1. Opening new doors with Chemistry THINK SIMULATION! Electrolyte Modeling Basics Process Simulation OLI Systems, Inc.

2. THINK SIMULATION Think simulation 2 Agenda  Introductions  Overview of Process Simulation  The basic OLI Process (Neutral 1) ■ Essentials ■ Controllers ■ Recycles  Sour Gas Sweetening  Simple Crude Distillation  OLI Pro (Neutral 1 again)

3. THINK SIMULATION Think simulation 3 Introductions  OLI Staff ■ Jim Berthold – Director of Customer Support ■ Robert Young – Director of product support ■ Chris Depetris – Director of product development ■ Hongang Zhao – OLI Engine Support  AQSim ■ Pat McKenzie – Director of OLI Business Development ■ AJ Gerbino – Senior Partner  Attendees

4. THINK SIMULATION Think simulation 4 Overview of Process Simulation  OLI Supports several Process Simulators ■ Aspen PLUS ■ Aspen Hysys ■ IDEAS ■ gProms ■ OLI ◊ESP ◊OLI Pro ■ ProII ■ Unisim

5. THINK SIMULATION Think simulation 5 Overview of Process Simulation  We will discuss only the OLI Simulators ■ Environmental Simulation Program (ESP) ■ OLI Pro ■ Analyzers

6. THINK SIMULATION Think simulation 6 Overview of Process Simulation  ESP ■ Development started in 1990 ■ Funded by a consortium of companies ◊Aker Kvaerner (formerly Davy McKee) ◊Chevron ◊Dupont ◊ExxonMobil (formerly Exxon) ◊ICI ◊Shell ■ Development Continues

7. THINK SIMULATION Think simulation 7 Overview of Process Simulation  OLI Pro ■ Created from Honeywell’s Unisim Design ◊Updated as Unisim is updated ■ Contains all of the OLI thermodynamics ■ Does not contain all of OLI’s specialized unit operations

8. THINK SIMULATION Think simulation 8 Overview of Process Simulation  OLI has a vast experience in simulation ■ Upstream flow assurance ■ Subsurface flow modeling ■ Acid gas scrubbing ■ Organic pollutant stripping ■ Dynamic pH control ■ Biological treatment ■ Crude distillation ■ More…

9. THINK SIMULATION Think simulation 9 The basic OLI Process (Neutral1)

10. THINK SIMULATION Think simulation 10 The basic OLI Process (Neutral1)  We will be using ESP ■ Defining the chemistry model ■ Create the process ◊Mix block ◊Phase separate block ◊pH neutralizer block’ ■ Run the process ■ Review the results

11. THINK SIMULATION Think simulation 11 The basic OLI Process (Neutral1)

12. THINK SIMULATION Think simulation 12 The basic OLI Process (Neutral1)  Controllers  Frequently the adjustment of pH requires the Neutralizer Block to perform a difficult calculation. ■ The calculation is difficult because the set point of the Neutralizer may be on the steep part of the titration curve. ■ There may be significant phenomenological changes that occur while the unit is adjusting the pH.

13. THINK SIMULATION Think simulation 13 The basic OLI Process (Neutral1)  Controllers ■ Frequently the Neutralizer Block is not a suitable block because: ◊To control the pH you must adjust another upstream or downstream block ◊You need to control something other than pH ◊The set point may be an impossible case.

14. THINK SIMULATION Think simulation 14 The basic OLI Process (Neutral1)  Controllers ■ Frequently the Neutralizer Block is not a suitable block because: ◊To control the pH you must adjust another upstream or downstream block ◊You need to control something other than pH ◊The set point may be an impossible case.

15. THINK SIMULATION Think simulation 15 The basic OLI Process (Neutral1)  Controllers ■ Some other parameters that can be controlled are: ◊pH ◊Temperature ◊Pressure ◊Flow ◊Concentration ◊Oxidation/Reduction Potential

16. THINK SIMULATION Think simulation 16 The basic OLI Process (Neutral1)  Phase change limitations to pH control

17. THINK SIMULATION Think simulation 17 The basic OLI Process (Neutral1) Feed contains H 2 O Cl 2 CO 2 Scrubbed with NaOH

18. THINK SIMULATION Think simulation 18 The basic OLI Process (Neutral1) Cl 2(vap) = Cl 2(aq) Cl 2(aq) + H 2 O = H + + Cl - + HClO (aq) HClO (aq) =H + +ClO - As the pH increases with added NaOH, all these equilibria are shifted to the right. This scrubs the chlorine CO 2(vap) =CO 2(aq) CO 2(aq) +H2O=H + +HCO 3 - HCO 3 - =H + +CO 3 -2 HCO 3 - +Na + =NaHCO 3(s) But these equilibria are also shifted to the right.

19. THINK SIMULATION Think simulation 19 The basic OLI Process (Neutral1) Cl 2(vap) = Cl 2(aq) Cl 2(aq) + H 2 O = H + + Cl - + HClO (aq) HClO (aq) =H + +ClO - CO 2(vap) =CO 2(aq) CO 2(aq) +H2O=H + +HCO 3 - HCO 3 - =H + +CO 3 -2 HCO 3 - +Na + =NaHCO 3(s) As a species concentration becomes fixed by the equilibrium, then the pH remains constant.

20. THINK SIMULATION Think simulation 20 The basic OLI Process (Neutral1)  Controller ■ Remove the pH neutralizer ■ Add a manipulate block to control NaOH addition ■ Add a new mixer block to mix the separated liquid with the manipulated NaOH ■ Add a control block  Run the process  Review the results

21. THINK SIMULATION Think simulation 21 The basic OLI Process (Neutral1)

22. THINK SIMULATION Think simulation 22 The basic OLI Process (Neutral1)  Adding Recycle Loops ■ Frequently a process recycles part or all of certain streams back to up-stream units. ■ There are many reasons for using a recycle stream. ◊minimization of waste ◊increase of residence time ◊purification of product.

23. THINK SIMULATION Think simulation 23 The basic OLI Process (Neutral1)  Recycle Loops ■ Modify chemistry model ■ Add mix block for halite addition ■ Add a split block ■ Connect recycle stream to original mix block  Run process  Review results ■ How much “Caustic Reagent” was used? ◊More than in no-recycle case? ◊Less?

24. THINK SIMULATION Think simulation 24 Sour Gas Sweetening

25. THINK SIMULATION Think simulation 25 Sour Gas Sweetening  This application brief presents the case of sweetening (purifying) a sour gas from a natural gas well.  Several unit operations are employed to simulate a typical gas sweetening process configuration.  Once the sour gas components have been removed, the scrubbing liquor is regenerated to remove captured sour components.  These components are corrosive and metal selection can be an issue.

26. THINK SIMULATION Think simulation 26 Sour Gas Sweetening  For this example we will take a natural gas stream is approximately two mole percent (mol%) sour. ■ This means that for every 100 moles of gas there are 2 moles of hydrogen sulfide (H2S). ■ In addition to H2S, it is desirable to remove carbon dioxide (CO2) since this constituent lowers the heating value of the gas and increases the volume of gas that must be transported. ■ Most all alkanolamine plants are designed to maximize the removal of both of these “acid” gases.  In a typical gas cleaning plant, natural gas is fed to an absorber operating at high pressure. ■ The gas is scrubbed using an approximately 58 weight percent (wt%) diethanolamine (DEA) solution. ■ The scrubbed “sweet” gas is sent on for further processing or drying and transport via pipeline.

27. THINK SIMULATION Think simulation 27 Sour Gas Sweetening  The rich DEA solution exiting the absorber is sent to a flash drum operating at a much lower pressure. ■ This step removes any light-end hydrocarbons that were captured in the absorber. ■ The light-end gases are sent on for further processing.  Next, the hydrocarbon-free DEA solution is fed to a regeneration column. ■ Here heat is applied to strip the acid gas components out of the DEA solution. ■ Make-up water and DEA are added to maintain the lean 58 wt% DEA solution. ■ This solution is then recycled to the absorber.

28. THINK SIMULATION Think simulation 28 Sour Gas Sweetening  Why does adding DEA remove CO 2 and H 2 S? ■ The absorption of hydrogen sulfide gas follows these equilibria: ◊H 2 S (vap) = H 2 S (aq)(1) ◊H 2 S (aq) = H + + HS - (2) ◊HS - (aq) = H + + S -2 (3) ■ Adding a basic reagent such as DEA increases the pH of the solution. pH is defined as: ◊pH = - log a H+ (4) ■ where aH+ is the activity of the hydrogen ion. The activity of the hydrogen ion is defined as: ◊a H+ =  H+ [H+](5)

29. THINK SIMULATION Think simulation 29 Sour Gas Sweetening  Carbon dioxide follows a similar equation path: ■ CO 2 (vap) = CO 2 (aq)(6) ■ CO 2 (aq) + H 2 O = H + + HCO 3 - (7) ■ HCO 3 - = H + + CO 3 2- (8)

30. THINK SIMULATION Think simulation 30 Sour Gas Sweetening  Where does the basic reagent come from? ■ Adding DEA ((C2H5O)2NH) to a solution will make it more basic: ◊(C2H5O)2NH + H2O = (C2H5O)2NH2+ + OH-(9) ◊H2O = H+ + OH-(10) ■ Adding DEA to the solution forces water to dissociate (Eq. 10). ■ The hydrogen ion is complexed with the DEA molecule to create a protonated species and leaving free hydroxide ions. ■ This increases the pH and all of the vapor-liquid equilibria described above (by Equations 1, 2, 3, 5, 6 and 7) will shift to the right.

31. THINK SIMULATION Think simulation 31 Sour Gas Sweetening  There is a secondary equilibrium involving DEA carbamate ((C2H5O)2NCO2-): (C 2 H 5 O) 2 NH + HCO 3 - = (C 2 H 5 O) 2 NCO 2 - + H 2 O(11) ■ This species is stable at low temperatures and helps to remove carbon dioxide from the natural gas.

32. THINK SIMULATION Think simulation 32 Sour Gas Sweetening  Steps to create the process ■ New Process ■ New Chemistry ■ Build the process ■ Run the process ◊Select Tear(s) ■ Evaulate results

33. THINK SIMULATION Think simulation 33 Simple Crude Distillation  Overview ■ In this demonstration we will distill a typical crude using a simple distillation scheme with a single side stripper. ◊The OLI approach to modeling distillation is to rigorously account for the effects of water in the oil and also consider the effects of salts in both the water and oil phases. ◊Most other simulators only consider the water phase as a pure phase. ◊Our approach will allow us to model such species as chlorides and amine salts entrained and dissolved in the process streams.

34. THINK SIMULATION Think simulation 34 Simple Crude Distillation  Back Story ■ Our example considers a crude oil after it has left the production field. ◊In our case we have a relatively young well that has produced 100,000 barrels of oil per day. ◊10,000 barrels of this oil are produce water. In a “Real” sample, this produced water will consist of many different cations and anions as well as dissolved gases. ◊These dissolved species can cause a host of problems such as fouling, scaling and corrosion.

35. THINK SIMULATION Think simulation 35 Simple Crude Distillation  Back Story Continued… ■ In our example, the formation from which the oil was produced is essentially just a salt dome (NaCl). Our oil and our produced water will be saturated with halite. The chloride ion can be a problem downstream. ■ In normal processing this oil will be sent to an electrostatic desalter where the oil is washed and most of the salt is dissolved into the water phase. ◊The problem with the wash water is that it also may contain significant amounts of salt which are the introduced to the refinery. ■ The crude is usually maintained at moderate temperatures (150 oF to 250 oF) and at pressures sufficient to prevent boil-off (usually 75 PSI above saturation pressure). ■ The pH of the desalted crude is maintained at pH’s near neutral to prevent emulsion formation. ■ The desired salt content of the crude is usually near 3.5 mg/L (1 pound per thousand barrels, PTB)

36. THINK SIMULATION Think simulation 36 Simple Crude Distillation  Desalter simulation… …or a funny thing happened on the way to the CDU

37. THINK SIMULATION Think simulation 37 Simple Crude Distillation  Salt Composition Stream: NACL FORMATION Temperature75 oFoF Pressure75PSIA Flow128200Lb/hr [1] [1] H2O0.83Mole fraction NACL0.17Mole fraction

38. THINK SIMULATION Think simulation 38 Simple Crude Distillation  Crude Feed Stream: OIL Temperature75 oFoF Pressure75PSIA Flow1.1538E+06Lb/hr [1] [1] CRUDE0.9658Mole fraction CH40.0003Mole fraction C2H60.0006Mole fraction C3H80.0086Mole fraction n-C4H100.0193Mole fraction i-C4H100.0054Mole fraction [1] [1] This is approximately 90,000 bbd

39. THINK SIMULATION Think simulation 39 Simple Crude Distillation  Wash water is added to the separator SIMPLE DESALTER at a rate that is 6 % of the volume of the mixed oil and water stream FORMATION CRUDE. This is approximately 6,000 bbd. Caustic is added to keep the pH in the 7.0 range.  The stream DESALTED CRUDE is the stream that we will use in the distillation simulation. The composition of the stream is shown in the table to the right. Stream: DESALTED CRUDE (a/k/a RAW CRUDE) Temperature250 oFoF Pressure110PSIA Flow1.16773E+06Lb/h (100,000 bbd) H2O0.0087Mole fraction CRUDE0.9097Mole fraction CH40.0028Mole fraction C2H60.0056Mole fraction C3H80.0081Mole fraction n-C4H100.0181Mole fraction i-C4H100.0051Mole fraction NA2O0.0165Mole fraction HCL0.0330Mole fraction Density1914.6Lb/m 3 Enthalpy-4.25003E+06Cal/lmol