Thermodynamic Characterization of Reservoir Fluids

1
Thermodynamic Characterization of Reservoir
Fluids and Process Analysis
Adidharma/Towler/Radosz Department of Chemical
and Petroleum Engineering, University of Wyoming

• The thermodynamic characterization of reservoir
  and injected fluids allows us to perform rigorous
  analyses of the oil recovery processes.
• A continuous program that will reveal important
  factors that are still unknown or not well
  understood and affecting the efficiency of oil
  recovery.
• A synthesis of theoretical and experimental
  components.

2
Achievement

• Theoretical component
• Developed a unified advanced model (SAFT) to
  predict the thermodynamic properties of reservoir
  fluids, including brine, at reservoir conditions.
• Developed unified advanced models
  (FT-SAFT/FV-SAFT) to predict the viscosity of
  gas/liquid/supercritical fluids for carbon
  dioxide and alkanes.
• Developed an advanced model (Multiple Mixing
  Cells model coupled with key tie line approach)
  to predict Minimum Miscibility Pressure (MMP) for
  model oils.

Refereed publications 10 Submitted 2
3
Achievement

• Experimental component
• Built a slim tube apparatus for Minimum
  Miscibility Pressure (MMP) measurements
• Measured MMP for model oils and Wyoming oils.
• Investigated the effects of injected gas
  composition on MMP.

Refereed publications 2
4
Future Work (2007-2008)

• Theoretical component
• Extend our model to predict the MMPs of systems
  with increasing degree of complexity.
• Experimental component
• Continue supporting the modeling work and
  measuring the MMPs of Wyoming oils.
• Study the effects of operating conditions, gas
  composition, and brine on oil recovery in CO2
  flooding.

5
Viscosity of alkanes
Viscosity of pure n-alkanes at P 200 bar
broken lines are calculated using our model
(numbers n are for CnH2n2) circles
experimental data
6
Process simulation results Ternary system
Zhao, et al., 2006
7
MMP Measurements for Wyoming Oil
8
Effects of O2 and N2 on MMP
9
Publications
1. Yang, F. Zhao, G-B. Adidharma, H.Towler,
B.F. Radosz, M.. The effect of oxygen on minimum
miscibility pressure in carbon dioxide flooding,
Ind. Eng. Chem. Res. 2007, in print. 2. Zhao,
G-B. Adidharma, H.Towler, B.F. Radosz, M.
Using a multiple-mixing-cell model to study
minimum miscibility pressure controlled by
thermodynamic equilibrium tie lines. Ind. Eng.
Chem. Res. 2006, 45, 7913-7923. 3. Ji, X.
Adidharma, H. Ion-based SAFT2 to represent
aqueous single- and multiple-salt solutions at
298.15 K. Industrial Engineering Chemistry
Research 2006, 45, 7719-7728. 4. Ji, X. Tan, S.
P. Adidharma, H. Radosz, M. Statistical
Associating Fluid Theory Coupled with Restrictive
Primitive Model Extended to Bivalent Ions. SAFT2
II. Brine/Seawater Properties Predicted. Journal
of Physical Chemistry Part B 2006, 110,
16700-16706. 5. Tan, S. P. Ji, X. Adidharma,
H. Radosz, M. Statistical Associating Fluid
Theory Coupled with Restrictive Primitive Model
Extended to Bivalent Ions. SAFT2 I. Single Salt
Water Solutions. Journal of Phys. Chem. B 2006,
110, 16694-16699. 6. Kiselev, S. B. Ely, J. F.
Tan, S. P. Adidharma, H. Radosz, M. HRX-SAFT
Equation of State for Fluid Mixtures Application
to Binary Mixtures of Carbon Dioxide, Water, and
Methanol. Industrial Engineering Chemical
Research 2006, 45, 3981-3990. 7. Tan, S. P.
Adidharma, H. Towler, B. F. Radosz, M. Friction
Theory Coupled with Statistical Associating Fluid
Theory for Estimating the Viscosity of n-Alkane
Mixtures. Industrial Engineering Chemistry
Research 2006, 45, 2116-2122. 8. Ji, X. Tan, S.
P. Adidharma, H. Radosz, M. The SAFT1-RPM
Approximation Extended to Phase Equilibria and
Densities of CO2-H2O and CO2-H2O-NaCl Systems.
Industrial Engineering Chemistry Research 2005,
44, (22), 8419-8427. 9. Ji, X. Tan, S. P.
Adidharma, H. Radosz, M. Statistical Associating
Fluid Theory Coupled with Restricted Primitive
Model to Represent Aqueous Strong Electrolytes
Multiple Salt Solutions. Industrial Engineering
Chemistry Research 2005, 44, 7584-7590. 10. Tan,
S. P. Adidharma, H. Towler, B. F. Radosz, M.
Friction Theory and Free-Volume Theory Coupled
with Statistical Associating Fluid Theory for
Estimating the Viscosity of Pure n-Alkanes.
Industrial Engineering Chemistry Research 2005,
44, (22), 8409-8418. 11. Tan, S. P. Adidharma,
H. Radosz, M. Statistical Associating Fluid
Theory Coupled with Restricted Primitive Model to
Represent Aqueous Strong Electrolytes. Industrial
Engineering Chemistry Research 2005, 44,
4442-4452.
10
Enhanced Oil Recovery Using CO2

• There is a current supply shortage
• Other sources are the Exxon Shute Creek plant
• The Madden Gas Plant
• Big Supplies of CO2 from the flue gas of several
  coal fired Power Plants in Wyoming
• Separation technology is critical

11

• CO2 Separation
• Key to economically viable CO2-based
• enhanced oil recovery.
• Amine absorption process 40/ton CO2
• 2.25/MCF CO2
• CO2-separation alone will add 18
• cost to each barrel of oil

12
Current Subprojects

• New CO2 absorbents and adsorbents
• Poly(ionic liquid) absorbents
• Carbonaceous adsorbent
• New processes for CO2 desorption
• New polymer membrane for CO2 separation
• Poly(ionic liquid) membrane
• Nanocomposite membrane

13
CO2 Sorbents

• To develop and test novel adsorbents and
  adsorption cycles or processes for capture of CO2
  using pressure or temperature-swing process
• To determine the impact of process parameters
  (cycle time, cycle configuration, temperature) on
  CO2 capture efficiency.
• To determine capital and power requirements by
  using simulation tools to scale up to appropriate
  size.
• To acquire sufficient process performance data
  for the adsorption processes developed so as to
  permit technical and economic assessment of the
  viability of adsorption technologies

14
Example of CO2 PSA Process
15
Issues of Current CO2 Sorbents

• High energy consumption
• Amine loss and degradation
• Equipment corrosion.
• Costly zeolites (80,000/ton)

16
Our Focus

• Low heat capacity
• Non-volatility
• No-corrosion
• Versatility
• Tailored capacity/properties
• Low cost

17
Our New CO2 absorbents and adsorbents
Poly(ionic liquid) absorbents - patent
pending Carbonaceous adsorbents - patent pending
18
Poly(ionic liquid)s for CO2 separation

• Unexpectedly, we found that simply making the
  ionic liquids based on imidazolium into polymeric
  forms significantly increased the CO2 absorption
  capacity compared with ionic liquids.
• With fast CO2 absorption and desorption rate,
  reversible desorption and feasibility to
  fabrication, these polymers are very prospect as
  sorbent and membrane materials for CO2
  separation.

19
CO2 absorption of poly(ionic liquid) based on
ammonium and their monomers
CO2 absorption of the poly(ionic liquid) based on
ammonium and imidazolium, their corresponding
monomers and an ionic liquid as a function of
time (592.3 mmHg CO2, 22 C).
20
Cycles of CO2 sorption and desorption
a
b
Ionic liquid
Faster sorption and desorption Reversible sorption
a
b
21
High CO2/nitrogen selectivity
22
Carbonaceous Adsorbents

• Much lower cost
• High capacity
• Tested in lab
• Plan to test in the UW power plant
• Patent pending

23
New CO2-desorption process

• Current approach- steam heating
• Low efficiency
• Deteriorate the sorbents, making the sorbents be
  used only for several cycles

Our New approach High Efficiency Do not affect
the sorbents sorbents can be numerous
cycles Patent pending
24
New Polymer membranes
25
Ionic Liquid Polymer Membrane
26
BPPOdp/10 nm-silica nanocomposite membranes
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Polymer-Carbon Nanotube Membranes
28
Academic Achievement 10 refereed journal
papers 6 refereed preprints 1 paper
highlighted in Chemical and Engineering News

• Refereed Journals
• A..Blasig, X. Hu S. P. Tan J. Tang Y. Shen, M.
  Radosz, Carbon Dioxide Solubility in Polymerized
  Ionic Liquids Containing Ammonium and Imidazolium
  Cations from Magnetic Suspension Balance
  PVBTMABF4 and PVBMIBF4, submitted to
  Industrial Engineering Chemistry Research.
• H. Cong, X. Hu, J. Tang, M. Radosz, Y. Shen,
  Nanocomposite membranes of brominated
  poly(2,6-diphenyl-1,4-phenylene oxide) for gas
  separation, Industrial Engineering Chemistry
  Research, accepted
• H. Cong, J. Zhang, M. Radosz, Y. Shen, Carbon
  nanotube composite membranes of brominated
  poly(2,6-diphenyl-1,4-phenylene oxide) for gas
  separation, Journal of Membrane Science,
  submitted.
• X. Hu, H. Cong, Y. Shen, M. Radosz,
  Nanocomposite membranes for CO2 separations
  Silica/brominated poly(phenylene oxide)"
  Industrial Engineering Chemistry Research,
  accepted.
• H. Cong, M. Radosz, B. F. Towler, Y. Shen,
  Polymer-inorganic nanocomposite membranes for gas
  separation, Separation and Purification
  Technology, in press.
• X. Hu, J. Tang, A. Blasig, Y. Shen, M. Radosz,
  CO2 permeability, diffusivity and solubility in
  polyethylene glycol-grafted polyionic membranes
  and their CO2 selectivity relative to methane and
  nitrogen. Journal of Membrane Science 2006, 281,
  130-138.
• J. Tang, W. Sun, H. Tang, M. Radosz, Y. Shen,
  Low pressure CO2 sorption in ammonium based
  poly(ionic liquid)s, Polymer, 2005, 46,
  12460-12467.
• J. Tang, W. Sun, H. Tang, M. Radosz, Y. Shen,
  Poly(ionic liquid)s as new materials for CO2
  absorption, Journal of Polymer Science Part A
  Polymer Chemistry, 2005, 43, 5477-5489.
• J. Tang, H. Tang, W. Sun, H. Plancher, M. Radosz,
  Y. Shen, Poly(ionic liquid) A new material for
  enhanced and fast absorption of CO2, Chemical
  Communication, 2005, 3325-3327 (also introduced
  in Chemical Engineering Newss cover story
  Membranes For Gas Separation 2005, 83 (40)
  49-57).
• J. Tang, H. Tang, W. Sun, M. Radosz, Y. Shen,
  Enhanced CO2-absorption of poly(ionic liquid)s,
  Macromolecules 2005, 38, 2037-2039.
• Refereed Preprints
• H. Cong, X. Hu, M. Radosz, Y. Shen. Silca
  nanocomposite membranes of poly(2,6-dimethyl-1,4-p
  henylene oxide) derivatives for gas separation.
  PMSE Preprints 2006, 95, 338-339.
• X. Hu, J. Tang, A. Blasig, A, Y. Shen, M. Radosz.
  Grafted poly(ionic liquid) membranes for CO2
  separation. PMSE Preprints 2006, 95, 268.
• J. Tang, H. Tang, W. Sun, M. Radosz, Y. Shen.
  Carbon dioxide absorption of poly(ionic liquid)s
  with different ionic structures. PMSE Preprints
  2005, 93 1006-1007.
• H. Cong, J. Tang, M. Radosz, Y. Shen. Synthesis
  of poly(ionic liquid)s by condensation
  polymerization. PMSE Preprints 2005, 93,
  546-547.
• J. Tang, H. Tang, W. Sun, M. Radosz, Y. Shen.
  Poly(ionic liquid)s novel materials for CO2
  absorption. PMSE Preprints 2005, 92, 681-682.
• J. Tang, H. Tang, W. Sun, M. Radosz, Y. Shen.
  CO2 absorption of polymers of ammonium-based
  ionic liquid monomers. PMSE Preprints 2005,
  92, 56-5

29
Proprietary Documents and Plans 1 patent is
granted 4 patents are pending Pilot testing
scheduled in the UW Power Plant (this spring if
the weather allows or summer)

• To determine the impact of process parameters
  (cycle time, cycle configuration, temperature) on
  CO2 capture efficiency
• To determine capital and power requirements from
  simulation to scale up
• To acquire performance data to permit technical
  and economic assessment