3D PETROLEUM SYSTEM MODELLING

INTEGRATED ANALYTICAL TECHNIQUES

FOR A

GEOCHEMICAL STUDY

1
Fig.1

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Sometime, conventional geochemical techniques

(GC, GC-MS and Isotopes) cannot be enough to
completely describe the “genetical” features of
oil samples.

Consequently, only limited information on their

origin and maturity can be extracted from the
classical data set based on such techniques.

An example is reported in the next slides where a

case of a well with four oils levels is presented.
2
Fig.2

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Example

A case study of an exploration well

The aim of a classical geochemical study performed

on oil samples is to define the oil origin and
maturity.

Moreover, if necessary, hydraulic continuity (both

lateral and vertical) from different oil levels can
be object of the study too.

3
Fig.3

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Oils characterization

Data set

Sample Date Bottle Pressure Chamber Depth Sample Volume Destination

no. no. barg no. m nature cc
4,02 06/09/2002 PT 1183 120 MRSC 187 1773,5 Oil 410 Agip Milan MDT run4
2,04 04/09/2002 TS 11214 90 MPSR 1045 1790,5 Oil 230 Agip Milan MDT run2
2,01 04/09/2002 PT 2067 120 MPSR 988 1712,3 Oil 410 Agip Milan MDT run2
1,01 03/09/2002 TS10910 120 MRMS 1049 1865,6 Oil 420 Agip Milan MDT run1

4
Fig.4

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Oils characterization – Classical Analytical

Procedures

- MPLC fractionations in SAT, ARO, RES and ASF (preparative)

- GCMS analysis of SAT and ARO fractions (origin and maturity)

- Carbon Isotopic analysis of SAT, ARO, RES and ASF fractions

(origin)
- GC-Fingerprint of whole oils (hydraulic communications in the
reservoir)

5
Fig.5

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 GC-MS
3D PETROLEUM analysis
SYSTEM MODELLING
1712.3 m (PT2067)
Abundance
1790.5 m (TS11214)
Abundance
TIC: 7955HCS.D
2000000
TIC: 7957HCS.D
1800000
1800000
1600000
1600000
1400000
1400000
1200000
1200000
1000000
1000000
800000
800000
600000
600000
400000
400000
200000
200000
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Time--> 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Abundance Abundance

Time-->
Ion 191.20 (190.90 to 191.90): 7955HCS.D Ion 191.20 (190.90 to 191.90): 7954HCS.D
190000 95000

180000 90000

170000 85000

160000 80000

150000 75000

140000 70000

130000 65000

120000 60000

110000 55000

100000 50000

90000 45000

80000 40000

70000 35000

60000 30000

50000 25000

40000 20000

30000 15000

20000 10000

10000 5000

0 0
25.00 30.00 35.00 40.00 45.00 50.00 55.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00

1773.5 m (PT1183)
Time--> Time-->

1856.6 m (TS10910)
Abundance Abundance

TIC: 7954HCS.D TIC: 7956HCS.D

2000000
1800000
1800000
1600000
1600000
1400000
1400000
1200000
1200000
1000000
1000000
800000
800000
600000
600000
400000
400000
200000 200000

10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Time-->
Abundance Time-->
Abundance

Ion 191.20 (190.90 to 191.90): 7954HCS.D

Ion 191.20 (190.90 to 191.90): 7957HCS.D
95000

90000 80000

85000 75000

80000 70000

75000
65000
70000
60000
65000
55000
60000
50000
55000

45000
50000

45000 40000

6
40000 35000

35000 30000

30000
25000
25000
20000
20000
15000
15000

Fig.6
10000
10000

5000
5000

0 0
25.00 30.00 35.00 40.00 45.00 50.00 55.00 30.00 35.00 40.00 45.00 50.00 55.00
Time--> Time-->

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Oils Isotopic Characterization
-24,00

-25,00
Carbon Isotopic Ratio (Sat. v s. Aro.)

-26,00

-27,00
δ C ARO.

-28,00 1773,50
1865,60
-27,00
13

1712,30
-29,00
1790,50
Carbon Isotopic Ratios in Oil Fractions Legend:
-30,00
-27,50 1 = Saturates
2= Aromatics
AROM. 3= NSO
-31,00
-28,00 4= Asphaltenes
ASPH

δ C
-32,00

13
SAT.
-32,00 -31,00 -30,00 -29,00 -28,00 -27,00 -26,00 -25,00 -24,00
-28,50
13
δ C SAT

-29,00 NSO

1773,50
-29,50 1712,30
1865,60
1790,50

-30,00
1 2 3 4

Carbon Stable Isotopes Analysis shows homogeneous

results which indicates a common origin
(i.e. same organic matter and source rock) 7
Fig.7

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GC-MS and Isotopic analyses

Conclusions

Based on GC-MS and Isotopic analyses, all the oils are

similar one to each others and belong from the same source
rock.

The oils appears to be generated by a marine carbonate

source rock deposed in a anoxic depositional environment.

Maturity can be located in the first part of the oil window

(Ro eq. about 0.8-0.9%).
8
Fig.8

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GC-Fingerprint analysis

A/B
3.5
o/p C/D
3
* * * * * H I E R A R C H I C A L C L U S T E R A N A L Y S I S * * * * * *
k/l 2.5 G/H

2
Dendrogram using Average Linkage (Between Groups)
1.5
Rescaled Distance Cluster Combine i/j I/J
1
1712.3
C A S E 0 5 10 15 20 25 0.5 1773.5 QC
Label Num +---------+---------+---------+---------+---------+ 1773.5
0
1790.5 QC
g/h K/L 1790.5
1773.5 QC 2
1865.6
1773.5 3
1712.3 1
1790.5 QC 4 a/b M/N

1790.5 5
1865.6 6
Y/Z Q/R

U/V S/T

Apparently, there are three vertically separated

levels in the studied well
9
Fig.9

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This is what can be said on the case under examination if only

conventional techniques for the oil characterization are applied.

In the following, results of some “less conventional” techniques

applied to the oils (Light Hydrocarbons, Asphaltenes Tmax,
Phenols and GC-MS-MS), with the aim to go deeper in the oil
characterization, are shown.

10
Fig.
10
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Oils characterization – Unconventional

Analytical procedures

-Light Hydrocarbons analysis of whole oils (origin and maturity)

- Phenols analysis of oils (migration)

- Asphaltene Tmax analysis (maturity)

- GC-MS-MS of saturates for specific age related biomarkers

investigation (constrain the age of the source)

11
Fig.
11
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 Light Hydrocarbons
3D PETROLEUM SYSTEM MODELLING

Thompson Diagram Ctemp

60.0000
0.1200

Supermature

50.0000 0.1100 1790.5 m QC

1865.6 m
1790.5 m

q/t (2,2-DMP+3,3-DMP/3-EP+2,3-DMP+2,4-DMP)
0.1000
40.0000
Heptane value

Aliphatic curve
0.0900
1773.5 m QC
30.0000
Mature 1773.5 m
1712.3 m
1865.6 m
0.0800
Normal 1790.5 m1773.5
1773.5
QC m
1712.3m
mQC
Aromatic curve
20.0000

Biodegraded 0.0700

10.0000
0.0600

0.0000 0.0500
0.0000 0.5000 1.0000 1.5000 2.0000 2.5000 3.0000 3.5000 4.0000 4.5000 5.0000 105.0 107.0 109.0 111.0 113.0 115.0 117.0 119.0 121.0 123.0 125.0
Isoheptane value Ctemp (2,4/2,3-DMP)

Mango Parameters Mango Parameters

100000 250000

1790.5 m
90000 1790.5 m
1790.5 m QC
1790.5 m QC 1773.5 m
80000 200000
1773.5 m 1865.6 m
1865.6 m

70000
1773.5 m QC
1773.5 m QC
1712.3 m
60000 150000
1712.3 m
P3

50000

40000
P2 100000

30000

12
20000
50000

10000

0
0
0 50000 100000 150000
P2+N2
200000 250000 300000 350000
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 Fig.
0.9 0.95 1
N2/P3
12
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Light Hydrocarbons

- there are two groups of oils whose are different for both
maturity and “kitchen” of the source rock;

- not necessarily this means that there are two different

sources in terms of age and/or organic matter faces.

13
Fig.
13
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Phenols and Asphaltenes Tmax analyses

Asphaltene T max was determined on two oil samples, each one

representative of the two “groups” highlighted by the Light hydrocarbons
analysis. Both the oils show exactly the same T max! 440°C …. and,
consequently, the same maturity!

Similarly, Phenols analysis was performed on the same samples. The

results, expressed as Migration Molecular Index (MMI) are: 1.12 and 2.13.
Indicating two different migration pathways from the sources to the
reservoirs.

14
Fig.
14
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GC-MS-MS of saturates

Taking into account the age of the possible sources as well the
stratigraphic sequence of the study area, some specific age-
related biomarkers were investigated. In particular, because
Triaromatic Dinosteroids were proved to be absent in samples
coming from Permian sources while they were found in
hydrocarbons extracted from sources younger than Permian
and older than Carboniferous, particular attention was focused
in searching for these compounds.
15
Fig.
15
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GC-MS-MS of saturates
2a & 3b-Methyl-24-EthylSteranes
4a-Methyl-24-EthylSteranes
DINOSTERANES
Devonian Oil

Studied Oil

16
Fig.
16
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Consequently, the fact that no Triaromatic

Dinosteroids were detected in the oils, was used as an
indication that Permian-Carboniferous sources should
be considered as the most suitable candidates to the
generation of the oils themselves.

17
Fig.
17
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Oil characterization
Conclusions
A main oil family was recognized to be responsible for the four
studied oils.

A mature, marine carbonate source rock, probably Permian-Upper

Carboniferous in age, is the most suitable source.

Nevertheless, some small but significant differences, both in

terms of maturity and source rock dependent parameters, between
the two shallower oils and the deeper ones were highlighted.

Two hypothesis can be suggested to explain these differences

.....................................................................

Fig.
18
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Oil characterization
a) there is a single source rock in terms of age and organic matter
as suggested by biomarkers and isotopes, but physically
separated into two different kitchens (source dependent light
HC’s and Phenols), one more deep and more mature than the
other (maturity dependent Light HC’s);

b) there are two different source rocks, one younger and less
mature (mainly responsible for asphaltenes Tmax, isotopic and
biomarker data) and another one, older, deep seated and very
mature (depleted in biomarkers and asphaltenes). This second
source has generated a light oil which has mixed with the
former one modifying drastically its light HC’s fraction and
introducing all the elements of diversity discussed before.
Depending on the mixing between the two oils, it is also
possible to explain the differences in maturity between the
shallower and the deeper oils.
18
Fig.
19
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Oil characterization

Considering the two hypothesis already proposed about

the origin of the oils, the Permian-Carboniferous
sequence should be considered as the only single
source but separated into two different kitchens at
slightly different maturity (hypothesis a) or, at least,
the younger co-source in case of a multiple source
origin (hypothesis b).
19
Fig.
20
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When available rock samples can be used for a

source rock evaluation study aimed to select
samples suitable to perform a “direct” oil-source
rock correlation

20
Fig.
21
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Source rock evaluation

Exploration & Production CASPIAN SEA - BLOCK XI - 5a

Division
WELL: KALAMKAS 1
GEOCHEMICAL LOG

Stratigraphy TOC S2 HI TMAX Ro

700 700 700 700 700
P F G VG P F G VG III II I IMM M VM IMM M V M

900 900 900 900 900

CRETACEOUS
LOWER

1100 1100 1100 1100 1100

1300 1300 1300 1300 1300

UPPER
JURASSIC
Depth (m)

1500 1500 1500 1500 1500

1700 1700 1700 1700 1700

MIDDLE
JURASSIC
1900 1900 1900 1900 1900

2100 2100 2100 2100 2100

L. JURASSIC
TRIASSIC
ASSELIAN
ASSELIAN (Carb.)
2300 2300 2300 2300 2300
CARBONIFEROUS Indigenous Vitrinite
Vitrinite "B"
T.D. 2360 Serie1 Serie1 Serie1
Caved Vitrinite
Serie1
Oxidated Vitrinite
2500

21
2500 2500 2500 2500
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0.0 1.0 2.0 3.0 4.0 5.0 400 420 440 460 480 500 0.1 0,55 1.0 1,35 10.0
0 200 400 600 800 1000
(%) (kg HC/ton of rock) (mg HC/g TOC) (°C) (%)

LEGEND
(P= Poor F= Fair G= Good VG= Very Good ) ( III= Type III II= Type II I= Type I ) (IMM= Immature M= Mature VM= Very Mature) MARCH 2003

Fig.
22
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 3D PETROLEUM SYSTEM MODELLING
S2 vs T.O.C. HI vs Tmax
100.0
Very Poor Poor Fair Good Very Good 1000
immature oil zone gas zone
Ro 0,5
Type I

Very Good
800
10.0

MATURITY PROFILE
Petroleum Potential (Kg Hc/Ton of Rock)

LOWER CRETACEOUS
4,

HYDROGEN INDEX (mgHC/g TOC)

UPPER JURASSIC
0 0

Good
600 MIDDLE JURASSIC QUATERNARY-
2,0 Type II LOWER JURASSIC Indigenous Vitrinite - TERTIARY

Fair
TRIASSIC
1.0 PERMIAN (ASSELIAN) Vitrinite "B"

Poor
PERMIAN (ASSELIAN Carbonates)

UPPER CRETACEOUS
0,5 CARBONIFEROUS Caved Vitrinite
400
Oxidated Vitrinite
500

Very Poor
LOWER CRETACEOUS
0.1
UPPER JURASSIC
MIDDLE JURASSIC Ro 1,35
200 ?
LOWER JURASSIC
Type III

LOWER CRETACEOUS
TRIASSIC
PERMIAN (ASSELIAN)
PERMIAN (ASSELIAN Carbonates) 1000
CARBONIFEROUS

Depth (m)
0.0
0
0.0 0.1 0,2 0,5 1.0 2,0 10.0 100.0
380 400 420 440 460 480 500 520
Total Organic Carbon (T.O.C. %)
HI vs OI Tmax (°C)
1000

Type I
UPPER
1500 JURASSIC

800

MIDDLE
JURASSIC
HYDROGEN INDEX (mgHC/g TOC)

Type II
600 2000

L. JURASSIC
LOWER CRETACEOUS
TRIASSIC
ASSELIAN
UPPER JURASSIC ASSELIAN (Carb.)
CARBONIFEROUS
MIDDLE JURASSIC
400
LOWER JURASSIC T.D. 2360
TRIASSIC
2500
PERMIAN (ASSELIAN)
0.1 0,55 1 1,35 2 10
PERMIAN (ASSELIAN Carbonates)
CARBONIFEROUS Ro%
200

22
Type III

0
0 100 200

OXYGEN INDEX (mg Co2 /g. T.O.C.)

300 400
Fig.
23
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Hydrocarbons were extracted from all the source

rock intervals identified in the source rock study.

The best oil-source rock correlation was obtained

with Permian extracts as shown by the next slide

23
Fig.
24
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DIRECT OIL-SOURCE ROCK CORRELATION
Abundance
Abundance
TIC: 8137TQ.D
550000
TIC: 7956HCS.D
2000000

HC’s Extracted from 1856.6 m (TS10910)

500000

1800000
450000

1600000

Permian source
400000

1400000
350000

1200000
300000
1000000
250000
800000
200000
600000
150000
400000
100000
200000
50000

10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Abundance
10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 Time-->
Time-->
Abundance Ion 191.20 (190.90 to 191.90): 7956HCS.D

Ion 191.20 (190.90 to 191.90): 8137TQ.D

100000
14000

13000 90000
12000
80000
11000

10000 70000

9000
60000
8000

7000 50000

6000
40000
5000
30000
4000

3000 20000
2000
10000
1000

0 0
35.00 40.00 45.00 50.00 55.00 60.00 65.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Time-->
Abundance Abundance
Time-->

Ion 217.20 (216.90 to 217.90): 7956HCS.D

Ion 217.20 (216.90 to 217.90): 8137TQ.D 40000
8000
35000
7000
30000
6000
5000 25000

4000 20000

3000 15000
2000 10000
1000 5000
0 0
42.00 43.00 44.00 45.00 46.00 47.00 48.00 49.00 50.00 51.00 52.00 53.00 33.00 34.00 35.00 36.00 37.00 38.00 39.00 40.00 41.00 42.00 43.00
Time--> Time-->
Abundance Abundance

Ion 218.20 (217.90 to 218.90): 7956HCS.D

Ion 218.20 (217.90 to 218.90): 8137TQ.D 40000
8000
35000
7000

24
6000 30000

5000 25000

4000 20000

3000 15000
2000 10000
1000 5000

Fig.
0 0
42.00 43.00 44.00 45.00 46.00 47.00 48.00 49.00 50.00 51.00 52.00 53.00 33.00 34.00 35.00 36.00 37.00 38.00 39.00 40.00 41.00 42.00 43.00
Time--> Time-->

25
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