined Shell’s Fine Chemicals Research Group in Amsterdam in 1979 and moved ‘upstream’ to the Geochemistry Department of Exploration and Production in 1982. After 7 years in research, Peter worked as geochemical advisor in Canada, Oman and the United States, before returning to Shell International in early 2005. In the last three years, Peter has worked on projects in support of E&P ventures in North Africa and the Middle East.
• Peter served on the board of the European Association of OrganicGeochemists from 1991 to 1998 and was a member of the first editorial board of GeoArabia when it was launched in 1995. Peter and co-authors have received best paper awards from both the AAPG and SPWLA for their work on the Athel Formation in Oman
• Dr. Peter Nederlof is currently the Lecturer for EAGE’s Student Lecture Tour for the Middle East 2008 and will be covering the ‘New Applications in Petroleum Geochemistry’.
3
New Applications in Petroleum Geochemistry (Part I)
Peter NederlofPetroleum Geochemist with Shell International E&[email protected]
the Netherlands
New Orleans
Calgary
Stanford
Muscat
4
Contents
Part I Background - Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
Part II Introduction to Petroleum Geochemistry- Thermal Cracking of Source Rocks, Oil Typing and
Oil-to-Source Rock Correlation
Part III New Applications- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources
Carbon
• 4th most abundant chemical element in the universe (after H, He and O)
• unique property to bond with itself and form millions of hydrocarbon molecules
• occurs in all organic life and is the basis for organic chemistry
• molecular weight of 12 (6 protons, 6 neutrons, 6 electrons)
5
• unique property to bond with itself and form millions of hydrocarbon molecules
Gases: one to four carbon atoms
MethaneCH4
EthaneCH3CH3
n-ButaneCH3CH2CH2CH3
iso-Butane CH(CH3)3
HH C
H
H
H HC
H
C
H
H
H
C
H
H
H HC
H
H
C
H
H
C
H
H
H
C
H
H HC
H
H
C
C
H
HHH
H C
H
H
HC
H
H
C
H
H
PropaneCH3CH2CH3
CH3CH2
CH2CH2
CH2CH3
Liquids: Five to 40+ carbon atomsC
C C
C CC
H
H
HH
H HHexaneC6H12
BenzeneC6H6
CH3CH2
CH2CH2
CH2(CH)n2
Large molecules
• occurs in all organic life and is the basis for organic chemistry
C H S N O
Carbohydrates 44 6 0 0 50
Lignin 63 5 0.1 0.3 31.6
Proteins 53 7 1 17 22
Lipids 76 12 0 0 12
Petroleum 80 13 1 0.5 0.5
Elemental Composition
6
• Isotopes are atoms with the same number of protons, but different number of neutrons
• Two naturally occurring, stable isotopes: 12C (98.9%) and 13C (1.1%)• One naturally occurring, unstable isotope: 14C, (half life of 5730 y)
• 12C-12C and 12C-13C have different bond strength and (bio)chemical reactions therefore show carbon isotope fractionation
• Organic matter is depleted in 13C compared to carbon in carbonate rocks or CO2 in the atmosphere
CarbonIsotopes
6 protons + 7 neutrons
Carbon isotope abundances are expressed as the ratio of 13C to 12C isotopes in the sample compared to the same ratio in a standard.Because the differences in ratios are very small, they are expressed as parts per thousand or 'per mil' (‰) deviation from the standard
The standard is defined as 0‰. The international standard is ‘Pee Dee Belemnite’, a fossil collected from the banks of the Pee Dee River in South Carolina with a
13C/12C ratio of 0.0112372.Carbon compounds with ratios of 13C/12C > 0.00112372 have positive delta values, and those with ratios of 13C/12C < 0.00112372 have negative delta values.
δ13Csample = x 1000(13C/12C sample) - (13C/12C standard)
(13C/12C standard)
δ13C(delta C 13)
7
Isotopic composition of crude oils reflects their source rock
Kalash Fm.
Sirt Fm.
Rachmat Fm
Cretaceous/Nubian
Silurian Shales
Tertiary
Etel Fm.
-36 -34 -32 -30 -28 -26 -24 -22 -20-36 -34 -32 -30 -28 -26 -24 -22 -20
Isotopically “Light” Isotopically “Heavy”
Triassic
Source Rock from the SirteBasin in Libya have different carbon isotope ratios.
Oil can often be attributed tosource rock on the basis ofcarbon isotope ratios
The global scale exchange of carbon among its reservoirs, namely the atmosphere, oceans, vegetation, soils, and geologic deposits and
minerals.
www.climatechange.ca.gov
Carbon Cycle: Definition
8
Carbon Cycle – Schematic Diagram
www.physicalgeography.net
Carbon Cycle and Carbon Sink
‘C’Plant Life
CO2Atmosphere
Photosynthesis
DegradationRespiration
After John M. Hunt, Petroleum Geochemistry and Geology (1995)
Sediment Sink
and Sediment Sink
99.9 % 0.1 %
9
Deposition of Carbon over Geologic Time
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
600 500 400 300 200 100 0
TKC PP TR JO S DCPC
TKC PP TR JO S DCPC
Time (Ma)
Cum
. are
a of
SR
(‘00
0 km
2 )
Glaciations
Carbon Cycle: the Sediment Sink
‘C’Plant life
CO2Atmosphere
Photosynthesis
DegradationRespiration
Sediment Sink
0.02 %
99.98 %
10
Reduced Carbon Oxidized Carbon
Atmosphere 600Oceans
Surface water Biota 3DOC 700
Carbonate Carbon 39,000Geosphere
Land biota 610Soil and Detritus 1,560
Sediments 12,000,000 48,000,000
Carbon Reservoirs in Gt
Atmospheric CO2 (ppm) as a function of time (Ma)
CO2 levels during early Phanerozoic were 25 times current level (350 ppm)
11
Conclusion
- Most of the organic matter sits in the subsurface (and is depleted in 13C)
Question: how did it get there?
Source Rock Evaluation
(Petroleum Geochemistry)
“Petroleum Geochemistry is the application of chemical principles to the study of the
origin, migration, accumulation and alteration of oil and gas and the use of this knowledge in exploring for and recovering petroleum”
John M. Hunt, Petroleum Geochemistry and GeologyW.H. Freeman and Company (1996)
12
What does a petroleum geochemist do all day?
1. Try to understand the filling history of oil accumulations
2. Build models that explains oil fields in terms of(1) presence and maturity of source rock, (2) migration history(3) retention and alteration
3. Use the model to predict where more oil can be found and to optimize oil recovery from the field
Egypt: Abu Gharadig Basin - Stratigraphy
Abu Roash Source Rock
40% of oil reserves
60% of oil reserves
13
What is a source rock?
“A rock which contains sufficient organic matter to generate commercial quantities of hydrocarbons
upon reaching thermal maturity”
Hydrocarbons have a biological origin
• Oils and gases can be linked to specific source rocks by the presence of certain components and their isotopic signature.
• Chemical compounds within the source rock and produced hydrocarbons can be linked to molecules within living plants
14
Primary Sources of Organic Carbon in Sediments
• Phytoplankton• Zooplankton• Algae, bacteria etc.• Land plants
• Anything else that has ever lived < 1%< 1%
> 99%> 99%
Cairo Daily News July 30, 2008
Source Rock Deposition: Productivity and Preservation
Torbanite Algal Coal, Scotland Silurian ‘hot’ shale, Middle East
‘C’Plant life
CO2Atmosphere
Photosynthesis
DegradationRespiration
Sediment Sink
0.02 %Carbon Cycle
15
Areas of high primary productivity in the present day oceans
Primary productivity is only one control on source rock deposition
Primary Productivity
Sun
light
Nut
rient
s
Phy
topl
ankt
on
Zoop
lank
ton
January July December
Primary Productivity in Northern Hemisphere Inshore Waters
• Sunlight• Carbon Dioxide - Oxygen• Nutrients; N, P, Si, Fe, Ni, V, Zn, Cu
16
Algal blooms off the coast of Florida as a result of African dustNASA/Goddard Space Flight Center
Ceratium hirundinella, (Dinoflagellate)
River inputRiver input
Black Sea
Bosphorus
Sea ofMarmora
Preservation: bottom water euxinic conditions
The influx of fresh waters results in severe density stratification, which inhibits the mixing of the bottom waters with the surface waters. The dissolved oxygen is
removed from the water by the oxidation of organic matter. This leads to strong anoxia with dissolved H2S at depth.
17
Swamps LakesRiver input
Pro-deltaic shales
Low oxygen
stratification
Flux of terrigenousand marine OM
Swamps LakesRiver input
Pro-deltaic shales
Low oxygen
stratification
Flux of terrigenousand marine OM
River Input
Preservation: Pro-deltaic Shales
• Water column stratification• Bottom water anoxia
Restricted bottomwater circulation
Area of high productivityThermally stratified water column
Intra-basinal sagsCarbonate build-ups
Preservation: Carbonate Platforms
• Restricted Bottom water circulation• Low sedimentation rate
18
PN Si
OMZ
Cold nutricient rich waters
Area of high productivity
PN Si
OMZ
Cold nutricient rich waters
Area of high productivity
Offshore winds
Preservation: Upwelling
• Water column stratification• Oxygen minimum zone
Source rocks are not distributed equally in time
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
600 500 400 300 200 100 0
TKC PP TR JO S DCPC
TKC PP TR JO S DCPC
Time (Ma)
Cum
. are
a of
SR
(‘00
0 km
2 )
Glaciations
19
OMZ
high productivityshelf anoxia
strongly stratified water column
sluggish bottom water circulation
ice
dense oxygen rich btm water
less dense ‘warm’ surface watersPolar Region
Large difference in temperature between polesand equatorCompressed tropical and temperate climate
beltsIntense oceanic circulationUpwelling increasesOxygen rich bottom watersSea level drops - restricted basins common
Small difference in temperature between poles and equatorExpanded tropical and temperate climate beltsSluggish oceanic circulationUpwelling decreasesOxygen poor bottom watersSea level rises - anoxic shelves common
The “Greenhouse” World
The “Icehouse” World
example: Expanded Oxygen Minimum Zones
example: Oxygen Rich Bottom Waters
• Primary productivity• Water depth• Water Column Stratification• Redox state of the water column• Sedimentation rate
Source Rock Deposition: Productivity and Preservation
‘C’Plant life
CO2Atmosphere
Photosynthesis
DegradationRespiration
Sediment Sink
0.02 %Carbon Cycle
20
There is more to source rockanalysis than measuring TOC ...
Source Rock Analysis14,000
15,000
16,000
17,000
18,000
19,000
20,000
21,000
22,000
23,000
24,000
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
TOC wt%
S2 mgHC/g rock
TOC log for a well in the Gulf of Mexico
A complete source rock evaluation consists of:
TOC measurement ….. Richness
Rock Eval Analysis ….. Type and Maturity
Visual Kerogen Analysis ….. Contamination, Type, Maturity
Solvent Extraction ….. Type, Maturity
Petrophysical Log Evaluation . Thickness
SPI calculation ….. Charge volume estimate
Source Rock Kinetics ….. Conversion as a function of maturity
Compositional kinetics ….. Product Mix as a function of Maturity
….. and then there are complications like oil-based mud, mud additives, cuttings vs. core samples, picked samples vs. ‘raw ditch’, burnt-out source rocks,
carbonate vs. shale source rocks, differences between geochem labs …..
21
Generation Potential TOC in Shales (%) TOC in Carbonates (%)None 0.0 – 0.5 0.0 – 0.2Poor 0.5 – 1.0 0.2 – 0.5Fair 1.0 – 2.0 0.5 – 1.0
Good 2.0 – 5.0 1.0 – 2.0Excellent >5.0 >2.0
Total Organic Carbon (TOC): What makes a good source rock?
tem
pera
ture
time
Thermal extraction
Pyrolysis CO2 release
S1 S2S3
Trappingof CO2
Source Rock PyrolysisRock-Eval, PFID
S2 : is a good measure for source rockquality (at low maturities)
S2 > 5 mgHC/g rock is good SR
S1 : already generated HC + base oil contamination
S2 : remaining generative potential(mg HC/g rock)
Rock Eval Analysis
Tmax
22
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
3800
426 428 430 432 434 436 438 440 442 444 446 448Tmax (C)
Dep
th (m
)
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
3800
0 5 10 15 20 25TOC (% wt)
Dep
th (m)
Rock Eval S2
TOC
Source Rock Evaluation – SyriaTOC, Rock Eval S2 vs. Depth Rock Eval Tmax vs. Depth
Hydrogen Index (HI):100 * S2/TOC
Oxygen Index (OI):100 * S3/TOC
Tmax:Temperature at which S2
peaks (measure of maturity)
23
2200
2400
2600
2800
30000 5 10 15 20 25
TOC (%wt)
Dep
th (m)
Rock Eval S2
TOC
TOC and Rock Eval S2 vs. Depth
Source Rock Screening in Syria
0
10
20
30
40
0 1 2 3 4 5TOC
Rock
Eva
l S2
(mg
HC)
TOC vs. Rock Eval S2
HI = 770
38
51
74
Aliphatic C(%)
0.28
0.20
0.06
O/C
1.06
1.34
1.64
H/C
Phenol
Ester
Ether
Main functional
group
26,000Type III
26,000Type II
21,000Type I
MW(Dalton)
After Vandenbroucke(2003)
Kerogen Type and Molecular Composition
24
Type I Type II Type III
Kerogen Structures according to Behar et al.
Qusaiba Rock Eval Data – Saudi Arabiaafter Cole et al. Energy and Fuel (1994) pp 1425 - 1442
HI of 300
25
Visual Kerogen Analysis (VKA)
Microscopy with tungsten & UV light of polished whole rock samples
SR quality (maceral composition)
SR type (oil vs. gas)
Expulsion capacity
Environment of deposition
Maturity (Vitrinite Reflectance)
Visual Kerogen Analysis
Silurian, SyriaGood, post mature, Type II source rock (TOC-1.6%).
Photomicrograph, showing lenses of SOM associated with framboidal pyrite.
26
SPI = the mass of HC in metric tons that is generated at full maturity from a column of rock below 1 m2.
Every source rock evaluation should address
both quality and quantity
The SPI is a good measure of the source potential of a basin
Classification of “low” or “high” SPI depends on the size of the drainage area and hence on whether lateral or vertical migration is dominant
Influence of Drainage Area Size
27
Conclusions (Part I)
- Most of the organic matter sits in the subsurface (and is depleted in 13C)- Organic matter in the subsurface is concentrated in a wide variety source rocks
Next question:How are oil and gas generated from source rocks?
28
New Applications in Petroleum Geochemistry (Part II)
Contents
Part I Background - Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
Part II Introduction to Petroleum Geochemistry- Thermal Cracking of Source Rocks, Oil Characterisation,
Oil-to-Source Rock Correlation
Part III New Applications- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources
29
Hydrocarbon Generation and ExpulsionSource Rock Kinetics
The conversion of a source rock into oil and gas is governed by:
• Source rock thermal history:10% input uncertainty results in 10 - 40% output uncertainty
• Chemical kinetics of kerogen conversion:10% input uncertainty results in 20 - 50% output uncertainty
Kerogen conversion is a linear function of time and an exponential function of temperature. We model the conversion of kerogen to petroleum as a series of parallel first order reactions governed by the Arrhenius rate law.
Kerogen: the organic matter contained in source rocks Kinetics: a branch of chemistry which studies the relationship between rate of a reaction, the temperature
and the concentration of the reagents
Kerogen Petroleum
kk11
kk22
kk33
kknn
rate i = -dxi/dt = ki xirate i = -dxi/dt = ki xi
ki = Ai e -Ei / RTki = Ai e -Ei / RT
Xi = Concentration of kerogen component iKi = Rate constant (per sec) for reaction iAi = Frequency Factor (per sec) for reaction iEi = Activation Energy (KCal/mol) for reaction it = time (sec)T = Temperature
Arrhenius(Nobel laureate 1903)
30
The frequency factor (A) and activation energy (Ea) describe the kerogen response to temperature. Because kerogen is a complex mixtures of components with different kinetic properties, there is a distribution of activation energies.
Basin models commonly represent this distribution in one of three ways.
The distribution of Ea can be determined by laboratory measurements
Ea (kcal/mol)Kerogen Kinetics (1)1. Discrete Distribution of Ea
2. Gaussian about Ea Mean, σa
Ea mean
Ea start Ea end
3. Single start and end Ea
51 55 59 63 6751 55 59 63 6751 55 59 63 67
0.1
0.2
0.3
0.1
0.2
0.3
0.1
0.2
0.3
For a simple temperature history, a spreadsheet calculation produces curves of predicted source rock conversion vs. temperature.
Kerogen Kinetics (2)
Ea (kcal/mol)
Lacustrine Kerogen(Type I)
Coaly Kerogen (Type II/III)
Ea (kcal/mol)
58 59
65
120 140 160 180 200 220
0.2
0.4
0.6
0.8
1.0
120 140 160 180 200 220120 140 160 180 200 220
0.2
0.4
0.6
0.8
1.0
Temp (oC)
SR
Con
vers
ion
*5 oC/Ma
31
C15+ Sat
C6-14 SatC3-5
C2
C6-14 Aro
C15+ Aro
C15+ Sat
C6-14 SatC3-5
C2
C6-14 Aro
C15+ Aro
Predicted Product Mix from Shell’s GENEX5 modelling softwarePredicted Product Mix from Shell’s GENEX5 modelling software
Compositional KineticsResults from Laboratory and Mathematical Simulation
Laboratory Simulation(California Institute of Technology)
Laboratory Simulation(California Institute of Technology)
Mathematical Simulation(Shell)
Mathematical Simulation(Shell)
In Situ Conversion Process
Mahogany Research ProjectRio Blanco County, Colorado1400 bbl/d
32
90 °C
150 °C
Source Rock Burial History
Basin Modeling
Please remember: the model is only as good as its input material
33
Conclusions (Part II)
-Oil and gas are formed through the thermal cracking of kerogen, a processthat can be simulated in the lab and modeled accurately
Next question:Where does the generated oil go?
Tar Lake in Trinidad
34
Oil Analysis: Gas Chromatography
Oils can be separated into individualcomponents by gas chromatography
Some columns separate on boiling point,(molecular size), others on polarity.
Whole Oil Gas Chromatography: Source
Marine SRNorth Sea
Carbonate SROman
Algal SRThailand
Landplant SRFar East
35
Whole Oil Gas Chromatography: Maturity
Whole Oil Gas Chromatography: Biodegradation
10,000 ft 9,262 ft
8,120 ft
6,836 ft 9,262 ft8,120 ft
6,836 ft9,262 ft 10,000 ft
10,000 ft 9,262 ft
8,120 ft
6,836 ft 6,836 ft 9,262 ft8,120 ft8,120 ft
6,836 ft9,262 ft 10,000 ft
36
Molecular Fossils
Cholesterol
Cholestane
Oil Typing: Molecular Fossils
Hopanoids are the most abundant
natural chemicals on earth
37
Molecular Fossils are used foroil/source correlations
Egypt: Abu Gharadig Basin - Stratigraphy
Abu Roash Source Rock
Question:
Is there more than one oil source rock in the Abu Gharadig Basin, Egypt ?
38
BahariyaKharita
AlameinAlam El Bueib
MasajidKhatatba
Khoman B
Safa
BahariyaKharita
AlameinAlam El Bueib
MasajidKhatatba
Khoman B
Safa
BahariyaKharita
AlameinAlam El Bueib
MasajidKhatatba
Khoman B
Safa
Abu Gharadig Basin – Charge Concept
Abu Gharadig Basin – Seismic Section
BED 4-1
Source Rock
39
Badr El Din 4-1 n-Alkane CSIA low mature Abu Roash and highly mature Khatatba oils
-31.0
-30.0
-29.0
-28.0
-27.0
-26.0
-25.0
-24.0
-23.0
-22.0
-21.0
C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28
BED 4-1Kharita 3636mBED 4-1Kharita 3696mBED 4-1 AbuRoash 2946m
Low mature Abu Roash oil
Highly mature Khatatba oil
C27
C27
C17
C17
-31.0
-30.0
-29.0
-28.0
-27.0
-26.0
-25.0
-24.0
-23.0
-22.0
-21.0
C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28
BED 4-1Kharita 3636mBED 4-1Kharita 3696mBED 4-1 AbuRoash 2946m
Low mature Abu Roash oil
Highly mature Khatatba oil
C27C27
C27C27
C17C17
C17C17
C29
C28
C29C28C27
C27
Molecular Fossils: Sterane Distributions
BED 4-1Abu Roash-F Oil
2946 m
BED 4-1Kharita Oil
3636 m
C27 Sterane
C28 Sterane
C29 Sterane
40
BED 4-1Abu Roash-F oil
2946 m
BED 4-1Kharita oil
3636 m
Diahopane
24/4
C30
C30
C29
C29
Tm
Ts
TmTs24/4
Molecular Fossils: Triterpane Distributions
Egypt: Abu Gharadig Basin - Stratigraphy
Abu Roash Source Rock
Answer:
There are 2, may-be even 3 source rocks in the Jurassic Khatatba Fm.
Khatatba Source Rocks
41
Conclusions (Part II)
- Oil and gas are formed through the thermal cracking of kerogen, a processthat can be simulated in the lab and modeled accurately
- Petroleum Geochemistry can help identify new opportunities for oil and gas Exploration by mapping the hydrocarbon habitat of a sedimentary basin
42
New Applications in Petroleum Geochemistry (Part III)
Contents
Part I Background- Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
Part II Introduction to Petroleum Geochemistry- Thermal Cracking of Source Rocks, Oil Characterisation,
Oil-to-Source Rock Correlation
Part III New Applications- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources
43
New Directions in Petroleum Geochemistry1. Analytical equipment is moving to the well-site: real-time operational geochemistry
2. More powerful analytical instrumentation: dry hole analysis
3. Unconventional resources: different analytical programs
1. Operational Geochemistry
Mud Gas Logging
Mud Circulation System:
1. to cool the drill bit2. to control the pressure3. to remove drill cuttings and gas
released during drilling
44
LoggingWhile
Drilling
Mud Gas Logging: Gas Extraction
45
Advanced Mud Logging: Reserval and Flex Flair (1)
2. Quantitative Gas ExtractionConstant PVT conditions
Correction for ‘gas in’Analysis by Mass Spectrometry
(Geoservices Flex Flair)
Intake Probe
1. Qualitative Gas ExtractionConstant Volume Gas ExtractorAnalysis by Gas Chromatography(Geoservices Reserval)
3. Mudgas sampling program for carbon isotope analysis
Probe in flow line
Fluid Extractor - out
Sampling configuration at Seraj well
Advanced Mud Logging: Reserval and Flex Flair (2)
46
Data transmission system: Real time lithology, MWD,Mud gas compositions from any PC with internet access
Advanced Mud Logging: Reserval and Flex Flair (3)
Component FLEX FLAIR MDTMethane 78.5 76.1
Ethane 9.0 10.0Propane 5.5 6.6
i-Butane 1.2 1.2 n-Butane 2.5 2.9
i-Pentane 1.3 1.1 n-Pentane 1.3 1.2
GOR 1650 1605API 31 29.7
Viscosity 0.55 0.47
Advanced Mud Logging: Reserval and Flex Flair (4)
47
23000
23050
23100
23150
23200
23250
23300
23350
23400
23450
235000 3000 6000 9000 12000 15000
GOR predicted from Flex Flair
Continuous Fluid Logging in the Gulf of MexicoYellow Reservoir Prospect P.
Accuracy: Example from GoM well O.
48
Methane Carbon Isotope vs. Depth
Biogenic Thermal
10,000
12,000
14,000
16,000
18,000
20,000
22,000
24,000
26,000
-75.0 -65.0 -55.0 -45.0 -35.0
TT
KK
JU
S
MT
LK?
Methane Carbon Isotope vs. Depth
Biogenic Thermal
M16.5
Salt
7,000
8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
16,000
17,000
18,000
19,000
20,000
21,000
22,000
23,000
24,000
25,000
26,000
27,000
-75.0 -65.0 -55.0 -45.0 -35.075.0 -65.0 -55.0 -45.0 -35.0
49
Methane Carbon Isotope vs. Depth
Biogenic Thermal
7,000
8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
16,000
17,000
18,000
19,000
20,000
21,000
22,000
23,000
24,000
25,000
-75.0 -65.0 -55.0 -45.0 -35.0
A
BC
Prospect S (GoM): dry hole
Any evidence of charge? Up-dip potential? Sidetrack? PA/TA?
50
Prospect S (GoM): dry hole
Any evidence of charge? Up-dip potential? Sidetrack? PA/TA?
Fluid Inclusion Screening
Present-day formation fluids, trapped/adsorbed in the sediments. May not be actual fluid inclusions
Trapped fluids liberated by mechanical crushing
Released volatiles analysed by mass spectrometry
Migration pathways: Methane, Ethane, Paraffin, “C-3 plus” Naphthene
Proximity to Pay: Methane, H2S, CO2, Benzene, Toluene, Acetic Acid
51
Fluid Inclusion Screening: Proximity to Pay indicators (PTP)
Conclusions (Part III)
- There is new high-tech mud logging technology, which allows the evaluation of hydrocarbon charge systems, provide information on migration style, and can ‘sense’ nearby oil accumulations
52
2. Dry Hole Analysis
Looking for evidence of hydrocarbons in dry holes
FF27-6
D1-137
S13-6
L1-NC41L1-137
K1-NC41
K1-NC35A
J1-NC41
J1-NC35A
H1-NC41
H1-87
F1-NC41
E5-16
E1-NC41
E1-NC35A
D2-NC41
C1-NC41
C1-NC35A
C1-NC129
A1A-NC87C1-137
D1-88
A1-89
A1-88
A1-87
B3-NC41B1-NC87
A1-NC173
A1-NC146
A1-NC12A1-NC120
A2-137
A1-NC42
B1-NC41
B1-NC120
E1-87
nformation:979_UTM_Zone_34Nion: Transverse_MercatorEasting: 500000.0Northing: 0.0_Meridian: 21.0Factor: 0.9996e_Of_Origin: 0.0
xploration & Production Libya GmbH
Geochemical Well EvaluationsOffshore Libya
53
Potential Source Rocks
SilurianTannezuft Equivalent Marine Shales
Upper CretaceousSirte/Rachmat Shales/Etel? Marine shales
EoceneMarine shales (Boudabous)
FF27-6
D1-137
S13-6
L1-NC41L1-137
K1-NC41
K1-NC35A
J1-NC41
J1-NC35A
H1-NC41
H1-87
F1-NC41
E5-16
E1-NC41
E1-NC35A
D2-NC41
C1-NC41
C1-NC35A
C1-NC129
A1A-NC87C1-137
D1-88
A1-89
A1-88
A1-87
B3-NC41B1-NC87
A1-NC173
A1-NC146
A1-NC12A1-NC120
A2-137
A1-NC42
B1-NC41
B1-NC120
E1-87
nformation:979_UTM_Zone_34Nion: Transverse_MercatorEasting: 500000.0Northing: 0.0_Meridian: 21.0Factor: 0.9996e_Of_Origin: 0.0
xploration & Production Libya GmbH
• exploration wildcat, drilled in 1985• targeted basal carbonates of the Lower Eocene• all reservoir sections water bearing • no significant hydrocarbon shows• plugged and abandoned
• exploration wildcat, drilled in 1985• targeted basal carbonates of the Lower Eocene• all reservoir sections water bearing • no significant hydrocarbon shows• plugged and abandoned
54
Fluid Inclusion Screening
Output from FIT, Tulsa
Methane:CH3+ (m/e 15)
Ethane: C2H5+ (m/e 29)
Benzene:C6H5+ (m/e 78)
Cycloalkanes: C7H13+ (m/e 97)
Whole Extract GC
9270 - 9580 ft
9940 – 10,140 ft
10,400 – 10,750 ft
12,000 - TD
4 6 0 0
5 6 0 0
6 6 0 0
7 6 0 0
8 6 0 0
9 6 0 0
1 0 6 0 0
1 1 6 0 0
10600
11600
55
-33.0
-32.0
-31.0
-30.0
-29.0
-28.0
-27.0
-26.0
-25.0
-24.0
-23.0
C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33
Extract Analysis – (9,270 – 9,580 ft)
32 35Ts
24T
Terpanes27
28
29Steranes
30
22
17
Whole Extract GC n-alkane CSIA
Compound Specific Isotope Analysis (CSIA)
-60.0
-55.0
-50.0
-45.0
-40.0
-35.0
-30.0
-25.0
-20.0
-15.0C1 C2 C3 iC4 nC4 iC5 nC5
Micro-show analysis
• evidence for presence of micro-shows
• good match with Silurian sourced gases
gases of Silurian origingases of Silurian origin
1 gram
56
-55
-50
-45
-40
-35
-30
-25
-20C1 C2 C3 iC4 nC4 iC5 nC5
Compound Specific Isotope Analysis (CSIA)
Compound Specific Isotope Analysis (CSIA)
57
Conclusions (Part III)
-There is new high-tech mud logging technology, which allows the evaluation of hydrocarbon charge systems, provide information on migration style and can ‘sense’ nearby oil accumulations
- Developments in analytical chemistry have made it possible to identify ‘micro-shows’ in cuttings from wells that were drilled many years ago.
3. Unconventional Resources
Shale Gas
58
Discovered Recoverable (Gboe) per yearBinned by 3 Years periods and Volume classes
21430 Datapoints
0
20
40
60
80
100
120
1918
. 192
1
1921
. 192
4
1924
. 192
7
1927
. 193
0
1930
. 193
3
1933
. 193
6
1936
. 193
9
1939
. 194
2
1942
. 194
5
1945
. 194
8
1948
. 195
1
1951
. 195
4
1954
. 195
7
1957
. 196
0
1960
. 196
3
1963
. 196
6
1966
. 196
9
1969
. 197
2
1972
. 197
5
1975
. 197
8
1978
. 198
1
1981
. 198
4
1984
. 198
7
1987
. 199
0
1990
. 199
3
1993
. 199
6
1996
. 199
9
1999
. 200
2
2002
. 200
5
Discovery Year Periods
Dis
cove
rd R
ecov
erab
le V
olum
es (G
boe/
Year
)
> 500 MMBoe400 . 500 MMBoe300 . 400 MMBoe200 . 300 MMBoe100 . 200 MMBoe0 . 100 MMBoe
Conventional Oil and Gas discovered per year 1918-2006
1. Global energy demand is accelerating- Energy essential for economic growth and social development- Developing economies enter energy intensive phase- XOM: +30% by 2020, RDS: +100% 2050
2. Conventional resources will struggle to keep up with demand- HC’s provide 80% of global energy supply- Renewables will play increasing role, but will be unable to meet demand- Shift towards unconventionals: shale gas, heavy oil, tar sands
3. Increased coal use will cause higher CO2 emissions, possibly to levels we deem unacceptable- share of coal is set to grow (widespread geographic availability)- unless steps are taken to manage CO2 , emissions will continue to increase
The Energy World is Changing …
59
Migration losses
Sub-economictraps
Seepage tosurface
Expulsionlosses
Amount trapped
Amount generated
Petroleum Systems Inefficiencies
Fractured Shale Play, Continental US
60
Gas Production from Fractured Shales is not new …
Self-Sourced Reservoir
Organic-Rich Shale (TOC = 4-6 wt%)
Complex Lithology
Low Porosity (ave. 3-8%)
Low Perm (Generally <0.01μd)
Barnett Shale
61
BarnettMississippian Type II SR
Fractured Barnett Shale Gas (Ft Worth Basin, Texas)27 TCF Natural Gas Resource
wet
62
Barnett Production Sweet Spot
For Type I, II and III KerogensConversion
0
0.2
0.4
0.6
0.8
1.0
0.4 0.6 1.2 2.0Maturity (VRE)
Source Rock Conversion vs. Maturity1. Generation
2. Retention
3. Producibility1. Generation
2. Retention
3. Producibility
63
Shale Gas Evaluation Criteria (Jarvie)
Unconventional Resources: Phase Behaviour
Production of an adsorbed gas from a surface area follows different physical laws that production of gas from the pore space.
0
500
1000
1500
2000
2500
3000
3500
4000
-100 0 100 200 300 400 500 600T (F)
P (p
sia)
CalcDataCalc (cut Pdp - C16+)
Gas + Liquid(Saturated Wet Gas)
ResvP&T
0
500
1000
1500
2000
2500
3000
3500
4000
-100 0 100 200 300 400 500 600T (F)
P (p
sia)
CalcDataCalc (cut Pdp - C16+)
Gas + Liquid(Saturated Wet Gas)
ResvP&T
Conventional PVT properties are irrelevant?
64
adsorbent
a) Physical adsorption (van der Waals)
b) Chemical adsorption (chemisorption)
All gases tend to adsorb to solid surfacesbelow their critical P/T point
adsorbate
Gas adsorption on shales
1. Generation
2. Retention
3. Producibility 1. Generation
2. Retention
3. Producibility
0
20
40
60
80
100
0 1000 2000 3000 4000
Pressure (psi)
Sorp
tion
Cap
acity
(scf
/ton)
T =145 FT =175 F
Langmuir IsothermsBarnett Shale
65
Langmuir Adsorption Isotherm
bPbP
sat +=
1θθ
bPbPVV sat +
=1
q = fractional coverageqsat = saturated fractional coverageb = Langmuir parameterR = 10.73 psi ft3/lbmol/°RH = heat of adsorption (kJ/mol)
⎟⎠⎞
⎜⎝⎛=RTHbb exp0
Gas forms a film on the solid substrate
Barnett vs. Antrim Langmuir Isotherms
0
20
40
60
80
0 1000 2000 3000 4000
Reservoir Pressu re (psia)
Sorp
tion
Cap
acity
(scf
/ton)
Barnett Shale (TOC =4.00wt%)
Antrim Shale (TOC=7.8wt%)
0
20
40
60
80
0 1000 2000 3000 4000
Reservoir Pressu re (psia)
Sorp
tion
Cap
acity
(scf
/ton)
Barnett Shale (TOC =4.00wt%)
Antrim Shale (TOC=7.8wt%)
66
Are there any other selection criteria?Burial History of Barnett Shale in Wise County, Texas
“Though the core area is commonly referred to as Denton, Wise and Tarrant counties, the true sweet spot has been the Newark East Field, which has been extensively drilled.
Results outside Newark East have not been as impressive. However, another sweetspot appears to be developing in Johnson County, which looks superior to much of the ‘core’ acreage beyond Newark East.”
Inside a ‘sweet-spot’, well productivity depends on completion 1. Generation
2. Retention
3. Producibility 1. Generation
2. Retention
3. Producibility
67
Conclusions (Part III)
-There is new high-tech mud logging technology, which allows the evaluation of hydrocarbon charge systems, provide information on migration style and can ‘sense’ nearby oil accumulations
-Developments in analytical chemistry have made it possible to identify ‘micro-shows’ in cuttings from wells that were drilled many years ago.
-Development of Unconventional Resources will require entirely new tools and new capabilities and unconventional screening methods
68
Acknowledgments
Andy Bell (Shell)Johan Buiskool Toxopeus (Shell)
Andrew Murray (Woodside)
Shannon de Groot (EAGE)
Thank you for your attention
Questions, Comments? [email protected]
69
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