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Application of Equation of State Based Methods to Correct

for Oil Based Drilling Fluid Contamination in Condensates


and Near Critical Systems

John Ratulowski
Shell Exploration and Production Technology Company
Houston TX
Outline

• Sources of Error in Fluid Property Measurement


• Development of EOS models for OBM
Contaminants
• Dead Oil Data
• Live Oil Data
• A Field Example for a Condensate
• Conclusions
Sources of Error from Downhole
Samples
• Sampling
– Phase splits due to drawdown
– Contamination
• Transfer and Handling
– Leaks
– Lack of equilibration
• Laboratory Analysis
– Poor technique
– Lack of equilibration
– Quantification of contamination
Philosophy of the EOS Approach

• The chemistry of the contaminants is better known than that


of the oil
• Develop contaminant EOS description based on the known
structure, physical properties, and available VLE data.
– Actual compounds in the contaminant
– Model compounds structurally similar
– Pseudo-components with fixed properties
• Tune oil pseudo-component properties to match measured
VLE data of the contaminated system
• This approach reduces the number of adjustable parameters
Petrofree (Not Petrofree LE)

Five fatty acid esters with carbon


numbers 16 to 24 and an ethyl side Ester Boiling Points
chain 450

400

Boiling points extrapolated from 350

Normal BP C
known values 300

250
Group contribution techniques used to 200

estimate EOS parameters 150

100
Viscosity model fit to data from 10 C 50
4 6 8 10 12 14 16 18 20 22 24
to 65 C Number of Carbons
Branched Straight Chain
Methane BIP’s fit to gas solubility data
Petrofree EOS Model Results
Petrofree Density Petrofree Viscosity
0.9 Atmospheric Pressure
12

10
0.85
8
gm/cc

Viscosity cp
6
0.8
4

2
0.75
0 2000 4000 6000 8000 10000 0
Pressure psia 0 20 40 60 80 100
T Celcius
75 F 150 F 300 F
Model Data

Methane Solubility in Petrofree


1500
GOR SCF/BBL

1000

500

0
1000 2000 3000 4000 5000 6000
Pressure psia

100 F 300 F
Escaid Mineral Oil

Refined product with low aromatic


content C11 to C15 on SimDist analysis SimDist of Escaid Mineral Oil
100

In-house ECHO correlation used to


generate pseudo-component properties
This was sufficient to match stock tank

wt %
10
density
Viscosity model to data between 4 C
and 38 C 1
5 10 15 20
Methane BIP correlation fit to gas Carbon Number

solubility data for mineral oils


EOS Results for Escaid

Escaid Viscosity Methane Solubility in Escaid


Avg Error 2.6% 2500

3
2000

2.5

SCF/BBL
1500
Viscosity cp

2 1000

1.5 500

1 0
40 50 60 70 80 90 100 2000 3000 4000 5000 6000 7000 8000
Temperature F Pressure psia

EOS Model Measured 100 F 200 F 300 F 250 F


Low Molecular Weight Olefins

Novaplus, Petrofree LE, IsoTeq, and


Ultidrill are all compositionally similar
C14, C16, and C18 alpha or internal
olefins. They may be branched or linear
and may consist of single compounds or
groups of isomers
C14, C16, C18 alpha olefins are used as
model compounds
Literature data used to develop EOS
description
Methane BIP correlation fit to gas
solubility data
EOS Results for the Olefins

Methane Solubility in
Novaplus at 200 F
8000

6000

Pressure psia
IsoTeq Viscosity
4000
Avg Error 0.09%
Measured
7
2000

6
0
Viscosity cp

5 0 500 1000 1500 2000 2500 3000


GOR SCF/BBL
4

3
Methane Solubility in
2 Novaplus at 250 F
40 50 60 70 80
Temperature F 8000

EOS Model Measured


6000

Pressure psia
4000

Measured
2000

0
0 500 1000 1500 2000 2500 3000
GOR SCF/BBL
Other Contaminant Models

• Aquamul
– C20 alkyl ether
– Approach similar to Petrofree esters
– Limited success matching gas solubility data
• Novasol
– Alpha-olefin isomers groups one near C20 the other near C30
– Normal paraffins n-C30 and n-C40
– Viscosity, density, and gas solubility matched adequately
Density of Dead Oil Blends

IsoTeq/Oil API Gravity


50

•Linear mixing rule for API gravity. 45

API Gravity
40
•Variability in base fluid properties
35
caused some error in the Petrofree trace 30

•Aquamul and Novasol results similar 25


0 20 40 60 80 100
Mass % Contaminant

Measured EOS Model

Escaid/Oil API Gravity Petrofree/Oil API Gravity

50 35

45 34

API Gravity
API Gravity

40 33

35 32

30 31

25 30
0 20 40 60 80 100 0 20 40 60 80 100
Mass % Contaminant Mass % Contaminant

Measured EOS Model Measured EOS Model


Viscosity of Dead Oil Blends
Petrofree/Oil Viscosity
•Two oils of different gravity Avg Error 3.2% All Points
30

•Temperature range from 40 to 100 F 25

Viscosity cp
•Contamination range from 5 to 60 wt % 20

15
•Novasol 3.7 % average error
10
0 10 20 30 40 50 60
•Aquamul 2.7 % average error Mass % Contaminant

EOS Model Measured

Escaid/Oil Viscosity IsoTeq/Oil Viscosity


Avg Error 6.3% All Points Avg Error 4.1% All Points
30 30

25 25
20

Viscosity cp
Viscosity cp

20
15
15
10

5 10

0 5
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Mass % Contaminant Mass % Contaminant

EOS Model Measured EOS Model Measured


GOM Black Oil

• The oil was a black oil with a GOR of approximately


1200 SCF/BBL and a stock tank gravity of 27 API
Gravity
• CCE’s at 130 F and 163 F run with 0, 5, and 10 wt %
basis dead oil of three contaminates
• Results presented as deviations uncontaminated-
contaminated
• Poor quality GOR data
• In general, model and experiments compared favorably
EOS Results for the Black Oil (Live Oil)
Escaid Contaminated Black Oil Escaid Contaminated Black Oil
Live Oil Viscosity 7000 psia 162 F
1400
0.03
1200
0.02
1000
Delta Psat psia

Delta Viscosity cp
0.01
800
0
600
-0.01
400
-0.02
200
-0.03
0
-0.04
0 2 4 6 8 10 0 2 4 6 8 10
Wt % Escaid Wt % Escaid
Measured 163 F EOS Model 163 F
Measured 130 F EOS Model 130 F Measured EOS Model

Petrofree Contaminated Black Oi Petrofree Contaminated Black Oil


Live Oil Viscosity 7000 psia 162 F
1200
0
1000
-0.02
Delta Psat psia

Delta Viscosity cp
800
-0.04
600
-0.06
400
-0.08
200
-0.1
0
-0.12
0 2 4 6 8 10
0 2 4 6 8 10
Wt % Escaid
Wt % Escaid
Measured 163 F EOS Model 163 F
Measured 130 F EOS Model 130 F Measured EOS Model
EOS Results for the Black Oil (Flash Data)
Black Oil Flash GOR ESCAID Petrofre Contaminated Black Oil

1350 0

1300 -0.2

-0.4
GOR SCF/BBL

1250

Delta API
-0.6
1200
-0.8
1150
-1
1100 -1.2

1050 -1.4
0 2 4 6 8 10 0 2 4 6 8 10
Mass % Contaminant Wt % Escaid

Measured EOS Model Measured EOS Model

Black Oil Flash GOR Petrofree Escaid Contaminated Black Oil


1450 0

1400
-0.5
1350
GOR SCF/BBL

Delta API
-1
1300

1250 -1.5
1200
-2
1150

1100 -2.5
0 2 4 6 8 10 0 2 4 6 8 10
Mass % Contaminant Wt % Escaid

Measured EOS Model Measured EOS Model


• Volatile oil with a 1950 SCF/BBL GOR and 33.8 API tank
gravity
• Mixture of Novasol contaminated and uncontaminated
samples available from several wells and zones
• Question: How confident are we in our corrected PVT data
from the contaminated samples?
• Minimal PVT rum for three contamination levels up
to 10 %
EOS Results for a Volatile GOM Oil
Flash GOR Oil Formation Volume Factor
1.9
2000

1900 1.85
GOR SCF/BBL

Bo RB/STB
1800
1.8

1700
1.75
1600

1500 1.7
0 5 10 15 20 0 5 10 15 20
% NOVSOL % NOVSOL

Measured EOS Model Measured EOS Model

Saturation Pressure Flash API GRavity


5300 36.5

36
5200

35.5
Psat psia

5100

API
35
5000
34.5

4900
34

4800 33.5
0 5 10 15 20 0 5 10 15 20
% NOVSOL % NOVSOL

Measured EOS Model Measured EOS Model


Near Critical Gas Condensate

•Near critical gas condensate 2300


SCF/BBL or 435 BBL/MMSCF Phase Envelope

12000
•31 API stock tank oil (condensate) Reservoir

11000
•Retrograde behavior at 130 F and 180 F

Pressure psia
confirmed in four experiments at two 10000

laboratories 9000
Critical Point

•Uncontaminated sample available from 8000

first well drilled in water base mud


7000
0 100 200 300 400 500 600
•Question: Would even small amounts of Temperature F
Novaplus contamination effect the phase
behavior?
EOS Results for GOM Near Critical Fluid

GOM Near Critical Fluid 180 F CCE GOM Near Critical Fluid 130 F CCE
Phase Diagram Phase Diagram
1 0.05 1 0.03

0.8 0.04 0.8


Vol Frac Upper Liq

Vol Frac Lower Liq

Vol Frac Upper Liq

Vol Frac Lower Liq


0.02
0.6 0.03 0.6

0.4 0.02 0.4


0.01
0.2 0.01 0.2

0 0 0 0
5000 6000 7000 8000 9000 10000 4000 5000 6000 7000 8000 9000 10000
Pressure psia Pressure psia
Expt. Uncontaminated Expt.5 wt % Novaplus
EOS Uncontaminated EOS 5 wt% Novaplus Uncontaminated 5 wt % Novaplus
• Single stage flash CGR of 37.8 BBL/MMSCF with a tank gravity of
48.4 API
• Same three contaminants as black oil study
• Two different EOS characterizations were used. Results of the models
are sensitive to the detail of EOS characterization
• Reasonably good agreement for flash data between experiment and
model
• Contaminant-gas binary interaction parameters should be fit in the
retrograde region for accurate prediction of saturation pressure
EOS results for the Lean Condensate
(Live Oil Data)
Escaid Condensate Dewpoint 160 F Escaid Condensate Live Oil Density
9000 psia 163 F
250
0
200 -0.002

Delta Density gm/cc


Delta Psat psia

150 -0.004

100 -0.006

-0.008
50
-0.01
0
0 5 10 15 20 25 -0.012
Mass % Contaminant 0 5 10 15 20 25
Mass % Contaminant

Measured 25 Component 3 Component Measured 25 Component 3 Component

Petrofree Condensate Dewpoint 160 F Petrofree Condensate Live Oil Density


9000 psia 163 F
200
0
0

Delta Density gm/cc


Delta Psat psia

-0.005
-200

-400 -0.01

-600 -0.015

-800
0 5 10 15 20 25 -0.02
Mass % Contaminant 0 5 10 15 20 25
Mass % Contaminant

Measured 25 Component 3 Component Measured 25 Component 3 Component


EOS Results for the Lean Condensate
(Flash Data)
Escaid Condensate LGR Escaid Condensate Flash Gravity
0 0.16

-2 0.14
Delta LGR BBL/MMSCF

0.12
-4
0.1

Delta API
-6
0.08
-8
0.06
-10
0.04
-12 0.02
-14 0
0 5 10 15 20 25 0 5 10 15 20 25
Mass % Contaminant Mass % Contaminant

Measured 25 Component 3 Component Measured 25 Component 3 Component

Petrofree Condensate LGR Petrofree Condensate Flash Gravity


0 4
Delta LGR BBL/MMSCF

-2
3

Delta API Gravity


-4

-6 2

-8
1
-10

-12 0
0 5 10 15 20 25 0 5 10 15 20 25
Mass % Contaminant Mass % Contaminant

Measured 25 Component 3 Component Measured 25 Component 3 Component


Field Case: Lean Condensate

• Small samples of dead contaminated condensate were


available (about 33 wt % of Petrofree LE)
• No mud filtrate - uncertainties in mud EOS
characterization and in the estimated contamination level
• PVT available on contaminated samples
• The measured saturation pressure is the same as the bottom
hole pressure for the contaminated sample
Results of EOS Correction

Contam inated Corrected M easured

4-Stage Separator 55 40 32
LGR BBL/M M SCF
Potential Problems 4-Satge Separator
API Gravity
50 49 47

Density at reservoir 0.2963 0.2947 0.2832


1. Sample handling and transfer conditions gm/cc

2. Problems in the lab


3. Problems with the EOS model Liquid Fallout Curves
4. Areal and vertical variation in fluid
10
properties in the reservoir 9
8 Contaminated
7 Uncontaminated

% PV Liquid
6
5
4
3
2
1
0
0 2000 4000 6000 8000
Pressure psia
Summary

• EOS models for oil based mud contaminants were constructed using
chemical, physical, and VLE data from the base fluids
• These models do a reasonable job of correcting black and volatile oil
data
• Condensates are difficult to correct. The contaminant model should be
fit to the retrograde region for accurate correction of dew points
• In practice, many things can cause differences between data measured
on bottom-hole samples and production data these include:
– Sample handling and transfer
– Problems in the lab
– Problems with the EOS model
– Areal and vertical variation in fluid properties in the reservoir

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