0 évaluation0% ont trouvé ce document utile (0 vote)
15 vues31 pages
Asphaltenes precipitated in the production system (reservoir - wellbore - tubing - pipeline - topside facilities) may lead to their deposition = reduced or shut-in production
Asphaltenes precipitated in the production system (reservoir - wellbore - tubing - pipeline - topside facilities) may lead to their deposition = reduced or shut-in production
Asphaltenes precipitated in the production system (reservoir - wellbore - tubing - pipeline - topside facilities) may lead to their deposition = reduced or shut-in production
and a contribution from Offshore Europe The Society is grateful to those companies that allow their professionals to serve as lecturers Additional support provided by AIME Society of Petroleum Engineers Distinguished Lecturer Program www.spe.org/dl 2 Origin and Behaviour of Oil Asphaltenes Integration of Disciplines Artur Stankiewicz Society of Petroleum Engineers Distinguished Lecturer Program www.spe.org/dl 4 Acknowledgments The data and supporting examples are primarily based on the research and field application that took place 1998- 2009 at various Shell locations. Author is grateful to Shell and Schlumberger for permission of presenting this material to the SPE audience. Cooperating service companies, scientific institutions and all who, over the years, worked with me on the R&D and implementation of technologies in the area of asphaltenes. Introduction into the World of Asphaltenes Setting the scene Basic facts and definitions Origin of asphaltenes (source and changes in geological time) Few remarks on asphaltene structure & analytical techniques Theory of the oils critical range Fluid properties and live oil behaviour Stock tank liquid screens Live oil behaviour and screens Examples of diversity in the world of asphaltenes and implications Field application Conclusions Outline 5 Asphaltenes why do we care? Asphaltenes precipitated in the production system (reservoir wellbore tubing pipeline topside facilities) may lead to their deposition = reduced or shut-in production Topside facilities Pipes blocked due to asphaltenes (photo courtesy of Nalco) Asphaltenes one of many solid phases encountered in production systems 0 2000 4000 6000 8000 10000 12000 14000 16000 0 10 38 65 93 121 Temperature (C) P r e s s u r e
( p s i a ) Hydrate Asphaltenes Wax Asphaltenes Waxes Hydrates Diamondoids Inorganic Scales Sulfur Asphaltenes when unstable typically precipitate at higher T and P than other solids Reservoir Flow line 7 After John Ratulowski Asphaltenes deposition how? Composition Changes Instability due to commingling of incompatible fluids Carryover & blending with LNG fouls gas side equipment Gas lift mandrills foul Injection gas can cause reservoir impairment, wellbore deposition, and fouling of pumps Pressure Changes Near-perforation reservoir impairment Deposits in wellbores & flowlines cause excessive pressure drop & additional plugging Precipitated solids accumulate in low energy regions IMPLICATIONS: It is a solubility class = NOT well defined molecule Various analytical procedures prevent standardization ASPHALTENES are defined as the material that precipitates out of crude oil or reservoir rock extract on the addition of excess light alkanes 9 0 1 2 3 4 5 Pentane Heptane Decane Precipitant type Asphaltenes in Oil [wt. %] Asphaltenes % C n of n-alkane Asphaltene Content of Unstable Oils 0.5 - 5 1 - 9 0.4 0.2 0.5-2 2 - 5 0.9 - 3.5 0.1 - 4.2 4 - 15 0.9 - 1.9 7 - 9 0.3 ~0.8 10 Asphaltene problems are localized, <1% of total world production Some countries have serious challenges (e.g., Venezuela, Kuwait) Asphaltenes an Engineering Domain, but Cant we just all get along? Main Technical Areas: Prediction (Deposition Potential) Prevention (Monitoring & Control) Remediation (Recovery & Removal) Inhibition (Chemical treatment) Geochemistry brings a fresh view on natures diversity a global asphaltene molecule does NOT exist influenced by source rock type and oil generation/expulsion/migration processes. Majority of issues are driven by fluids phase behaviour, production scenarios, topside separation or the Enhanced Oil Recovery processes. 11 Simple solubility model can explain asphaltene stability Asphaltene Aromatic Resin Saturate S A R A Geochemical and Engineering-View on Asphaltenes 12 H N S S OH S N H S OH 0 H Modified from Pelet et al., 1986 After Steve Larter & Eugene Frolov NRG Petroleum Group Source Rock Kerogen Composition Thermal Maturity (t & T) Secondary Processes (in reservoir) Biodegradation (bacteria) Hybridization (mixing) Gas Washing (late gas charge) Oil Composition Asphaltene Content/Stability Natural Processes that can Affect Asphaltene Stability in Crude Oil 13 Marine deltaic and open marine settings Type II Flood Plain Coals Type III Lacustrine Shales Lagoonal shales and coals Type I Where They Come From? Source Rock Kerogen Types and Origin 14 Maturity and its Importance A rock with sufficient organic matter of suitable chemical composition to generate and expel hydrocarbons at appropriate maturity levels is called a source rock Thermal degradation of kerogen (burial, T ) breakdown and release of hydrocarbons Maturity = structural simplification 15 Origin and Maturity Affects Structure and Behaviour (T, from bio- to geomacromolecule) 0 N 0 H0 N 0 0 0 0 N 0H H0 S S HS 0H H0 H0 0 0 0 0 0 0 H0 0H N N N N V-0 0 H0 0 N 0 16 0 N 0 H0 N 0 0 0 0 N 0H H0 S S HS 0H H0 H0 0 0 0 0 0 0 H0 0H N N N N V-0 0 H0 0 N 0 N H0 N N H0 S S H0 0 S N HS N N With maturity (irrespective of their source origin): Molecular ratios H/C, O/C, N/C and S/C Molecular weight (size) Metals (e.g., Ni, V) Sulfur % Asphaltenes General Trends IMPLICATION: Oils in the specific maturity range show increased potential for asphaltene precipitation low maturity, heavy and biodegraded oils, and high maturity condensates are generally stable 17 Pitch Lake Trinidad GOM 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 15 20 25 30 35 40 45 50 Oil Gravity [API] O i l
A s p h a l t e n e
C o n t e n t
[ w t .
% ] West Africa Venezuela North Sea Italy Canada Primary fluids only Approx. Region of Fluids with Asphaltene Problems Middle East Oil Asphaltene Content and the Oil Gravity as Indicators of Maturity 18 Maturity Controlling Fluid Stability thus Asphaltene Precipitation Hypothesis Maturity increase Maturity indicators: e.g. API increase, Asphaltene % decrease F l u i d
I n s t a b i l i t y
w r t
A s p h a l t e n e
P r e c i p i t a t i o n
Low Maturity Fluids (Heavier) High Maturity Fluids (Condensates) Critical Range NOTE: Natural processes and production scenarios can affect asphaltenes behaviour 19 Compositional Asphaltene Stability Screens Stable Unstable Marginal Asphaltene / Resin S a t u r a t e
/
A r o m a t i c Unstable Stable 20 Stankiewicz et al., 2002 Colloidal instability index Critical asphaltene to resin ratio SARA plot (shown) Dead Oil Titration Tests Neat Oil Oil +1 ml of Hexadecane P =1.5 P-Value 2 mW NIR Laser Detector Titrator TC Magnetic Stirrer Volume of Titrant Floc Point Computer T r a n s m i t t e d P o w e r FPA Floc Point Analyzer Heptane 21 Discrete or continuous titration Detection Visual Spot test Light scattering Does not contain effect of gas Stable Unstable High p&T System to Evaluate Asphaltene Behaviour in Live Oil 22 DBR Solids Detection System (Light Transmittance) Neat oil Oil with asphaltenes Example of Non-problematic Fluid from Venezuelan Well 0 2000 4000 6000 8000 10000 Pressure (psig) Power of Transmitted Light (mW) Water-like Droplets Water-like Droplets Pres P SAT ~ 1930 psi 23 Non-problematic = no deposition observed Problematic = deposition in the wellbore observed Example of Problematic Fluid from Venezuelan Well 0 2000 4000 6000 8000 10000 Pressure (psig) Power of Transmitted Light (mW) Pres 10mm 10mm 10mm 10mm 10mm P SAT ~ 1860 psi P OAP ~ 3500 psi Information that can be used to optimize operations 24 Example of Variation in Molecular Composition of Asphaltenes 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 0.00 0.01 0.02 0.03 0.04 0.05 S/C H / C
o f
A s p h a l t e n e s VEN NS GOM World MW~1000 MW~2200 MW~3500 25 MW based on GPC (SEC) 0 200 400 600 800 1000 0 10 20 30 40 50 60 70 80 90 100 0 20 40 60 80 100 0 200 400 600 800 1000 0 10 20 30 40 50 60 70 80 90 100 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 P a r t i c l e
C o u n t Size [mm] Venezuelan Oil (deposition problems) North Sea Oil (no deposition observed) 9000 psi 5250 psi 3500 psi 9000 psi 5000 psi 4500 psi 3500 psi 0 200 400 600 800 1000 5000 psi Variations in Flocc Size is Critical 0-60 0-15 26 Depressurization experiments at reservoir T Oil/Asphaltene Molecular Composition vs Activity of Field Chemicals C B D A Different Chemical Inhibitors North Sea Oil Asphaltene = 1 % API = 38.5 Sulfur oil = 0.11 % Venezuelan Oil Asphaltenes = 5 % API = 32 Sulfur oil = 1.4 % 27 The same chemical react differently with different asphaltenes Venezuela type asphaltenes North Sea type asphaltenes After: Ting et al, Petrophase Trondheim, 2004 Variations in PVT Behavior 10 38 65 93 121 149 0 2000 4000 6000 8000 10000 P r e s s u r e
( p s i a ) Temperature (C) L & V Liquid Phase L & V L & V & Asph Phases L & Asph Phases Liquid Phase L & Asph & Wax Phases 10 38 65 93 121 149 0 2000 4000 6000 8000 10000 Temperature (C) 12000 Regions of asphaltenes instability L & Asph Phases L & V & Asph Phases L & Asph & Wax Phases Asph Stability Bubble point Asph Stability 28 Example of Carbonate Reservoir 1 6 0 0 0 5000 meters N 31 22.2 26 28.7 31.8 API 31 29.4 28.5 28.6 30.6 29 28.5 28.3 29.5 1.7 2.34 2.13 2.01 1.54 S% 1.83 1.78 1.72 1.73 1.8 1.81 1.9 1.99 1.83 5.6 11.2 13.1 8.8 4.3 Asphaltene Content 6.0 7.9 7.9 7.8 6.5 7.2 7.8 7.0 6.7 1 1 1 2 3 2 2 2 3 3 4 3 4 Problem ranking 1 Heavy deposition 4 No deposition Lighter fluids with asphaltene challenges Heavier fluids without asphaltene deposition 29 Molecular composition of asphaltenes varies and depends on factors such as source rocks and maturity an average asphaltene structure does not exist. Knowledge of physical/chemical properties of oil and its asphaltenes may be successfully used for prediction of their behavior ahead of production best practices: Routine measurements of fluid property for each new well or reservoir Comprehensive database of fluid properties for each field (existing and new) Constant calibration of empirical observations against field experience Integrated approach and cooperation of various disciplines Conclusions 30 Food for thought Asphaltene deposition problems to date are confined to specific areas and relatively light fluids, however: Increased focus on the EOR/IOR unravels new potential challenges in the area of precipitation/deposition of previously stable hydrocarbon fluids. An integrated approach and cooperation of engineers and geoscientists (e.g. geochemists) is necessary to understand oil asphaltene behavior and its influence on fluid properties. 31