API Tech Data Book 9 th Edition For

API® Tech Data Book, 9 th Edition For the Improved Design and Operation of Petroleum Refineries

API® Tech Data Book 9 Technical Overview § An API Standard - Developed/Maintained under API Funding for over 50+ years. § Mission Statement: provide a critically reviewed compilation of the physical and thermodynamic data and correlations that are of most interest to petroleum refiners for process evaluation and equipment design § § § Provides the technical expert’s recommendations on what data and methods should be employed to accurately predict the phase equilibrium and thermophysical properties of chemical and refining streams. This information is necessary for the cost effective design of and for the safe and efficient operation of process units. Stewardship/Critical Review – API Technical Data Committee Over 10, 000 copies of the printed Data Book have been sold in the US and abroad Unmatched accuracy for key technical data used in the design and operation of chemical and refining facilities in the 9 th Edition: § Hydrocarbon – Water Solubilities § Physical Properties of Sulfur Containing Components § Petroleum Fraction Characterization § An educational tool in thermodynamics for the practicing Chemical Engineer

API® Tech Data Book 9 Product History § 1966 - First edition released § 1970 to 1997 – Five new editions based on twelve interim revisions § 1996 – Technical Data Committee decides to develop an electronic Data § § § § Book counterpart – RFP process completed in 1997 and contract awarded to EPCON International 1998 – First electronic version was introduced as the API Tech Database – 40% coverage of the Tech Data Book topics 1999 – 13 th revision package - the last update to the printed version 2001 – Version 2 electronic – 70% coverage of the Tech Data Book topics 2002 – Version 3 electronic – 100% coverage of the Tech Data Book topics (distribution of the printed 6 th Edition is discontinued) 2005 – The 7 th Edition marks the completion of the re-mastering process of the Data Book into searchable text format and the 4 th version of the software interface (first new, printed Data Book available since 1999). 2007 – The 8 th Edition released as the 40 th Anniversary Edition 2009 – Version 8. 1 with all data book updates released. 2013 – Version 9 with all new software components will be released

Current API Technical Data Committee Membership § § § API® Tech Data Book 9 Cal Spencer, Chair (KBR) David Bluck (Invensys) Joel Glassett (BP) Jack Heidman (Exxon. Mobil) Homy Maerefat (CBI/Lummus) Patrick Malone (Shell Global Solutions) Paul Mathias (Fluor) Henry Ren (Chevron) Greg Cantley (Marathon Petroleum) Howard Wilson (Phillips 66) Todd Willman (EPCON International, ex-officio) Duane Brown (API Staff Support)

API® Tech Data Book 9 Technical Coverage Volume I - General Properties and Characterization Chapter 1 - General Data Chapter 2 - Characterization of Hydrocarbons Chapter 3 - Petroleum Fraction Distillation Interconversions Chapter 4 - Critical Properties Chapter 5 - Vapor Pressure Chapter 6 – Density Volume II - Thermal Properties and Phase Equilibria Chapter 7 - Thermal Properties Chapter 8 - Vapor-Liquid Equilibrium K-Values Chapter 9 - Phase Equilibria in Systems Containing Water Volume III - Surface & Transport Properties and Combustion Chapter 10 - Surface and Interfacial Tension Chapter 11 - Viscosity Chapter 12 - Thermal Conductivity Chapter 13 - Diffusivity Chapter 14 - Combustion Chapter 15 - Adsorption Equilibria Chapter 16 – Software Applications

API® Tech Data Book 9 API Funded Data Book Development § 1959 to 1999 Conducted at Pennsylvania State University § Principal Investigators: Fenske, Braun, Daubert, Danner § Total API funding of $3. 5 MM § 2000 to 2013 § Total API funding of $900 K+ § Core research of $50 K-$75 K each year § Development/Maintenance revision handled by • EPCON International – oversees all software and data revisions • Sr. Consultant: Costa Tsonopoulos (Exxon, 20 year Technical Data Committee member, Chairman 1999 -2000) • Membership in DIPPR Over $4 MM in Direct Research & Development Funded by API

API® Tech Data Book 9 API Funded Related Research § 1989 to 1995 § § § 1989 to 1994 § § § Crude Oil Characterization Study $750 K 1996 to 1997 § § § VLE of prototype systems at Hydroprocessing conditions (H 2, NH 3, H 2 S, H 2 O in Hydrocarbons/Oils) $250 K 1989 to 1998 § § § Phase equilibrium on Oxygenates (MTBE, TAME, ETBE) in Hydrocarbons and prototype Gasolines $315 K Reid Vapor Pressure data on prototype petroleum products and crude oils $50 K 2000 to 2005 § § Phase equilibrium of sulfur compounds in gasoline/diesel $175 K

API® Tech Data Book 9 API Funded Related Research (2) § 2011 to 2013 § § § Phase equilibrium of Mercury - Light Naphtha systems $20 K 2012 to 2013 § § Improved correlation for viscosity of Heavy Oils (+1000 ºF NBP) $150 K Over $2 MM in Related Research Funded by API and its Members

API® Tech Data Book 9 API TDB Corporate Licensees Corporate – Unlimited Use § § § § § Bechtel (1999 -2009) BP (1998 -2013) Chevron (1999 -2013) Citgo (1999 -2013) Conoco. Phillips (1998 -2013) Foster Wheeler (1999 -2013) KBR (1998 -2013) Marathon (1998 -2013) Phillips 66 (2008 -2013) Shell Oil (1998 -2013) Over $1 MM in Software Development funded by EPCON using Licensing Fees

API® Tech Data Book 9 Common Uses for API Tech § § § § Independent cross-check of process simulator results Research and development tool for conceptual design and feasibility studies User-friendly design tool for engineers who infrequently use simulation software Can be used as a basis for guarantees, commodity transfer, etc. as a commonly accepted industry standard Useful in companies without readily available/timely technical support through a central engineering group Good estimation tool for refineries and operating facilities (allows consistency with the central office) Education/Training tool for young engineers and undergraduates in chemical engineering programs Low-cost alternative for the consulting engineer to provide highly accurate flash and mixture properties of chemical and petroleum streams

API® Tech Data Book 9 Example Data Book Strength 1. Thermal Conductivity (API Crude Oil Characterization Study in 2000 – closest shown blue) Sample: San Joaquin Valley Crude Temp, F Experimental Btu/hr-ft-F API Tech 8 Btu/hr-ft-F Simulator 1 Btu/hr-ft-F Simulator 2 Btu/hr-ft-F Simulator 3 Btu/hr-ft-F SG=. 9483 BP=696 F 104 212 302 . 0694. 0658. 0626 . 0729. 0684. 0670 . 0627. 0587. 0552 . 0975. 0912. 0858 . 0602. 0564. 0531 SG=. 9872 BP=926 F 104 212 302 . 0747. 0704. 0665 . 0768. 0721. 0681 . 0585. 0554. 0527 . 1019. 0964. 0916 . 0556. 0527. 0501

API® Tech Data Book 9 Example Data Book Strength 2. Kinematic Viscosity (API Crude Oil Characterization Study in 2000 – closest shown blue) Sample: Composite Petroleum Cut Temp, F Experimental c. S API Tech 8 c. S Simulator 1 c. S Simulator 2 c. S Simulator 3 c. S SG=. 973 BP=1127 212 302 81. 4 14. 8 70. 5 14. 8 470. 0 115. 4 76. 0 21. 1 444. 6 95. 8 SG=. 9872 BP=926 F 158 212 302 46. 0 16. 8 5. 4 30. 8 13. 3 5. 1 1169. 7 373. 4 93. 9 41. 6 21. 4 9. 9 18554 4185 556

API® Tech Data Book 9 Example Data Book Strength 3. Hydrogen Solubility (comparison to experimental data from several sources) System: Temp, F Pressure, psia Experimental Liq. mol. frac. Predicted Liq. mol. frac % deviation Hydrogen – n-Butane 10 40 75 822 2390 1130 . 04. 111. 062 . 0361. 110. 0648 -9. 75 -. 90 4. 52 Hydrogen – n-Hexane 100 160 650 1000 . 04. 064 . 0373. 0684 -7. 50 6. 88 Hydrogen – n-Decane 372. 7 726 1463. 7 . 0678. 131 . 0648. 121 -4. 42 -7. 63 Hydrogen Cyclohexane 137. 9 211. 7 348. 1 390. 2 636. 7 . 01247. 01785. 02951 . 0117. 0168. 0276 -6. 17 -5. 88 -6. 47 Hydrogen Benzene 320 500 1500 . 0175. 0592 . 0185. 0604 5. 72 3. 43

API® Tech Data Book 9 Example Data Book Strength 4. Mutual Solubilities of Water-Hydrocarbon Systems § Can be Calculated on 3 Platforms in the API Tech Data Book § Direct Solubility Equation (semi-empirical, temperature dependent correlation) § NRTL (Flash/Mixture Calculations) § SRK-Kabadi-Danner (Flash/Mixture Calculations) § § The Solubility Equation provides the best fit of the experimental data (i. e. the correct answer) NRTL parameters for 100+ hydrocarbons and water have been highly tuned to fit the experimental data and essentially provide the same results of the Solubility Equation plus extremely accurate solubility for: § Mixtures versus pure components § Pressures other than Atmospheric § Temperatures other than Ambient § SRK-KD provides reasonable estimates for Water-Hydrocarbon when accurate NRTL parameters are not available

API® Tech Data Book 9 Water – Propane Solubilities Data Type Water in Propane (mole%) Propane in Water Experimental Data . 184 . 0202 API Solubility Equation . 186 . 0200 API-NRTL . 186 . 0200 API-SRK-KD . 250 . 0270 (140 Deg. F)