Format Presentation NExT2010Day 2 - ADx

Flow Assurance
Ahmed Dahroug
Schlumberger Flow Assurance
Copyright ©2009 NExT. All rights reserved

Solids Characterization & Modeling
Characterization methodologies
Asphaltenes
Wax
Hydrate
Emulsions
Scales
Mercury
Soaps
Sands
2 AJ
11/4/2010
Production Assurance Domains
Production Chemistry Production Engineering Production Surveillance

Prediction, prevention and/or Thermal-hydraulic design and Production optimization and
remediation of flow stoppages assessment of subsea early detection of flow
multiphase flow systems stoppages
3 AJ
11/4/2010
Production Chemistry
Mercury
Athabasca Asphaltene
Bitumen ρ>1
Wax
Diamondoids
Gas
Hydrate
4 AJ
11/4/2010
Organic Scale
Asphaltene Definition
Insoluble in Alkenes: Pentane, Hexane, Heptane.
Soluble in Aromatic Solvents: Benzene, Toluene, Xylene.
Semi crystalline solid particles of black or maroon color.
Undefined melting point.
High polar molecular weight in the range of 500 to 1,000
gr/grmol. Average: 750 gr/grmole (Mullins)
Typical components:
─ Carbon (80-85%)
─ Hydrogen (7-9%)
─ Also Oxygen (0.3-5%), S (0.3-10%), N (0.5-3.5%),
plus traces of Nickel, Iron and Vanadium
5 AJ
11/4/2010
Asphaltenes: Polymer or Monomer?
(size counts! e.g. ethylene vs polyethylene)
Asphaltene Molecules either…

OR... Polymer
Monomer
Many ‘Fused’ rings
6 AJ
11/4/2010
Effect of Pressure on Molar Volume Fraction
Partial molar volumes increase Partial molar volumes increase

dramatically as pressure is lowered slightly as pressure is lowered
C1-C4 C7+
Pres
Oil
Pressure
Liquid
Saturation
Psat
Curve
Vapor + Liquid
Temperature
7 AJ
11/4/2010
Partial Molar Volume for Live Oil Components
Peng-Robinson EOS l
1.35
Normalized partial molar volume
1.3
Methane
1.25 Propane
Pentane
1.2
C7-C12
1.15
1.1
1.05
1
400 500 600 700 800 900 1000
Pressure bar
8 AJ
11/4/2010
Experimental Facts
The definition of “Asphaltene” is somewhat

arbitrary (Speight et al. 1984; Hammami et al.
1995)
Stock-Tank-Oil is an effective asphaltene solvent

(Jamaluddin & Fuhr, 1996)
Increasing the Concentration of Resins in North

Sea Dead Oil Yielded Higher “Asphaltene”
Stability (Hammami et al. 1997)
9 AJ
11/4/2010
Asphaltene Precipitation Using Different n-Alkanes
Whole STO
STO STO STO STO STO
+ + + + +
C2 C3 n-C4 n-C5 n-C6
A2 A3 A4 A5 A6
“Asphaltenes”
10 AJ
11/4/2010
North Sea Precipitated “Asphaltenes”:
Effect Of Solvent Chain Length
4.8
Precipitated Asphaltene wt %
3.2
1.6
0
C2 C3 nC4 nC5 nC6
Paraffinic Titrant
11 AJ
11/4/2010
Effects of Resins on “Asphaltenes” Stability
Whole STO
STO STO
Saturates Aromatics Resins Asphaltenes
+
+
+
12 AJ
11/4/2010
Effects of Resins on “Asphaltenes” Stability
66
Vol Precipitant at ""Asphaltene" Onset
63
Wt % nn-C5
60
Original Oil Composition
57
54
0 5 10 15 20 25
Wt % Resin in North Sea Dead Oil
13 AJ
11/4/2010
Field Observations: North Sea & Kuwait
(de Boer et al., 1995)
Crudes with no Crudes with

or few problems severe Problems
Dead Oils
Saturates ≤ 62 wt % ≥ 75 wt %
Aromatics ≥ 26 wt % ≤ 22 wt %
Resins > 11 wt % < 4 wt %
Asphaltenes > 3 wt % ≤ 1 wt %
14 AJ
11/4/2010
Asphaltene Characterization Workflow
S
Instability Assessment
SARA Screening
Instability (De Boer plot)
Detailed assessment N
Thermodynamic Precipitation H
Particle Size & Kinetics
Deposition
Modeling
Thermodynamic Precipitation
Deposition (??)
15 AJ
11/4/2010
Topping - Crude Oil Distillation
Water out
Condenser
Left unboiled
residue
Cooling
water in
HOT PLATE
T1 = 200°C 200>300 °C IBP 200°C

T2 = 340 °C cut cut
16 AJ
11/4/2010
Packed Column For SAP Separation
Feed:
1. Sample + C5/C7
(Aromatics)
Alumina
2. Medium Polar Solvent
3. Strong Polar Solvent
(Polars)
Effluent:
Silica
1. Saturates
2. Aromatics
3. Polars/Resins
17 AJ
11/4/2010
SARA Separation
WHOLE
DEAD OIL
IBP -200 °C 200-340 °C >340 °C

14.2 WT % 26.7 WT% 59.1 WT%
PARAFFINS
NAPHTHENES
AROMATICS
SATURATES AROMATICS POLARS

70.3 WT% 25.7 WT% 4.0 WT%
GC/M
S
SATURATES AROMATICS POLARS ASPHALTENES

34.6% WT% 31.9 WT% 32.0 WT% 1.5 WT%
GC/M
S
18 AJ
11/4/2010
Dead Oil Asphaltene Stability SARA Screen
(Stankiewicz et al. 2002)
5.00
Unstable
4.50 Marginal
Stable
4.00
3.50
Saturate/Aromatic
3.00
2.50 Unstable
2.00
1.50
1.00
0.50
Stable
0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60
Asphaltene / Resin
19 AJ
11/4/2010
The “de Boer” Plot (de Boer et al., 1995) -
Asphaltenes
20 AJ
11/4/2010
Experimental: Near-infra Red Technology for Onset of
Asphaltene Precipitation
Power
2,000
15,000
11,000
13,000
3,000
4,000
5,000
6,000
7,000
9,000
Pressure
21 AJ
11/4/2010
NIR Pressure Depletion Traces of OIL A & OIL B Above Psat
Asphaltene Onset
4
Laser Power ((mW)
Psat
Psat
2
OIL A @ 175F
OIL B @ 155F
0
4000 6000 8000 10000
Pressure (psi)
22 AJ
11/4/2010
Asphaltene Reversibility Test for OIL C @ Tres
160
Asphaltene
Onset / Endpoint
120 Pasp to Psat = 3,000 psi
Laser Power (mW)
80
Depressurization
40
Re-pressurization
Psat
0
2000 4000 6000 8000 10000 12000
Pressure (psi)
23 AJ
11/4/2010
Visual Detection Of Asphaltene Flocculation
Mixer (0 to 1400 rpm)

Oil
Asphaltene Particle
Coned Piston
Pyrex Tube
Light Source
24 AJ
11/4/2010
Visual Detection Of Asphaltene Flocculation
Effects of Pressure and Time
12000 psia 7000 psia 7000 psia 7000 psia

time = 0 time > 0 time >> 0
25 AJ
11/4/2010
High Pressure Microscope (HPM) – Asphatene
Asphatene/Wax /Wax
Precipitation Assessment (20,000 psi & 200oC; Resolution ~ 2 mm)
HP
HPM M
26 AJ
11/4/2010
DBR Solid Detection System (SDS) Scan
with Photomicrographs from DBR HPM
Power
Pressure
27 AJ
11/4/2010
Particle Size Analysis (PSA)
during depressurization at 184ºF
10000
1000
100 14500 psi
10
1
10000
1000
100 13500 psi
10
1
10000
1000
100 12500 psi
10
1
10000
P
1000
100
11500 psi
10
A 1
10000
R 1000
10500 psi
100
T 10
1
I 10000
C
1000
100 9500 psi
10
L 1
10000
E 1000
8500 psi
100
10
1
C 10000
O
1000
100
7500 psi
10
U 1
10000
N 1000
6500 psi
100
T 10
1
10000
1000
100
6000 psi
10
1
10000
1000
100
5500 psi
10
1
10000
1000
100
5000 psi
10
1
10000
1000
100 4500 psi
10
1
10000
1000
100
4000 psi
10
1
10000
1000
100
3500 psi
10
1
10000
1000
100 3000 psi
10
1
10000
1000
100
2500 psi
10
1
10000
1000
100
1500 psi
10
1
1 11 21 31 41 51 61 71
Particle Size, micrometer
28 AJ
11/4/2010
Sampling Chamber Selection - Asphaltene
DBR/Chevron/BHP - IBC Aberdeen - Oct. ‘99
SPMC
Power
MPSR
Asphaltene Asphaltene
Precipitation Onset Precipitation Onset MRSC
7,800 psi 10,000 psi
Pressure
29 AJ
11/4/2010
Effect of OBM Contamination @ Tres with Syn-Tec
DBR/Chevron/BHP - IBC Aberdeen - Oct. ‘99
Psat 2.6 wt % OBM
7.6 wt % OBM
Power
14.2 wt % OBM
19.4 wt % OBM
Asphaltene
Precipitation Onset
Pressure
30 AJ
11/4/2010
Chemical Screening
Dead Oil
Titration tests (fast)
Dispersion tests
Live oil
Asphaltene onset (fast)
Particle size and morphology
Deposition
Cell rinses
Shear deposition cell
31 AJ
11/4/2010
HPM/SDS Oil Compatibility Study
14
12
Power of Laser Light ((mW)
10
0
0 5 10 15 20 25 30 35 40 45
Vol % C5
32 AJ
11/4/2010
HPM Depressurization Chemical Screening
500 psi
above Ponset
Ponset
500 psi
below Ponset
Chemical-1 Untreated Chemical-2

33 AJ
11/4/2010
Paraffin Wax Definition
• Waxes are higher molecular weight saturated carbons (>C20)
mainly from normal paraffins CnH2n+2 plus minor isoparaffins,
naphthenes and appreciable aromatic content.
• Tend to precipitate when significant amount of alkane with
carbon chain length higher than 18 are present
• Precipitates as crystalline waxy solids.
34 AJ
11/4/2010
Terminology “Cloud Point”
“Cloud point” is a terminology adopted by the

American Society for Testing and Materials (ASTM) to
refer to the temperature at which “cloudiness” of
relatively transparent fluid is observed upon cooling.
Alternate terminologies like “wax appearance

temperature” (WAT) and “wax precipitation
temperature” (WPT) have also emerged and are used
interchangeably.
35 AJ
11/4/2010
Thermodynamic vs. Measured Cloud Point
Thermodynamic Cloud Point is defined as the

highest temperature at which a solid phase (wax)
will exist at a given pressure
Measured Cloud Point is the temperature at which

a detectable amount of a solid phase forms upon
cooling in the time frame of the measurement at a
given pressure.
36 AJ
11/4/2010
Mechanism Of Wax Precipitation
Crystallization Rate
Nucleation Diffusion
Temperature
37 AJ
11/4/2010
Mechanism Of Wax Precipitation
GROWTH NUCLEATION EXTENTION LIQUID SATE

(Attachment) (WAT) (Alignment) (Random)
Crystal Stability/ Heat Of Fusion
n-paraffins
only
n- + iso-
paraffins
n- + iso-
+ cyclo-
paraffins
Temperature
38 AJ
11/4/2010
Wax Characterization Workflow
Normal paraffin from C20 to C60
• High Temperature Gas Chromatography
Thermodynamics of wax formation
• Cloud point (STO & Live Fluid)
• Pour point (STO & Live Fluid)
Transport Characteristics
• Viscosity - Rheology
• Gelling Characteristics
Modeling
• Thermodynamic Precipitation Modeling
• Deposition Modeling
39 AJ
11/4/2010
Wax Content of Dead Oil by High Temperature Gas
Chromatography
10+1
% N – Paraffin in crude (weight)
1.0
10-4
10-2
10-3
10-4
10 20 30 40 50 60 70 80 90
Carbon Number
40 AJ
11/4/2010
Composition Of Petroleum Waxes
C18 Paraffin waxes have carbon chains

ranging from C20 to C60+
Parent
C31 Oil Non n-alkanes with long n-alkyl chains
C49
may be part of waxes
C20
C44
Light compounds and non paraffins may
be trapped as inclusions in wax
Deposit
0 10 20 30 40
Retention Time (min)
41 AJ
11/4/2010
Key Engineering Properties of Waxy Crudes
Highly Non-Newtonian Mildly Non-Newtonian Newtonian
(viscosity strong function (viscosity dependent on (viscosity independent

of shear rate) shear rate) of shear rate)
15-25 oC
Pour Point Cloud Point

Temperature
42 AJ
11/4/2010
Cold Finger Technology – Old Technology
Cold Finger (CF)
Coolant In Coolant Out
Copper Rod
Oil Maintained
@ 55°C
Hot Plate with

Magnetic Stirrer
43 AJ
11/4/2010
Viscometry
Stationary Plate/Disc
µ = A e-Ea/RT (Newtonian Behavior)
Oil A = Pre-exponential factor

Ea = Activation Energy of viscous flow
R = Universal Gas Constant
T = Absolute Temperature
Mobile Disc
η* = η’ - i η’’
Rotating/Oscillating Motor η* = Complex Viscosity

η’ = Dynamic Viscosity
η’’ = Storage Viscosity
44 AJ
11/4/2010
Graphical Estimation of Cloud Point From
Viscosity Data
Log (m) (Pa.s)
WP
T
2.7 2.9 3.1 3.3 3.5 3.7

1000/T
(K)
45 AJ
11/4/2010
Schematic Diagram of Cross Polar Microscope (CPM)
Measurement of WAT of Stock Tank Oil
CC
D
Hot Stage
Analyzer Top View
4 50
25
Hot Stage
360o Rotatable Stage Cooling
Polarizer Gas
IR Filter
Light Source
46 AJ
11/4/2010
Wax Appearance Temperature (WAT) Measurement by
Cross Polar Microscopy (CPM)
0 °C (32 °F) WAT = 42 °C (108 °F) 44 °C (111 °F)
Temperature
47 AJ
11/4/2010
High Pressure Microscope (HPM) – Asphatene
Asphatene/Wax /Wax
Precipitation Assessment (20,000 psi & 200oC; Resolution ~ 2 mm)
HPM HPM
48 AJ
11/4/2010
Isobaric Cooling of South American Oil @ 4000 psi
100.00
Power of Transmitted Light (nW)
10.00
Asphaltene Onset
Well Head
~ 170°F
Temperature = 100°F
1.00
0.10
Cloud Point = 91°F
0.01
50 70 90 110 130 150 170 190 210 230
Temperature (°F)
49 AJ
11/4/2010
Cross Polarized HPM Photomicrographs
Co-precipitation of Solids – Live Oil
WAT = 66.7 oC (152 oF)
66.5 oC (151.7 oF)
50 AJ
11/4/2010
Effect of Pressure on Live Fluid WAT
50
System Pressure (MPa)
Psat PSAT
0
45 50 55
Temperature (ºC)
Above PSAT, Cloud point is proportional to Pressure

Below PSAT, Cloud point is an inverse function of Pressure
A minimum is attained at the saturation pressure
51 AJ
11/4/2010
Live Oil Pour Point Measurement
52 AJ
11/4/2010
Live Oil Pour Point with Solution Gas
Live Oil Pour Point - Oil 1
-20
Pour Point (oC)
70 oC Reduction In Pour Point
-40
-60
0 150 Psat (psig) 1,500 3,000
53 AJ
11/4/2010
HP Rheometer
Drive Unit
Heise G auge
BPR
TC 1
Cylinder
Cylinder
TC 2
Sample
Gas
54 AJ
11/4/2010
Dynamic Viscosity of Treated & Untreated Crude Oil
105 Temperature = 22 oC
104
Dynamic Viscosity (Pa.s)
103
102
10
10-1
10-1 1 10 102
Frequency (rad/s)
55 AJ
11/4/2010
Model Pipeline Test (MPT)
N2 Pressure
For Ungelling
HP Circulation Pump
Back-Pressure
Regulator
Heated Lines
Test Coils (2)

Fluid • 7.0 mm ID
Sample • 7.64 m long
Cylinder • 3,000 psi (35 Mpa)
• 170oF (75oC)
Temperature Applications:
Controlled Bath • Measure Yield Strength
• Evaluate Effectiveness Of Flow Improvers
56 AJ
11/4/2010
Live Oil Gel Strength
250
Gel Strength (kPa)
150
Over 75% Reduction In Gel Strength
50
0
0.1 1.7 34
Saturation Pressure (MPa)
57 AJ
11/4/2010
Effect of PPD
Pour Point Yield Stress
Oil Sample ASTM D97 (MPT)
Untreated 30 oC 0.49 kPa
Treated 18 oC 0.14 kPa
The oil samples in both cases were

aged for 12 hours at 9°°C.
58 AJ
11/4/2010
Precipitation vs. Deposition
Growth
Fluid Flow
Large Pressure Drops
Formation Deposition
Offshore Fields Cold Deep Water
TUBING
59 AJ
11/4/2010
Deposition Mechanisms—Hydrodynamics
Laminar versus turbulent flow

Laminar flow—waxes are softer
and contain larger amount of
entrapped oil
Turbulent flow—waxes are harder
and contain smaller amount of
entrapped oil
(Jessen and Howell, 1963, Aggrawal et al., 1990, Khan et al., 1997, Burger et al., 1983)
60 AJ
11/4/2010
RealView* Live Oil Deposition Measurement
SLB shear cell mimics production

conditions in the pipeline
Solids deposit in pipe Solids deposit on wall

of SLB shear cell
61 AJ
11/4/2010
RealView Live Solids Deposition Cell:
Configuration & Configuration
Concentric cylinders Specifications:
Inner cylinder rotates •Volume:
Creates an environment similar to pipe-
flow •150cc batch mode
Proven analogy between Taylor- •Up to 2 L flow through
Couette flow and pipe flow*
b •Temperature- 4 C to 150C
a
•Pressure- Ambient to 15000
ω L psi
•Spindle Speed= 100 Hz
* Zougari et al., Energy & Fuels, 2006, 20, pp. 1656-1663

62 AJ
11/4/2010
Scalability Between TC Flow and Pipe Flow
Scalability Criteria TC Device Pipe

Reynolds number ρ ( 2πω .rs )(ri − rs ) ρud
Re = Re =
µ µ
Wall Shear Stress Gρν 2 1
τw = τ w = ρuf 2
2πri 2 2
ν ν
Boundary Layer δL ~ δL ~
u* u*
Thickness
63 AJ
11/4/2010
Pipe to RealView Design
RealView Live Solids Deposition Device:
64 AJ
11/4/2010
65 AJ
11/4/2010
How Will I Remediate Deposition if it is a Problem?
RealView* case study—wax inhibitor evaluation

Injected inhibitor—untreated, chemical 1, chemical 2, chemical 3
Untreated Chemical 1 Chemical 2 Chemical 3
Deposit buildup mg/h = 30, 20, 11, 3
66 AJ
11/4/2010
RealView Results– Comparison with Field Data
Sample Production OSDC Prediction Field Data
1-Wax (BP) 30,000 Bpd / 10” 30mm / Year Pigging: 6 Months
2- Wax (Petronas) 12,000 Bpd / 12” 47mm / Year Chemical Injection
3-Asphaltene 14,000 Bpd / 4” 0.28mm / Year No Action

(Shell)
4-Asphaltene (BP) 15,000 Bpd/3.6” 13.5mm/Year Chemical Injection
67 AJ
11/4/2010
Summary- Benefits of Studying True Deposition
Minimize CAPEX: Prevent Solids from Forming

Study true requirement for Insulation/Heat to maintain fluid above thermodynamic
formation temperature (Wax) - reduce over-design
Understanding of co-deposition of wax and asphaltenes during design phase -
employ design strategies to handle co-deposition
Examine various operating scenarios and effect on deposition- ie, gas lift, effect
of production rate changes, wax-in-place stategy for marginal field
Increase confidence in budget projections and target setting
Optimize OPEX: If Solids Formation Unavoidable
Remove deposits by pigging (Wax) - reduce pigging frequency
Study effect of chemical effectiveness (Wax and Asphaltenes) under live
conditions – select the best chemical and optimize the chemical dosage

Hydrates – Definition & Characterization
Hydrates are ice-like compounds

They form in the presence of water and small
molecular gas components at low T, high P
69 AJ
11/4/2010
Hydrate Characterization Workflow
Composition
• Gas phase
• Oil phase
• Water phase
Hydrate Locus
• Function of salinity
• Effect of thermodynamic Inhibitors
Formation kinetics
Modeling
• Thermodynamic Modeling
70 AJ
11/4/2010
Hydrate Equilibrium
Equilibrium curve
wellhead
Hydrates
No hydrates
Hydrates may not form immediately below Teq,
but will dissociate above Teq
71 AJ
11/4/2010
Why Measurements
Program A
Program B
Program C
Pressure (psi)
Predicted hydrate equilibrium with

28.4wt% CaCl2
0 10 20 30 40 50 60
Temperature (oF)
72 AJ
11/4/2010
Conservative and realistic
Pure water prediction Formation water, measurements
Initial proposed design line

Pressure (psi)
12oF (7.5oC)
40 45 50 55 60 65 70 75 80 85 90
o
Temperature ( F)
73 AJ
11/4/2010
Hydrate Equilibrium Measurements
Visual observations & Video

Up to 20,000psi and –20oC, accurate
Slow process, requires “baby sitting”
Autoclave (blind cell p-T trace)
Fast, accurate, fully automatic
Up to 10,000psi and –5oC
74 AJ
11/4/2010
Visual Determination of the Hydrate Locus
100 Wt % Methanol
60 0.0
40
20.0 10.0

20

10
Pressure, MPa

4
L2 G
2  Locus


0.8

0.4

0.2

0.0 
8
0.0
4 - 0 10 20 30
10
75 AJ
11/4/2010
High Pressure Microscopy (HPM)
--Visual Equilibrium determination
CCD HPM
P: <20K psi
T: >-20oC
76 AJ
11/4/2010
Autoclave
torque
p T
Gas
Gas
Hydrate
Crystals
Liquid
77 AJ
11/4/2010
Equilibrium Determination by p-T trace
Pressure (psi)
prediction
Measurement
o
Temperature ( F)
78 AJ
11/4/2010
Generic Hydrate Equilibrium Curves
Conditions above & left of lines are favorable for hydrate

79 AJ
11/4/2010 formation
Other measurements by Autoclave
Kinetic inhibitor evaluation

By observing hydrate formation rate
Thermodynamic inhibitor dosage estimation
By quantifying inhibitor synergies
Anti-agglomeration screening
By identifying plug formation
80 AJ
11/4/2010
Oilfield Emulsion – The Problem
Naturally occurring surface active agents stabilize water in oil

emulsions in produced fluids. Emulsion increases viscosity and hence
increase pressure drops causing problems in gathering systems and
treatment facilities. Require specialized treatment vessels, chemicals
or excessive residence time resulting in increased CAPEX and OPEX.
81 AJ
11/4/2010
Emulsion Theory
Water in Oil Emulsion

A mixture of two immiscible liquids, one of which is dispersed as very small droplets in
the other, this dispersion being stabilized by an emulsifying agent
Oil
Water
Dispersion
Mechanical
Energy
Emulsification
Surfactan Chemical Surfactant
t Stabilizers
O
CH -(CH ) 16 C -
3 2 O -
+
O
-
Ca ++ Na C CH -(CH ) 16
O O 3 2
CH 3
-(CH )
2 16 C
O
Non-Polar Tail Polar Head Polar Head Non-Polar Tail
The separation of the emulsion phases depends on the stability of the emulsion
82 AJ
11/4/2010
Droplet Size Distribution
Droplet Size Distribution of Crude oil Emulsion
Medium Emulsion
Frequency
Tight Emulsion
Loose Emulsion
1 10 100
Droplet Diameter (mm)
83 AJ
11/4/2010
Emulsion Viscometry –
Stock-Tank or Reservoir Fluid
Rolling ball viscometer

Capilary tube viscometer
Electromagnetic viscometer
New technology Sensors
• Vibrating wire
84 AJ
11/4/2010
Emulsion Viscosity
120
Water-in-Crude Oil Phase Inversion
emulsion Crude Oil-in-
100
102 S-1 Water emulsion
80 170 S-1
Viscosity, cP
340 S-1
60
510 S-1
40 1021 S-1
20
0
0 10 20 30 40 50 60 70 80 90 100
Water Cut, %
85 AJ
11/4/2010
Inorganic Scales
“Hard Adherent Mineral Deposits that Precipitate From Brine Solution”
thickness of Quartz
calcite
scale
Rock Matrix
Quartz
Barit
Anhydrite e
Tubulars
Scaled up pipe: Topside Example from an Oilfield in Sumatra,

86 AJ
11/4/2010 Indonesia
Common Oilfield Inorganic Scales and Solubility in Water
Name Synonym Formula Molecular Specific Hardness Solubility Solubility

Weight Gravity (Mohs) Cold Water Hot Water
(mg/l) (mg/l)
Barium Barite BaSO4 233.29 4.5 3.3 2.2 3.4

Sulfate
Calcium Calcite CaCO3 100.09 2.71 3 14 18
Carbonate
Strontium Celestite SrSO4 183.68 3.96 3 113 140
Sulfate
Calcium Anhydrite CaSO4 136.14 1,96 3 2,090 6,190
Sulfate
Calcium Gypsum CaSO4.2H2O 172.17 2.32 2 2,410 2,220
Sulfate
Sodium Halite NaCl 58.44 2.165 2 357,000 391,200

Chloride
87 AJ
11/4/2010
Causes of Scale Formation
Decrease in the solubility of inorganic

constituents (calcium and magnesium
carbonate) due to pressure and
temperature changes
Mixing of incompatible waters e.g. sea
water and formation water
pH changes due to loss of dissolved
gas
88 AJ
11/4/2010
Cause of Scale Formation: Autoscaling
View of a perforation throat
Pressure drop over NWB matrix

4 feet
Precipitation
produces further
pressure drop,
leading to further
precipitation
89 AJ Pressure drop causes CO2 to break out of solution

11/4/2010
causing precipitation of calcium carbonate scale
Cause of Scale Formation: Mixed Water
• BaSO4 occurs where mixing of incompatible water
co-mingle
• CaCO3 occurs where Ca2+ and HCO3- exceed the
solubility product
• Increased by draw down
• Scale can occur in the matrix and/ or the production
tubular
“Skin” zone SW
Injected Seawater FW
Scale
Formation Water
90 AJ
11/4/2010
Cause of Scale Formation: Evaporation
Evaporation of water into an expanding gas, as the gas bubble travels

to surface
Salt precipitates from the solution
Major problem in HTHP gas wells
Serious problem with NaCl saturated formation waters
Serious but uncommon source of scale
Inhibited by saturating the gas bubble with water at the point of
entry into the wellbore
91 AJ
11/4/2010
Cause of Scale Formation: Gas Flood
Flooding a formation for secondary recovery

Water containing CO2 becomes acidic and will dissolve calcite from
the formation
Subsequent pressure drop may cause CO2 release and calcite
precipitation
Perforation and formation pores near the wellbore may become
blocked
Similar to Autoscaling
Self-generating process that can completely seal perforations and
reduce production
92 AJ
11/4/2010
Mechanism of Scale Precipitation
Nucleation and Growth (two step process)
Ba2+ + SO42- = BaSO4
Super-saturation Ion pairs Clusters / Nuclei

Ba2+ SO42 Ba2+ SO42
Transient Stability
2
Ba2+ SO4
Further growth at sites of crystal Imperfect Crystallites

imperfections
93 AJ
11/4/2010
Scale Analysis Techniques
Water Analysis
Standard bottle mixing test
Near Infrared Spectroscopy (NIR)
Coreflood tests
Simulation involving water and ionic chemistry
94 AJ
11/4/2010
Water Analysis
Parameters Seawater Formation Water
Dissolved Solids mg/l
Total Dissolved Solids 30,000-41,000 100-336,000
ASTM 10 ion Analysis Sodium

Potassium
11,000-16,000
300-500
40-135,000
0-1,000
Titration technique Calcium

Magnesium
300-500
1,100-1,500
0-50,000
0-5,000
ICP (Inductively Coupled Barium

Strontium
0.1-0.5
6-8
0-2,000
0-2,000
Plasma) technique Iron 0 0-100

Chloride 17,000-24,000 60-200,000
Sulfate 2,400-3,200 0-50,000

Carbonate 0 0-1,000
bicarbonate 120-150 100-3,000

Specific Gravity 1,020-1,032 1,000-1,250
Dissolved Oxygen 6-11 0
Carbon Dioxide 0 0-2,000
Hydrogen Sulfide 0 0-1,000
pH 8.0-8.4 4-10
Temperature 0-30 20-150
Total Suspended Solids 0.1-20 1-100
95 AJ
11/4/2010
Bottle Mixing Test
Filter : Weigh and

Analyze solid with
XRD
V1 V2
Measure turbidity
with UV over a
period of time (12
hrs).
96 AJ
11/4/2010
NIR Spectroscopy
Similar to bottle mixing test but in a HPHT system

Measure scale onset pressure at a specified temperature
Can be used to test the effect of mixing at downhole
conditions
97 AJ
11/4/2010
Commercial Simulation Packages
ScaleChem (OLI)
Multiscale (Petrotech)
Geochemist Work Bench
(Bekthe)
Representative Water samples and accurate lab analysis is

required
98 AJ
11/4/2010
Properties of Water
Hardness
Total mg/L of Ca++, Mg++, Fe++ converted into CaCO3 equivalent in
mg/L
Alkalinity
Total mg/L of HCO3-, CO3--, OH- converted into CaCO3 equivalent in
mg/L
99 AJ
11/4/2010
Exercise – Hardness and Alkalinity
Ion Concentration (mg/L)

2-
CO3 0
OH- 0
-
HCO3 122
Ca2+ 105
Mg2+ 56
Fe2+ 18
Calculate the hardness and alkalinity for a sample of water with ionic
composition given in the table
100 AJ
11/4/2010
Exercise – Hardness and Alkalinity
Solution
Hardness = Ca2++Mg2++Fe2+
Equivalent weight of CaCO3 = 50
Ion Concentrati Molecular Equivalent Equivalent

on (mg/L) weight weight CaCO3
2-
CO3 0 60 30 0
Alkalinity = 100
OH- 0 17 17 0
HCO3- 122 61 61 100 = (122x50/61)
Ca2+ 105 40 20 262.5
Mg2+ 56 24.4 12.2 229.5 Hardness = 524.2
Fe2+ 18 55.8 27.9 32.3
Equivalent CaCO3 Example (Conc x EW of CaCo3 / EW of Ions)
101 AJ
11/4/2010
Ionic Strength
Factors for converting ion composition to ion strength
102 AJ
11/4/2010
Example Water Analysis
103 AJ
11/4/2010
Scale Phase Envelop
12000
Precipitation phase envelop for CaCO3 at
11000 ST<1 for BaSO4
50% water cut
10000 Precipitation phase envelop of BaSO4 at
50% water cut
9000 Precipitation phase envelop for SrCO3 at
50% water cut
Pressure (psia)
8000
ST=1 for BaSO4
7000
6000
ST>1 for BaSO4 ST=1 for CaCO3
5000
ST<1 for SrCO3
4000
ST< 1 for CaCO3
3000
ST>1 for CaCO3
2000 ST=1 for SrCO3
1000
0 ST>1 for SrCO3

0 50 100 150 200 250 300
Temperature (F)
104 AJ
11/4/2010
Natural Occurrence of Mercury Compounds in Hydrocarbon
Streams
Natural Gas Condensate
Trace suspended Trace ionic Some organic

Some suspended
Elemental
Dominant Trace
Trace
Types of Hg suspended organic
Elemental
Organic
Some ionic
Ionic
Suspended
Crude Oil
105 AJ
11/4/2010
UOP 5241G-03
Hg Impacts to Oil & Gas Industry
Product
Quality HSE
• Crude oil
• Natural Gas • Health (hazards)
• Condensate Mercury • Safety (people &operations)
• Environment
Equipment Catalyst
• Corrosion due to attack of

• Catalyst poisoning
Hg towards metal (Al, Mg…)
• Deactivation of active sites
Al + Hg → HgAl
• Contaminated spent
HgAl + 3H20 → Al2O3 + 3H2 + Hg
catalyst/ adsorbent
• Stress cracking, leaking,
explosion in plant.
106 AJ
11/4/2010
Napthenates
Calcium salts of napthenic acids

Arn is the main constituent and prerequisite (C80H142O8)
Arn is present in acidic or high TAN crudes
Courtesy : Statoil
107 AJ
11/4/2010
Arn Acid Molecular Structure
108 AJ
11/4/2010
Calcium Naphthenate Characterization
Statoil/ConnocoPhillips Paper – SPE 93011
13C Nuclear Magnetic Resonance (NMR)

High-Temperature Gas Chromatogram (HTGC)
Liquid Chromatography – Mass Spectroscopy (LC/MS)
109 AJ
11/4/2010
Calcium Naphthenate Characterization - Example
from Statoil/ConnocoPhillips Paper SPE 93011
110 AJ
11/4/2010
Calcium Naphthenate Characterization - Example
from Statoil/ConnocoPhillips Paper SPE 93011
111 AJ
11/4/2010
Sand Production
Lun - 1 , 3 , 4 & 6 Core Data
Cumulative Weight -vs- Particle Size
100
90
80
70
Cum ulative Weight [%]

60
Condensate-Water Separator 50
(Courtesy of A. Kooijman/Mike Gunningham) 40
30
20
10
0
10000 1000 100 10 1
Particle Size [micron]
Reservoir Characterization
• Porosity,
• Permeability,
• Particle Size - d50
• Fines
112 AJ
11/4/2010
Factors Affecting Sand Production
113 AJ
11/4/2010
• Overburden
• Cementing
• Capillary
• Drag
114 AJ
11/4/2010
Overburden, Friction, Differential Stresses

Cementing Material, Degree of Consolidation
Fluid Viscosity, Production Velocity, Drag Forces
Capillary Forces, Water Production
115 AJ
11/4/2010
Cause of Sand Production
Once the destabilizing forces overcome the formation

strength, the rock will fail.
Sand production will follow if sand can be transported.
116 AJ
11/4/2010
Reasons Controlling Sand Production
HSE
• Sand Erosion
• Casing / Liner Failure
• Sand Disposal
Reduced Production
• Sand fill in wellbore
• Sand settling in flow lines
117 AJ
11/4/2010
Sand Production
Producing sand can be an option
Increases Opex
Sand separation equipment
Large volume of solids to handle
Clean
Transport
Dispose
118 AJ
11/4/2010
Casing / Liner Collapse
Failure may occur due to
─ Non uniform lateral loading
as rock is produced.
─ High axial compressive load

due to slumping of the
overlying casing-bearing
formation.
119 AJ
11/4/2010
Sand Erosion
Sand production can cause erosion in both surface and
downhole equipment such as :
Downhole Surface
Blast Joints Chokes
Gas lift Equipment Elbows / Tees
Standing Valves Swages
Pumps Valves
Safety Valves Metering Devices
Circulating sleeves Flanges
Nipples Wellhead
Tubular
120 AJ
11/4/2010
Sand Bridges
Bridges may form in casing or
tubing and obstruct well flow.
They must be removed by
bailing or washing with
concentric strings.
If bridging is severe sand
control will be required.
121 AJ
11/4/2010
Sand Production Prediction
Experience
Analogy
Special Well Test
Core Inspection and Testing
X-Ray, SEM
Flow Tests
Uniaxial and Triaxial Compressive Strength Measurements
BHN (Brinell Hardness Number)
Log Interpretation
IMPACT
122 AJ
11/4/2010
Rock Classification
Term BHN Remarks
Unconsolidated < 2 No cementing material
Partially 2-5 Crushed with fingers
Friable 5 - 10 Crushed when rubbed
Consolidate 10 - 30 Crushed with forceps
Hard > 30 Can not be broken with
Medium Hard 30 - 50 forceps
Hard 50 - 125
Very Hard > 125
(BHN - Brinell Hardness Number)
123 AJ
11/4/2010

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Flow Assurance

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Production Chemistry Production Engineering Production Surveillance

Asphaltene Molecules either…

Many ‘Fused’ rings

Partial molar volumes increase Partial molar volumes increase

The definition of “Asphaltene” is somewhat

Stock-Tank-Oil is an effective asphaltene solvent

Increasing the Concentration of Resins in North

STO STO STO STO STO

Saturates Aromatics Resins Asphaltenes

Wt % Resin in North Sea Dead Oil

Crudes with no Crudes with

T1 = 200°C 200>300 °C IBP 200°C

IBP -200 °C 200-340 °C >340 °C

SATURATES AROMATICS POLARS

SATURATES AROMATICS POLARS ASPHALTENES

Mixer (0 to 1400 rpm)

12000 psia 7000 psia 7000 psia 7000 psia

Particle Size, micrometer

Psat 2.6 wt % OBM

Chemical-1 Untreated Chemical-2

“Cloud point” is a terminology adopted by the

Alternate terminologies like “wax appearance

Thermodynamic Cloud Point is defined as the

Measured Cloud Point is the temperature at which

GROWTH NUCLEATION EXTENTION LIQUID SATE

C18 Paraffin waxes have carbon chains

Highly Non-Newtonian Mildly Non-Newtonian Newtonian

(viscosity strong function (viscosity dependent on (viscosity independent

Pour Point Cloud Point

Hot Plate with

Oil A = Pre-exponential factor

Rotating/Oscillating Motor η* = Complex Viscosity

Log (m) (Pa.s)

2.7 2.9 3.1 3.3 3.5 3.7

Analyzer Top View

0 °C (32 °F) WAT = 42 °C (108 °F) 44 °C (111 °F)

Cloud Point = 91°F

WAT = 66.7 oC (152 oF)

66.5 oC (151.7 oF)

Above PSAT, Cloud point is proportional to Pressure

Live Oil Pour Point - Oil 1

70 oC Reduction In Pour Point

Test Coils (2)

Pour Point Yield Stress

Oil Sample ASTM D97 (MPT)

Untreated 30 oC 0.49 kPa

Treated 18 oC 0.14 kPa

The oil samples in both cases were

Offshore Fields Cold Deep Water

Laminar versus turbulent flow

SLB shear cell mimics production

Solids deposit in pipe Solids deposit on wall

* Zougari et al., Energy & Fuels, 2006, 20, pp. 1656-1663

Scalability Criteria TC Device Pipe

RealView Live Solids Deposition Device:

RealView* case study—wax inhibitor evaluation

Untreated Chemical 1 Chemical 2 Chemical 3

Deposit buildup mg/h = 30, 20, 11, 3

Sample Production OSDC Prediction Field Data

1-Wax (BP) 30,000 Bpd / 10” 30mm / Year Pigging: 6 Months

2- Wax (Petronas) 12,000 Bpd / 12” 47mm / Year Chemical Injection