Geoqumica de Crudos

CONCEPTOS GENERALES Y APROXIMACION A LOS CASOS COLOMBIANOS

Geoqumica de Crudos

EVALUACION PRELIMINAR
Definicin

Origen y Ocurrencia

Caracterizacin preliminar de los crudos Colombianos

Hiptesis de los procesos de Origen

Geoqumica de Crudos

Hidrocarburos
Resinas Asfaltenos

Petrleo: Producto natural compuesto principalmente de hidrocarburos

Geoqumica de Crudos
Definiciones

Crudo Pesado:

Frecuentemente no producible por tcnicas convencionales 10-12 hasta 20 API 100-10 000 centipoises
Crudo Extrapesado

No tiene movilidad a condiciones de reservorio No puede ser producido por tcnicas convencionales <10-12 API; >10.000 centipoises a condiciones de yacimiento

Geoqumica de Crudos
107

106

VISCOSIDAD A 50 c = 122 F (cP)

105

CRUDOS EXTRA-PESADOS (Arenas Bituminosas) R + A = ca.50% o ms

104

CRUDOS PESADOS R + A = ca.25-40%

103

CRUDOS NORMALES R + A 20%

102

10 25 20 15 10 5

Geoqumica de Crudos

EVALUACION PRELIMINAR
Definicin

Origen y Ocurrencia

Caracterizacin preliminar de los pesados Colombianos

Hiptesis de los procesos de Origen

N-C11

N-C12

N-C13

N-C14 N-C15 N-C16 Pristano Fitano N-C17 N-C18 N-C19 N-C20 N-C21 N-C22 N-C23 N-C24 N-C25 N-C26 N-C27 N-C28 N-C29 N-C30 N-C31 N-C32 N-C33 N-C34 N-C35

Geoqumica de Crudos

LOS LLANOS ARAUCA 1

Geoqumica de Crudos

OILS - TYPE III SOURCE

GC
10

13

20

25 30

PT

35

30

TERPANES (m/z 191)

29

STERANES (m/z 217)

C29 (ZOR) C27 (ZOR) C29 (ZOR)

19-3

24-4 23-3

T2

Geoqumica de Crudos

OILS - TYPE I SOURCE

GC
15

10

20
PT

25

30

TERPANES (m/z 191)

33 G 29

STERANES (m/z 217)

C27 (ZOR)

C29 (ZOR)

C29 (ZOR)

23-3 24-4 T2

Geoqumica de Crudos

OILS - TYPE II SOURCE

GC
10

13 20
PT

25

30

35

TERPANES (m/z 191)

29 30

STERANES (m/z 217)

C29 (ZOR)

C27 (ZOR)

C29 (ZOR)

23-3

T2 24-4

19-3

Geoqumica de Crudos
ALTERATION OF PETROLEUM IN RESERVOIRS

Depth

Water Washing Accumulated Oil Biodegradation Processes

Bailey, 1973

Original Oil 18 - 27 API less than 1.5 % Sulfur

GAS
API Gravity

Alteration

Source

Carbonate - Evaporite Source

Clastic Source Continental Marine

Geoqumica de Crudos
GEOCHEMICAL CORRELATION
Depositional environment

Reservoir Processes

Oil - Oil Correlation

Oil - Source Correlation

Source rock non available

Geoqumica de Crudos
MAIN FACTORS INFLUENCING OIL COMPOSITION

SOURCE ROCK CHARACTER Kerogen Type Depo. Environ. Maturity

PRIMARY MIGRATION Timing of generation & migration

SECONDARY MIGRATION Pathway Character: (Distance, Lithology, OM, Fluids)

R E S E R V O I R E D

TEMPERATURE (Thermal cracking)

WATER FLOW & BACTERIA (Water washing & biodegradation)

PRESSURE / FAULTING (Phase segregation)

SEAL EFFICIENCY (Leakage)

RESERVOIR / SEAL CHARACTER & CONDITIONS P&P, Mixing, PVT

O I L

GAS INFLUX (Gas deasphalting)

Geoqumica de Crudos
0

2 (0.6)

Depth,103 ft(m)

4 (1.2)

6 (1.8)

8 (2.4)

10 (3.0)

12 (3.6) 10 20 30 40 50 60 From Hunt 1979

Oil Gravity, API

Geoqumica de Crudos
DRECREASE IN THE PERCENTAGE OF COMMERCIAL OIL FIELDS VERSUS GAS FIELD WITH DEPTH AND THE CORRESPONDING INCREASE IN API GRAVITY
0

1 ---(4)

OIL
Depth, Km (10 ft)

2 ---(8)

3 ---GAS
(12)

4 ----

5 ----

(16)

6 ---0 25 50 75 100 0 20 40 60
Percenten of total fields produccing oil and gas Oil gravity, API

Geoqumica de Crudos
HETEROGENEITY OF OIL CHARACTER WITHIN A FIELD
Samaan Field, Trinidad
2,000

4,000

6,000

8,000

10,000

14,000
Class 1: 40 API Lighter HC Class 2: 32 API Normal HC Class 3: 33 API Waxy HC Class 4: 20 API Biodegraded HC

TRINIDAD

12,000

15 Miles

SAMAAN FLIED

Geoqumica de Crudos
RECOGNIZING UNTAPPED ACCUMULATION

SW

Tiger Shoal Field, Offshore GOM

NE
3.0

Toluene / n-Heptane

-10,000

2.5

Oil A
2.0

Condensate A

1.5

-11,000

1.0

Undiscovered OilB? Condensate B

0.5
-12,000

0.0 0.0 0.5 1.0 1.5 n-Heptane / Methylcyclohexane 2.0

?
-13,000

Geoqumica de Crudos
CAMBIOS EN LAS PROPIEDADES DEL PETROLEO BIODEGRADADO

Decremento en:

Gas Hmedo (C2 - C6) con Propano, selectivamente atacado El rango Gasolina - Kerosene (C6 - C15) Gravedad API (incremento en densidad) Todas las parafinas, contenidos de ceras y pou point GOR

Incremento en:

Compuestos asflticos (NSOS y Asfaltenos) Contenido de Azufre y Nitrgeno Viscosidad Contenido de Vanadio y Nquel

Geoqumica de Crudos
EXPERIMENTAL BIODEGRADATION OF NIGER DELTA OIL

C15

12 UA DAY 1 NO DEGRADATION
PRISTANE
PHYTANE

DAY 32 SLIGHTLY DEGRADED

C15
PRISTANE
PHYTANE

C20 C25

C20 C25

C30

C30

DAY 55 MODERATELY DEGRADED

PRISTANE PHYTANE PRISTANE PHYTANE

DAY 124 HIGHLY DEGRADED

(Sassen 1977)

Geoqumica de Crudos
EXAMPLES OF BIODEGRADATION EFFECTS IN NORTH APOI OILS
C15

4LA NO DEGRADATION 7360 196 F

C20
PHYTANE

PRISTANE

C15

11LA SLIGHTLY DEGRADADED 2520 161 F

C25

PHYTANE

C20 C25 C30

C30

PRISTANE

9LA MODERATELY DEGRADADED 4880 155 F

11LA HIGHLY DEGRADADED 4500 149 F

PHYTANE PRISTANE PHYTANE

(Sassen 1977)

Geoqumica de Crudos
BIODEGRADED HIGH PRAIRIE OIL VS UNALTERED STOUGHTON OIL

Geoqumica de Crudos
HYDROCARBON STABILITY ZONES

GTC (F/100) 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9

Temp (F) @30,000 580 550 520 490 460 430 400 370 340 310

Temp (F) @25,000 490 465 440 415 390 365 340 315 290 265

Temp (F) @20,000 400 380 360 340 320 300 280 260 240 220

Temp (F) @15,000 310 295 280 265 250 235 220 205 190 175

Temp (F) @10,000 220 210 200 190 180 170 160 150 140 130

Conditions where oils have been thermally cracked to gas Conditions where oils are undergonig thermal cracking Optimum conditions for oils perservation Conditions where oil biodegradation is possible

Geoqumica de Crudos
PROPERTY API gravity Metal Content Sulfur <C15 Content Gas/Oil Ratio C15+ Composition Pristane / nC17 Phytane / nC18 Carbon isotope C15/C16 Bicyclic Alkanes Rearranged C15 Bicyclics Terpanes Steranes Triaromatic Steranes Methylphenanthrenes WATER WASHING decrease decrease decrease decrease decrease decrease aromatics increase increase lighter NSO increase increase relative diterpane decrease relative C27 decrease relative increase in C20 & C21 relative phenanthrene decrease BIODEGRADATION decrease increase increase decrease decrease decrease saturates increase increase heavier sat, light asph increase decrease relative deterpane increase if severe decrease if severe relative increase in C20 & C21 DEASPHALTING decrease increase increase decrease decrease increase aspaltenes unchanged unchanged lighter aromatic unchanged unchanged unchanged unchanged unchanged relative phenanthrene increase MATURATION increase decrease decrease increase increase decrease NSO and asphaltenes decrease decrease heavier asphaltene FRACTIONATION (Residual) decrease increase increase decrease decrease decrease sat & increase aro & asph decrease unchanged unchanged

increase
increase relative diterpane increase unchanged relative increase C20&C21 relative phenanthrene decrease decrease C27 relative decrease C20 & C21 relative phenanthrene decrease

relative phenanthrene increse

Sources:

Bailey et al. (1973), Seifert & Moldowan (1978, 1979), Stahi (1980), Volkman et al (1983); Mackenzie (1984), Radke etal (1986) Dahi & Speers (1986), Williams et al (1986), Kennicult (1988), Lafargue & Barker (1988), Kuo (1994), Later & Mills (1990), Thompson (1987,1988), unpublished Texaco Data

Geoqumica de Crudos
PREDICTING API GRAVITY

50

40

API Gravity

30

20

10

0
Temperature of Maximum Vaporization (S1 Tmax) S1 / S2 of Bitumen S1 (mg HC / g Bitumen )

(Baskin & Jones, 1993)

Geoqumica de Crudos

EVALUACION PRELIMINAR
Definicin

Origen y Ocurrencia

Caracterizacin preliminar de los crudos Colombianos

Hiptesis de los procesos de Origen

N-C11

N-C12

N-C13

N-C14 N-C15 N-C16 Pristano Fitano N-C17 N-C18 N-C19 N-C20 N-C21 N-C22 N-C23 N-C24 N-C25 N-C26 N-C27 N-C28 N-C29 N-C30 N-C31 N-C32 N-C33 N-C34 N-C35

Geoqumica de Crudos

LOS LLANOS ARAUCA 1

Geoqumica de Crudos
DISTRIBUCIN DE LOS COMPONENTES MAYORITARIOS EN LAS CUENCAS LLANOS, YAR CAGUN, PUTUMAYO Y VMM.
CRUDOS PESADOS PROMEDIO MUNDIAL

16,1
0% 10% 20%

30,4
30% 40% 50% 60%

53,5
70% 80% 90% 100%

% AROMATICOS 100 10 90

Crudos Normales Crudos Pe sados Cuenca Llanos

20

CRUDOS NORMALES PROMEDIO MUNDIAL

57,2
0% 10% 20% 30% 40% 50% 60%

28,6
70% 80%

14,2
90% 100%

80 30

Cuenca YarCaguan Cuenca Putumayo Cuenca VMM

40

CRUDOS PESADOS - CUENCA LLANOS

70

38,15
0% 10% 20% 30% 40%

33,68
50% 60% 70%

28,18

60
80% 90% 100%

u u u u u u u u uu uu u u u u u u uu uu u u u u u

CRUDOS PESADOS - CUENCA PUTUMAYO

50

50

60

42,05

24,50

33,45

40
100%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

70

CUENCA V ALLE MEDIO DEL MAGDALENA (VMM)

30

80

32,58
0% 10% 20% 30% 40%

39,61
50% 60% 70%

27,81
80% 90% 100%

20

CRUDOS NORMALES (Promedio Mundial)

10
CUENCA YARI - CAGUAN

CRUDOS PESADOS (Promedio Mundial)

90

100 60 50 40 30 20 10

23,56
0% 10% 20%

28,36
30% 40% 50% 60%

48,08

100
70% 80% 90% 100%

90

80

70

% SATURADOS
% SATURADOS % AROMTICOS % RESINAS + ASFALTENOS

% RES.+ ASFALTENOS

Abundance

Geoqumica de Crudos to 191.90): 04200076.D Ion 191.20 (190.90

Geoqumica de Crudos

Geoqumica de Crudos
CROMATOGRAMAS DE GASES. CUENCA LLANOS.

CHICHIMENE-2

EL MIEDO-1

CASTILLA-14

Geoqumica de Crudos

EVALUACION PRELIMINAR
Definicin

Origen y Ocurrencia

Caracterizacin preliminar de los crudos Colombianos

Hiptesis de los procesos de Origen

Geoqumica de Crudos
COMPOSICIN ISOTPICA DE LOS CRUDOS.
-24 .0 0

ALM-1

-25 .0 0

GLORN-1 VAL-1

Terrestre
c 13 Arom atic o s

GLORN-1a STGO-6

CHIC HI-1 6

-26 .0 0

API-1 6 CHICHI-2 ENTR-1 GLOR-1b SV-2 GLOR-1c

RUB-12 LIN-3

CAST-1

CAST-7 APIE-1 CASTN-2 GUAT-1a BON-15 GALN-9 GALN-10 SANT-5 8 GAV-1

Marino

GALN-3 -27 .0 0 MIE- 4 STALUC -1

CUENCAS
LLANOS PUT UMAYO VMM

VELAS-2 24 TECA-164D TEC A-10 1 CANTG-6 ANGL-1 42 -5c COCOR-46 TOTU-4 CAIP-1 PAV-1 CANEG-1

-28 .0 0 -2 9 -2 8 -2 7 -2 6 -2 5

c 13 /c 12 Sa turad o s

Linkage Distanc e
0,0 0,2 0,4 0,6 0,8 1,0

Geoqumica de Crudos

DIAGRAMA DE AGRUPAMIENTO A PARTIR DE LOS RESULTADOS BSICOS

YARI VMM1 VMM2 LLANOS1 LLANOS2

MANADERO 4.16 MANADERO 3.5 MANADERO 2.24 MANADERO 4.8 COCORNA-46 ECA- 164D T LOS ANGELES-142a PAVAS-1 ECA-101 T LINDA-3 T CAS ILLA-7 ANT S A LUCIA-1 CAIPAL-1 T CAS ILLA-1a ANT S OS-58 BONANZA-15 GALAN-9 GALAN-3 VELASQIEZ-224 ABE-1 CAS OT T UMAL-4 GALAN-10 AGALLO-6 CANT IQUIA-1 GUAT ANT S IAGO-6 RUBIALES-12 LA GLORIA-1b LA GLORIA-1c E-1 LA GLORIA NORT E-1a LA GLORIA NORT LGLON-1 RERRIOS-1 ENT CHICHIMENE-2 VALDIVIA-1 EL MIEDO-4 CAO NEGRO-1 ALMAGRO-1

Linkage Distanc e

Geoqumica de Crudos

DIAGRAMA DE AGRUPAMIENTO A PARTIR DE RESULTADOS DE BIOMARCADORES

YARI LLANOS LLANOS 1 VMM 2 VMM 1

MANADERO-224 MANADERO-415 MANADERO-48 MANADERO-42 MANADERO-439 MANADERO-418 COCORNA-46 CHICHIMENE-16 T CAS ILLA-23 E-2 T CAS ILLA NORT T CAS ILLA-2 T CAS ILLA-13 APIAY-16 MANADERO-35 T APIAY ES E-1 RUBIALES-12 RUBIALES-1 RUBIALES-1a ANT S IAGO-6 LA G1ORIA-1 LA GLORIA-1A E-1 LA GLORIA NORT RERRIOS-1 ENT CAO NEGR0-1 QUEZ-224 VELAS GALAN-9 ABE-1 CAS GALAN-3 GALAN-10 CAIPAL-1 EL MIEDO-4 IQUIA-1 GUAT ECA 164d T T CAS ILLA-7 ECA-101 T ANT -58 S OS BONANZA-15 ANT S A LUCIA-1 PAVAS -1 OT T UMAL-4 LINDA-3 CHICHIMENE-2 VALDIVIA-1 ALMAGRO-1

Geoqumica de Crudos
PROCESOS DE ALTERACIN CON BASE EN INFORMACIN CROMATOGRFICA
nm en ts (T Mi ) ra xe ns d iti O o n rg al an i En c S vi o u ro r c nm es en t)

1 0. 0 0
Te rr es tr e

En

ic

vi

ro

CASTN-2 CAST-23

CAST-7 CAST-13

a in ar M g) a n i c ci n du rg Re O ia l er a at lg M (A

rg

ia

er

at

ac i

CAST-2

(P

Re
CHIC HI-1 6

ea

t-

M ad ur

du

oa

cc

i n

GLOR-1b

Ox

i da

ci

n
LIN-3 CANEG-1 CANTG-2 6 CANTG-6 YARI-5 7 d PAV-1

VELAS-224 APIE-1

Prista no/nC17

GLORN-1a 1 .0 0 CAST-7 CHICHI-2 API-1 6 VAL-1 ALM-1 GUAT-1 a GAV-1 STGO-6

UM B- 1

PEB-3 MIE- 4

TOTU-4 STALUC -1

i n

de gr ad ac

CUENCAS
LLANOS PUT UMAYO VMM

0 .1 0 0 .10 1.0 0 Prista no/nC18 10.00

Bi o

Geoqumica de Crudos