Crude feed and product properties and data

Refinery Feedstocks & Products
Properties & Specifications

Updated: July 12, 2018
Copyright © 2017 John Jechura (jjechura@mines.edu)
2
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphalting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes

Topics
Quantity & Quality
 Chemical composition
 Distillation analyses
 Properties of distillation fractions
Products as defined by their properties & specifications
 Composition, boiling point ranges, and/or volatility
 Properties specific for certain distillation fractions
• Autoignition tendency – octane & cetane number
3

Quantity & Quality

Crude Oil as Refinery Feedstock
Crude Oil
 Complex mixture of hydrocarbons & heterocompounds
 Dissolved gases to non‐volatiles (1000oF+ boiling
material)
 C1 to C90
+
Composition surprisingly uniform
5
Element Wt%
Carbon 84 ‐ 87
Hydrogen 11 ‐ 14
Sulfur 0 ‐ 5
Nitrogen 0 ‐ 0.2
Other elements 0 ‐ 0.1

Primary Hydrocarbon Molecular Types
Paraffins
 Carbon atoms inter‐connected by single bond
 Other bonds saturated with hydrogen
Naphthenes
 Ringed paraffins (cycloparaffins)
 All other bonds saturated with hydrogen
Aromatics
 Six carbon ring (multiple bonding)
 Bonds in ring(s) are unsaturated
Olefins
 Usually not in crude oil
 Formed during processing
 At least two carbon atoms inter‐connected
by (unsaturated) double bond
6
n‐Hexane i‐Hexane
Cyclohexane Methylcyclopentane Decalin
Benzene Naphthalene
1‐Hexene trans‐3‐Hexene cis‐3‐Hexene
Drawings from NIST Chemistry WebBook, http://webbook.nist.gov/chemistry/

Example Heterocompounds
7
Composition & Analysis of Heavy Petroleum Fractions
K.H. Altgelt & M.M. Boduszynski
Marcel Dekker, Inc., 1994, pg. 16
Modeling and Simulation of Catalytic Reactors for Petroleum Refining.
by Jorge Ancheyta, John Wiley & Sons, 2011

Distribution of Compounds
8
Carbon Paraffin
No. °C °F Isomers
5 36 97 3 Gasoline
8 126 259 18
10 174 345 75
12 216 421 355
15 271 520 4347 Diesel & jet fuels, middle distillates
20 344 651 3.66E+05 Vacuum gas oil
25 402 756 3.67E+07 Atmospheric residue
30 449 840 4.11E+09
35 489 912 4.93E+11
40 522 972 6.24E+13
45 550 1022 8.22E+15
60 615 1139 2.21E+22 Vacuum residue
80 672 1242 1.06E+31
100 708 1306 5.92E+39 Nondistillable residue
Boiling Point
Examples
Composition & Analysis of Heavy Petroleum Fractions
K.H. Altgelt & M.M. Boduszynski
Marcel Dekker, Inc., 1994, pp. 23 & 45

Crude Oil Assay
Indicates distribution quantity & quality of crude oil feedstock
Definitions based upon boiling point temperature ranges
 Represents expected products from crude & vacuum distillation
Completeness of data depends upon source
Quality measures
 Specific / API gravity
 Sulfur content
 Octane number
 Cetane number
 Viscosity
 Carbon residue
9

97.8F
180F
330F
520F
650F
800F
1000F
Temperatures define the
boundaries between fractions
Mixed property values for the
entire fraction
12

Crude Oils Are Not Created Equal
13

Crude Oil Properties
Distillation analysis / Boiling point range
 Amount collected from batch distillation at the indicated temperature
 Standardized tests — ASTM 2892 (TBP), D86, D1160, …
• Most useful is TBP (True Boiling Point)
Specific gravity, o – ratio liquid density @ 60oF & 1 atm to that of water @ 60oF
& 1 atm
 Air saturated: 8.32828 lb/gal
 Pure Water: 999.016 kg/m³ = 8.33719 lb/gal
API gravity
Higher density  lower oAPI
Watson characterization factor
12 – 13 (paraffinic) to 10 (aromatic)
14
    
 
141.5 141.5
°API 131.5
131.5 °API
o
o


3
in units of °R
b
W b
o
T
K T

Crude Oil Properties
Classification based on gravity
 Light API > 38o
 Medium 38o > API > 29o
 Heavy 29o > API > 8.5o
 Very heavy API < 8.5o
Sulfur, nitrogen, & metals content
 All can “poison” catalysts
 Sulfur
• “Sour” vs. “sweet” — ~0.5 wt% cutoff
• Restrictions on sulfur in final products
 Nitrogen
• Usually tolerate up to 0.25 wt%
 Nickel, vanadium, copper
• Tend to be in the largest molecules/highest
boiling fractions
Properties appropriate for certain boiling
point ranges
 Octane number
 Cetane number
 Viscosities
 Carbon residue
15

Distillation Analysis Types
True Boiling Point (TBP) –
ASTM D2892
 14 to 18 theoretical stages
 Near infinite reflux (5:1 reflux
ratio min)
 No hotter than 650oF to
minimize cracking
• Max vapor temperature 410oF
 Pressure levels
• 760 mmHg (1 atm)
• 100 mmHg
• 2 mmHg (min)
16
ASTM D 2892‐13, Standard Test Method for Distillation of Crude Petroleum (15‐
Theoretical Plate Column)

ASTM D86
 Low resolution — no packing,
reflux from heat losses
 1 atm; no hotter than 650oF —
minimize cracking
 Correlations to correct to TBP
basis
17
http://www.koehlerinstrument.com/products/K45601.html
0
100
200
300
400
500
600
0 100 200 300 400 500
D86 Temperature [°F]
TBP
Temperature
[°F]

ASTM D1160
 Used on resids (650oF+)
 Relatively low resolution
 Vacuum conditions — 10 to 40
mmHg; no hotter than 1000oF
AEBP
 Correlations to correct to
atmospheric pressure & TBP
basis
18
http://www.lazarsci.com/d1160.htm

Short Path Distillation
 Single stage flash
 Extremely low pressures —
0.1 mmHg or less
 Characterize deep cut resids
19
http://www.chemtechservicesinc.com/short‐path‐distillation.html

Simulated Distillation – ASTM D 2887, D 6352, D 7169
 Relatively low resolution gas chromatography
• Several thousand theoretical stages
 Essentially TBP temperatures — wt% basis
• Temperatures inferred from elution times
• Calibrated with n‐paraffin mixture
20

Crude Oil Assay – Hibernia (from Chevron site)
21
http://crudemarketing.chevron.com/cr
ude/north_american/hibernia.aspx
Whole Light Medium Heavy Kero Atm Light Heavy Vacuum Atm
Crude Naphtha Naphtha Naphtha Gas Oil VGO VGO Resid Resid
TBP Temp At Start, °C Start 10 80 150 200 260 340 450 570 340
TBP Temp At End, °C End 80 150 200 260 340 450 570 End End
TBP Temp At Start, °F Start 55 175 300 400 500 650 850 1050 650
TBP Temp At End, °F End 175 300 400 500 650 850 1050 End End
Yield at Start, vol% 2.3 8.0 20.8 30.0 39.5 54.0 73.2 85.8 54.0
Yield at End, vol% 8.0 20.8 30.0 39.5 54.0 73.2 85.8 100.0 100.0
Yield of Cut (wt% of Crude) 4.4 11.5 8.5 9.1 14.6 20.0 13.7 16.7 50.4
Yield of Cut (vol% of Crude) 5.6 12.9 9.2 9.5 14.6 19.1 12.6 14.2 46.0
Gravity, °API 33.5 81.9 54.8 47.3 40.2 33.9 27.3 20.2 10.0 19.6
Specific Gravity 0.86 0.66 0.76 0.79 0.82 0.86 0.89 0.93 1.00 0.94
Sulfur, wt% 0.53 0.00 0.00 0.01 0.05 0.27 0.57 0.91 1.46 0.96
Mercaptan Sulfur, ppm 0 0 0 1
Nitrogen, ppm 1384 0 0 0 1 56 579 2050 5860 2729
Hydrogen, wt% 16.2 13.9 14.2 13.7 13.2 12.9 12.5
Viscosity @ 40 °C (104 °F), cSt 6.73 0.48 0.67 1.04 1.72 4.10 19.04 3.05E+02 4.E+05 2.89E+02
Freeze Point, °C 51 -122 -96 -68 -39 -2 30 53 78 63
Freeze Point, °F 125 -188 -141 -90 -39 28 87 128 172 146
Pour Point, °C 7 -128 -101 -71 -42 -7 26 48 35 36
Pour Point, °F 44 -198 -151 -96 -43 20 79 119 95 96
Smoke Point, mm (ASTM) 7 35 32 27 22 17 11 5 2 4
Aniline Point, °C 77 71 53 55 61 70 84 95 106 94
Aniline Point, °F 171 160 127 131 142 159 183 204 222 201
Total Acid Number, mg KOH/g 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Cetane Index, ASTM D4737 40 47 56
Diesel Index 57 131 70 62 57 54 50 41 22 39
Characterization Factor (K Factor) 12.0 12.6 11.7 11.8 11.8 11.8 12.0 12.0 12.1 12.0
Research Octane Number, Clear 71.8 64.1 37.3
Motor Octane Number, Clear 70.3 62.5
Paraffins, vol% 84.9 48.8 45.4 38.6
Naphthenes, vol% 15.1 32.4 39.5 40.9
Aromatics, vol% 0.0 18.8 14.9 20.0
Thiophenes, vol%
Molecular Weight 244 102 115 144 175 226 319 463 848 425
Gross Heating Value, MM BTU/bbl 5.88 4.84 5.37 5.55 5.72 5.87 6.04 6.23 6.50 6.24
Gross Heating Value, kcal/kg 10894 11589 11212 11121 11009 10896 10765 10595 10310 10582
Gross Heating Value, MJ/kg 45.6 48.5 46.9 46.5 46.1 45.6 45.0 44.3 43.1 44.3
Heptane Asphaltenes, wt% 0.1 0.6 0.2
Micro Carbon Residue, wt% 2.6 14.8 5.2
Ramsbottom Carbon, wt% 2.3 13.2 4.6
Vanadium, ppm 1 5 2
Nickel, ppm 1 4 1
Iron, ppm 1 3 1
Simple analysis

Crude Oil Assay – Hibernia (from ExxonMobil site)
22
HIBER11Z
Whole
crude ‐
200 to
1499
Butane
and
Lighter ‐
200 to 60
Lt.
Naphtha
C5‐ 165F
60 to 165
Hvy
Naphtha
165 ‐
330F 165
to 330
Kerosene
330 ‐
480F 330
to 480
Diesel
480 ‐
650F 480
to 650
Vacuum
Gas Oil
650 ‐
1000F
650 to
1000
Vacuum
Residue
1000F+
1000 to
1499
Cut volume, % 100 1.51 5.68 14.83 14.76 17.03 28.89 17.29
API Gravity, 33.9 121.42 81.02 54.91 43.1 34.04 24.71 12.65
Specific Gravity (60/60F), 0.8555 0.5595 0.6658 0.7591 0.8104 0.8548 0.9058 0.9816
Carbon, wt % 82.43 83.95 85.88 86.21 86.51 86.39
Hydrogen, wt % 17.57 16.05 14.12 13.77 13.23 12.81
Pour point, F 37 ‐62 17 103 103
Neutralization number (TAN), MG/GM 0.095 0.054 0.116 0.212
Sulfur, wt% 0.54 0.0011 0.0213 0.2431 0.6814 1.4428
Viscosity at 20C/68F, cSt 12.49 0.35 0.41 0.75 1.79 6.88 120.83 472934.04
Mercaptan sulfur, ppm 1 1.5 2.1
Nitrogen, ppm 1350 0 0 0 0.2 88.5 1196.1 4868
CCR, wt% 2.45 0 0.26 11.9
N‐Heptane Insolubles (C7 Asphaltenes), wt% 0.3
Nickel, ppm 1.3 0 0 6.5
Vanadium, ppm 0.7 0 0 3.5
Calcium, ppm 0.5
Reid Vapor Pressure (RVP) Whole Crude, psi 3.4
Heat of Combustion (Gross), BTU/lb 19429
Heat of Combustion (Net), BTU/lb 18222 19288 18852 18626 18567
Hydrogen Sulfide (dissolved), ppm 0
Salt content, ptb 0.1
Paraffins, vol % 100 84.28 51.64 47.08 41.83 26.36
Naphthenes, vol % 0 14.13 31.88 32.71 34.07 37.12
Aromatics (FIA), vol % 16.48 16.9
Distillation type, D‐ 1160 86 86 86 86 86 1160 1160
ASTM IBP, F 17.9 ‐127.8 95.9 208.1 363.8 506 690.6 1038.8
5 vol%, F 135.3 ‐94.6 101.4 213.7 368.2 510.8 695.2 1043.4
10 vol%, F 201.5 ‐52.1 106 216.6 370.4 512.9 706.3 1055.3
20 vol%, F 306.9 10.5 110.9 223.6 375.5 518.9 728.3 1081.3
30 vol%, F 403.1 29.8 114.6 231.7 381.8 526.3 752.6 1111.3
40 vol%, F 497.7 35.9 117.1 240.8 389.1 535.3 778.5 1145.4
50 vol%, F 597 35.8 121.9 249.1 396.4 543.8 806.4 1183.7
60 vol%, F 705 38.8 129 258.8 405.1 553.8 835.7 1228.7
70 vol%, F 806.7 43.7 134.1 269 414 564.5 865.7 1277.3
80 vol%, F 925.9 47.3 139.3 279.9 423.8 576 897.7 1330.3
90 vol%, F 1082.4 46.1 141.8 291.1 434 587.8 929 1385.2
95 vol%, F 1213.2 46.1 144.4 297.4 439.8 594.4 947.8 1419.1
ASTM EP, F 1401.5 47.2 147 302.5 444.5 605 969.7 1458
Freeze point, F ‐48.2 29
Smoke point, mm 21.3
Naphthalenes (D1840), vol% 4.4
Cetane Index 1990 (D4737), 33.1 152.4 44.1 29.4 43.8 54.1 56.9 45.5
Cloud point, F ‐54 24
Aniline pt, F 138.2 161.3 191.7
Simple analysis &
comparison
http://www.exxonmobil.com/crudeoil/a
bout_crudes_hibernia.aspx

Comparison of Chevron & ExxonMobil Assays
23

Comparison of Chevron & ExxonMobil Assays
24

Crude Oil Assay – Bakken vs. other light crudes
25
Property Bakken WTI
API Gravity 41 39
Sulfur, wt% 0.2 0.32
Distillation Yield, volume %
Lt Ends C1‐C4 3.5 3.4
Naphtha C5‐360 °F 36.3 32.1
Kerosene 360‐500 °F 14.7 13.8
Diesel 500‐650 °F 14.3 14.1
Vacuum Gas Oil 650‐1050 °F 26.1 27.1
Vacuum Residue 1050+ °F 5.2 9.4
Bottoms Quality ‐‐ Vacuum Resid 1050+°F
Yield, Vol. % 5.2 9.4
API Gravity 14 11.4
Sulfur, Wt. % 0.75 1.09
Vanadium, ppm 2 87
Nickel, ppm 7 41
Concarbon, Wt. % 11.3 18.2
http://www.turnermason.com/Publications/petroleum‐
publications_assets/Bakken‐Crude.pdf
Hill, D., et.al.
North Dakota Refining Capacity Study, Final Technical Report
DOE Award No. DE‐FE0000516, January 5, 2011

Crude Oil Assay – Eagle Ford vs. other light crudes
26
METHODOLOGY AND SPECIFICATIONS GUIDE
The Eagle Ford Marker: Rationale and methodology
Platts, McGraw Hill Financial
October 2012
https://www.platts.com/IM.Platts.Content/MethodologyReferences/Method
ologySpecs/eaglefordmarker.pdf

Products as defined by their
properties & specifications

Petroleum Products
There are specifications for over
2,000 individual refinery products
 Took a full century to develop
markets for all fractions of crude
oil
Intermediate feedstocks can be
routed to various units to produce
different blend stocks
 Highly dependent on economics
specific to that refinery &
contractual limitations
28
Ref: Unknown origin. Possibly Socony‐Vacuum Oil Company, Inc. (1943)

Petroleum Products
Refinery Fuel Gas (Still Gas)
Liquefied Petroleum Gas (LPG)
 Ethane & Ethane‐Rich Streams
 Propanes
 Butanes
Gasoline
 Naphtha
Middle Distillates
 Kerosene
 Jet Fuel
 Diesel, Home Heating, & Fuel Oil
Gas Oil & Town Gas
Asphalt & Road Oil
Petroleum Coke
Lubricants
Wax
Petrochemicals
Sulfur
29
EIA, refinery yield data – updated April 12, 2018
http://tonto.eia.doe.gov/dnav/pet/pet_pnp_pct_dc_nus_pct_m.htm

Sources of Product Specifications
State & Federal regulatory agencies
 Environmental laws
 Reflect need to reduce pollution in
manufacturing & use of fuels
ASTM (American Society for Testing
and Materials) Specifications &
associated test procedures
 Specifications drafted considering
positions of industry & regulatory
agencies
Industry associations
 American Petroleum Institute
 Gas Processors Association
 Asphalt Institute
Between companies based on
“typical” specs
 Negotiated
 Deviations have predetermined
price adjustments
30

What Makes Gasoline Gasoline?
What Makes Diesel Diesel?
Gasoline
Must be a good fuel in a spark‐ignited internal
combustion engine
 Proper atomization & vaporization when mixed
with combustion air
 Boiling points of chemical species
 Boiling point range of mixture
 Ability to compress & not ignite prior to spark‐
ignition
• Measured as octane number
 Minimal combustion byproducts – want
complete combustion
Minimize environmental unfriendliness
 Volatility in storage tanks
• RVP – Reid Vapor Pressure
 Individual chemical species
• Sulfur content
• Benzene
Diesel
Must be a good fuel in a non‐spark‐ignited
fuel‐injected internal combustion engine
 Proper atomization when injected into
compressed air
 Boiling point range of mixture
 Ability to ignite when injected into compressed
air
• Measured as cetane number
 Minimal combustion byproducts – want
complete combustion
Minimize environmental unfriendliness
 Volatility in storage tanks
• Flash point
 Individual chemical species
• Sulfur content
31

Characteristics of Petroleum Products
32
Refining Overview – Petroleum Processes & Products,
by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000

Fuel Gas Specifications
Parameter Specification
Temperature Range 40F to 120F
Pressure 500 to 1,000 psig
Gross Heating Value 950 – 1150 BTU/scf
Hydrocarbon Dew Point1 10F – 20F
Water 4 or 7 lbs/million scf
Total Sulfur 5 to 20 grains/100 scf
Hydrogen Sulfide H2S 4 to 16 ppmv
Mercaptans 1 to 5 grains/100 scf
Total Nitrogen & CO2 4 mol%
CO2 (also Total N2 + CO2) 2 to 3 mol%
Oxygen 0.1 to 0.4 mole %
33
1At pipeline pressure

Liquefied Petroleum Gas (LPG)
Characteristic
Commercial
Propane
Commercial
Butane
ASTM Test
C3 & C3= C4 & C4= D1267‐02
Vapor Pressure @ 100F 208 70 D1267‐02
95 vol%@ max F ‐37F +36F D1837‐64
C4+ max 2.5% D2163‐77
C5+max 2.0% D2163‐77
34
Vapor pressure “spec” is actually an approximate guideline for defining the light ends content of the LPG mixture.

Natural Gasoline Specifications
Characteristic GPA Specifications ASTM Test
Reid Vapor Pressure 10 to 34 psig D‐323
Evaporation at 140F 25 to 85 % D‐216
Evaporation at 275F > 90 % D‐216
End Point D‐216
35

Aviation Gasoline Specifications
36

Motor Gasoline Specifications
37

Motor Gasoline Volatility Classes (ASTM D 4814‐13)
38

Other Gasoline Considerations
Reformulated gasoline (RFG) blended to
burn cleaner by reducing smog‐forming
and toxic pollutants
 Clean Air Act requires RFG used in cities
with the worst smog pollution
 Clean Air Act required RFG to contain 2
wt% oxygen
• MTBE & ethanol were the two most
commonly used substances
• MTBE legislated out of use because of
health concerns
• Oxygenate content regulation superceeded
by the Renewable Fuel Standard
RBOB – Reformulated Blendstock for
Oxygenate Blending
 Lower RVP to account for 1.5 psi increase
due to 10 vol% ethanol
Benzene content
 Conventional gasoline could have 1.0
vol% benzene (max) pre‐2011
 New regulations Jan 1, 2011 reduced
benzene in all US gasoline to 0.62 vol%
 Had been proposed by EPA under Mobile
Sources Air Toxics (MSAT) Phase 2
 Credit system for refiners that could not
meet the 0.62% limit
Sulfur content
 EPA calling for ultra low sulfur gasoline by
2017 – from 30 ppmw (Tier 2) to 10
ppmw (Tier 3)
39

What are Octane Numbers?
Tendency for auto‐ignition upon
compression
 Gasoline — bad
 Tendency of gasoline to cause
“pinging” in engine
 Higher octane number needed for
higher
compression ratios
Different types (typically RON > MON)
 RON — Research Octane Number
• Part throttle knock problems
 MON — Motor Octane Number
• More severe — high speed &
high load conditions
 (R+M)/2 – Road Octane Number
• Also known as AKI (Anti‐Knock Index)
• Reported at the pump in the U.S.
40
n‐Heptane  0 2,2,4‐trimethylpentane  100
(issoctane)

What is Reid Vapor Pressure (RVP)?
Specific test to measure volatility at
100oF (37.8oC)
Pressure at 100oF when liquid in
contact with air at volume ratio of 1:4
 Related to the true vapor pressure
 Similar to vapor formation in an
automobile’s gasoline tank
Usually just reported as “psi”
 Actually gauge pressure measured –
subtract off the contribution of the
atmospheric pressure
Relatively easy to measure
 Direct pressure measurement
instead of observation of bubble
formation
Procedures controlled by ASTM
standards (ASTM D 323)
 A: Low volatility (RVP less than 26
psi / 180 kPa)
 B: Low volatility – horizontal bath
 C: High volatility (RVP greater than
26 psi / 180 kPa)
 D: Aviation gasoline (RVP
approximately 7 psi / 50 kPa)
41

What are alternate RVP‐like tests?
ASTM D 5191 – Standard Test Method for Vapor Pressure of Petroleum Products (Mini
Method)
 Expand liquid from 32oF to 5 times its volume (4:1 volume ratio) at 100oF without adding air
 Referred to as the DVPE (Dry Vapor Pressure Equivalent) & calculated from measured
pressure value:
DVPE [psi] = 0.965 (Measured Vapor Pressure [psi]) – 0.548 [psi]
ASTM D 6378 – Standard Test Method for Determination of Vapor Pressure (VPX) of
Petroleum Products, Hydrocarbons, and Hydrocarbon‐Oxygenate Mixtures (Triple
Expansion Method))
 Expand liquid to three different volume ratios
 No chilling of initial sample – sample of known volume introduced to chamber at 20oC (76oF)
or higher
 Three expansions at a controlled temperature – 100oF equivalent to ASTM D5190
• Allows for the removal of the partial pressure effects from dissolved air
 RVPE (Reid Vapor Pressure Equivalent) calculated from correlation to measured pressure
minus dissolved air effects
42

Middle Distillates
General classifications
 Kerosene
 Jet fuel
 Distillate fuel oil
• Diesel
• Heating oil
Properties
 Flash point
 Cloud point / Pour point
 Aniline point
 Cetane number
 Viscosity
 Water & sediment
43

Diesel Cetane Number
One key to diesel quality
 Measures the ability for auto‐ignition (essentially the
opposite of octane number)
 References:
• n‐hexadecane (cetane)  100
• Isocetane (2,2,4,4,6,8,8‐heptamethylnonane)  15
 May be measured by test engine but frequently
approximated
• ASTM D 976 — Standard Test Methods for Calculated Cetane
Index of Distillate Fuels
• ASTM D 4737 — Standard Test Method for Calculated Cetane
Index by Four Variable Equation
Trends
 Cetane number had declined since the middle 1970s –
heavier crudes with higher aromatic content
 Trend starting to reverse because of tight oil from shale
formations
 More stringent emissions requirements necessitate
higher cetane numbers
44
Bowden, Johnston, & Russell, “Octane‐Cetane Relationship”,
Final Report AFLRL No. 33, March 1974,
Prepared by U.S. Army Fuels & Lubricants Research Lab & Southwest Research
Institute
0
5
10
15
20
25
70 80 90 100
Cetane
Number
(CN)
Octane Number (MON or RON)
RON Expression
MON Expression

What is Flash Point?
“… lowest temperature corrected to a pressure of 101.3 kPa (760 mm Hg) at
which application of an ignition source causes the vapors of a specimen of the
sample to ignite under specified conditions…”
Procedure strictly controlled by ASTM standards
 D 56 —Tag Closed Tester
 D 92 —Cleveland Open Cup
 D 93 —Pensky‐Martens Closed Cup Tester
 D 1310 — Tag Open‐Cup Apparatus
 D 3143 — Cutback Asphalt with Tag Open‐Cup Apparatus
 D 3278 —Closed‐Cup Apparatus
 D 3828 — Small Scale Closed Tester
 D 3941 — Equilibrium Method with Closed‐Cup Apparatus
45

OSHA Flammable Liquid Definitions
46
Category
Flash Point
°C (°F)
Boiling Point
°C (°F)
Class
Flash Point
°C (°F)
Boiling Point
°C (°F)
Flammable 1 < 23 (73.4) ≤ 35 (95) Flammable Class IA < 22.8 (73) < 37.8 (100)
Flammable 2 < 23 (73.4) > 35 (95) Flammable Class IB < 22.8 (73) ≥ 37.8 (100)
Flammable Class IC ≥ 22.8 (73) & 37.8 (100)
Combustile Class II ≥ 37.8 (100) & < 60 (140)
Flammable 4 > 60 (140) & ≤ 93 (199.4) Combustile Class IIIA ≥ 60 (140) & < 93.3 (200)
None Combustile Class IIIB ≥ 93.3 (200)
GHS
(Globally Harmonized System)
Flammable and Combustible Liquids Standard
(29 CFR 1910.106)
Flammable 3 ≥ 23 (73.4) & < 60 (140)
Source: OHSA RIN1218‐AC20
https://www.federalregister.gov/articles/2012/03/26/2012‐4826/hazard‐communication#t‐8

What are Cloud & Pour Points?
Indicate the tendency to form solids at low temperatures – the higher the temperature
the higher the content of solid forming compounds (usually waxes)
Cloud Point
 Temperature at which solids
start to precipitate & give a
cloudy appearance
 Tendency to plug filters at
cold operating temperatures
Pour Point
 Temperature at which the oil
becomes a gel & cannot flow
47
Solidification of diesel fuel in a fuel‐filtering device after sudden temperature drop
“Consider catalytic dewaxing as a tool to improve diesel cold‐flow properties”,
Rakoczy & Morse, Hydrocarbon Processing, July 2013
Melting Points of selected long‐chain normal & iso paraffins
typically found in middle distillates

Additional Specifications
Sulfur
 Control of sulfur oxides upon combustion
 Three levels, reduction for the traditional five categories
Aniline Point
 Minimum temperature at which equal volumes of aniline (C6H5NH2) and the oil are
miscible
 The lower the aniline point the greater the aromatic content
Viscosity
 Fluidity during storage at lower temperatures
Sediment & water content
 Controlling contamination
48

Kerosene Specifications
Parameter Specification ASTM Test Method
Flash Point 100F ASTM D‐56
10% distilled, max 401F ASTM D‐86
Final Boiling Point 572F ASTM D‐86
No. 1 sulfur, max
0.04% (No. 1)
0.30% (No. 2)
ASTM D‐1266
Burn quality pass ASTM D‐187
49

Jet Fuel Specifications
50

Stationary Turbine Fuel & Diesel Classes
51
0‐GT Includes naphtha, jet fuel B & other volatile hydrocarbons
1‐GT Approximates No. 1 Fuel Oil (D 396) & 1‐D diesel (D 975)
2‐GT Approximates No. 2 Fuel Oil (D 396) & 2‐D diesel (D 975)
3‐GT Approximates No. 4 & No. 5 fuel oils
4‐GT Approximates No. 4 & No. 5 fuel oils
No. 1
Mostly from virgin stock. “Superdiesel.” Used for autos & high‐
speed engines.
No.2
Wider boiling & contains cracked stocks. Very similar to home
heating fuel (w/o additives).
No.4
Traditionally largest volume produced. Used for marine, railroads,
& other low to medium speed power plants

Diesel Specifications
52

Diesel Sulfur Content
Sulfur levels dropping because of air quality regulations
 Since 1993 diesel fuel formulated with 85% less sulfur
 Low Sulfur Diesel had been 500 ppm sulfur
 ULSD 15 ppm & required for
on‐road usage since
January 2007
Worldwide, sulfur specs
continuing to drop to
meet U.S. & European
standards
 For example, Uruguay at
50 ppm since 2014.
53
Global status of maximum allowable sulfur in diesel fuel, parts per million (June 2012)
“Saudi Arabia’s plan for near‐zero‐sulfur fuels”, Hydrocarbon Processing, March 2013

Distillate Fuel Oil
Only grades 1 and 2 have boiling range
specs (max)
No. 1 Fuel Oil – minor product
No. 2 Fuel Oil — domestic heating oil
 Similar to medium quality diesel 2‐D
 Made in the winter season in refineries
when automotive fuel demand is lower.
No. 3 Fuel Oil — not produced since 1948
No. 4 Fuel Oil —for industrial burner
installations with no preheat facility
 Sometimes a mixture of distillate &
residual material
 Lower viscosity heating oil
54
http://www.eia.gov/energyexplained/index.cfm?page=heating_oil_use

Residual Fuel Oils
No. 5 Fuel Oil — premium residual
fuel oil of medium viscosity, rarely
used
No. 6 Fuel Oil — heavy residual fuel
oil
 Vacuum resid & cutter stock mix (to
decrease viscosity)
 Common use
• Boilers for steam turbines of
stationary power plants
• Marine boilers — variation of Bunker
C
• Industrial & commercial applications
 Least valued of all refinery products
• Historically only liquid product worth
less than raw crude
55

Residual Fuel Oils
No. 6 Fuel Oil — Market has been declining in last 20 years
 More power plants use coal or natural gas
 Ships use diesel for marine diesels or gas turbines
 Environmental reductions in sulfur levels
 “Emission‐control areas” (ECAs) will shift to low‐sulfur (0.1 wt%) marine gasoil
(MGO) or marine diesel oil (MDO)
starting January 1, 2015 – U.S.,
Canada, Caribbean, & northern
Europe
 Other option on‐board
emissions‐scrubbing systems
56
“Methanol takes on LNG for future marine fuels”, Hydrocarbon Processing, May 2015

ASTM Fuel Oil Specs
57

Comparison Kerosene / Jet / Diesel / Heating Oil
58
Property No. 2 Kerosene Jet‐A Jet‐B No. 2D S15 No. 2D S500 No. 2HO S500
Cetane Number min 40 40
Aromatics [vol%] max 25 25 35 35
Sulfur [wt%] max 0.3 0.3 0.3 0.0015 0.05 0.05
Flash Point [°C] 38 52 52 38
Distillation (D 86)
T10 [°C] max 205 205
T20 [°C] max 145
T50 [°C] max 190
T90 [°C] min 282 282 282
[°C] max 245 338 338 338
EP [°C] max 300 300
Distillation Residue [vol%] max
Distillation Loss [vol%] max
Freezing Point [°C] max ‐40 ‐50
Pour Point [°C] max ‐6
Carbon Residue [wt%] 0.35 0.35 0.35
Kinematic Viscosity
@ 40°C mm²/s min 1.9 1.9 1.9
mm²/s max 4.1 4.1 4.1
ASTM Specifications for Middle Distillates

Comparison of Boiling Ranges
59

Gas Oil & Town Gas
Historical usage
 Gas oils used to make town gas for illumination
 Decomposed over a heated checker‐work
 Composed of carbon monoxide and carbon dioxide
• Low heating value
• Burned cleanly
• Easily distributed for illumination fuel
 Displaced kerosene in the cities — electricity ultimately eliminated its use
Gas oil no longer a consumer product
 Traded between refineries
 Feedstock for catalytic cracking & hydrocracking
60

Lubricant Terminology
61
Phrase Meaning
Lube basestock Lube product that meets all specifications & is suitable
for blending
Lube slate Set of lube basestocks, usually 3 to 5
Neutral lubes Obtained from a side cut of the vacuum distillation tower
Bright stock lubes Processed of vacuum resid from the vacuum tower
bottoms

Lubricants
Terminology based solely on the Viscosity Index — independent of the crude
source or type of processing
 Paraffinic lubricants are all grades, both bright stock & neutral, with a finished
viscosity Index more than 75
 Naphthenic lubricants are all grades with a viscosity Index less than 75
Important properties
 Kinematic viscosity (viscosity divided by mass density)
 Color
 Pour point for cold weather operation
 Flash point
 Volatility for reduced evaporation
 Oxidation stability
 Thermal stability
62

SAE Viscosity Specifications
Kinematic viscosity measured
in centistokes but
specifications are labeled in
Saybolt Seconds (SUS)
Specifications are established
by the Society of Automotive
Engineers
 SAE viscosity well known
motor oil specification (e.g.,
10W‐30)
63
Grade
Max Viscosity
(SUS) @ 0oF
Max Viscosity
(SUS) @ 210oF
Min
Viscosity
(SUS) @
210oF
5W 6,000
10W 12,000
20W 48,000
20 58 45
30 70 58
40 86 70
50 110 85

Asphalt
Important product in the construction industry
 Comprise 20% of the “Other Products” category
Asphalt can only be made from crudes containing asphaltenic
material
Numerous detailed specifications on the many asphalt products
 Asphalt Institute, Lexington Kentucky
• Industry trade group for asphalt producers & affiliated businesses
 American Association of State Highway and Transportation Officials
• Sponsors the AASHTO Materials Reference Laboratory (AMRL) at the National
Institute of Standards and Technology (NIST)
 American Society of Testing and Materials (ASTM)
65

Petroleum Coke
Green Coke Calcined Coke
Fixed carbon 86% ‐ 92% 99.5%
Moisture 6% ‐ 14% 0.1%
Volatile matter 8% ‐ 14% 0.5%
Sulfur 1% ‐ 6% 1% ‐ 6%
Ash 0.25% 0.40%
Silicon 0.02% 0.02%
Nickel 0.02% 0.03%
Vanadium 0.02% 0.03%
Iron 0.01% 0.02%
66

Sulfur Specifications
Purity 99.8 weight % sulfur, based on dry analysis
Ash 500 ppmw maximum
Carbon 1,000 ppm(weight) maximum
Color
"Bright yellow" when solidified.
Sulfur recovered by liquid reduction‐oxidation processes have color due to
metals — some purchasers will include a requirement excluding sulphur
recovered from these processes
H2S 10 ppmw max (Important for international transport & sales)
State Shipped as either liquid or solid. International transport specifies solid.
67

Summary

Summary
Many of the properties are based upon distillation/evaporation
specifications
 % Distilled at specified TBP temperature
 Temperature for specified % distilled
 Reid vapor pressure (RVP)
Many specifications are specific for certain products
 Octane number
 Cetane number
Overlap of boiling point ranges allows flexibility of routing
intermediate streams to multiple products
69

Supplemental Slides

Standard Conditions (Temperature & Pressure)
“Standard conditions” may vary between countries, states within
the US, & between different organizations
 Standard temperature – 60oF
• Most other countries use 15oC (59oF)
• Russia uses 20oC (68oF)
 Standard pressure – 1 atm (14.696 psia)
• Other typical values are 14.73 psia (ANSI Z132.1) & 14.503 psia
“Normal conditions”
 Almost exclusively used with metric units (e.g., Nm³)
 IUPAC: 0oC & 100 kPa (32oF & 14.50 psia)
 NIST: 0oC & 1 atm (32oF & 14.696 psia)
71

Standard Liquid Volume vs. Standard Gas Volume
Standard liquid volume – volume of a stream if it could exist in the
liquid state at the standard conditions
 Mass flow rate converted to standard liquid volume flow rate using the
specific gravity values
 U.S. customary flow rate units usually “bbl/day”, “bpd”, or “sbpd”
Standard/normal gas volume – volume of a stream if it could exist
in the ideal gas state at the standard conditions
 Molar flow rate converted to standard ideal gas volume using molar
volume at standard conditions
 U.S. customary flow rate units usually “scfd”
Metric flow rate units usually “Nm³/day”
72

Standard Liquid & Gas Volumetric Flow Rates
Standard liquid volume flow (sbpd):
Standard ideal gas volume flow (scfd):
73
 
 

   
 
 
 
 
 
 
   



*
lb
100
hr
lb
0.4941 8.3372
gal
gal hr bbl
24.4 24
hr day 42 gal
bbl
13.9
day
L
o W
m
V
 

  
 
   
   
 



3
*
3
2.249
lb.mol ft hr
379.5 24
hr lb.mol day
ft
20,480
day
G IG
nV
V
Compound Mol Wt
Specific
Gravity
(60/60)
Rate
[lb/hr]
Rate
[lb.mol/hr]
Ethane 30.07 0.3562 19.0 0.632
Propane 44.10 0.5070 47.2 1.070
Isobutane 58.12 0.5629 4.3 0.074
N‐Butane 58.12 0.5840 19.0 0.327
Isopentane 72.15 0.6247 2.1 0.029
N‐Pentane 72.15 0.6311 8.4 0.116
Total 44.47 0.4919 100.0 2.249

Crude Oil Assay – Ten Section Field (Text pg. 416)
74
IncrementCumulative Corrected Corrected
Fraction mm Hg °F vol% vol% SpGr °F Cumulative Amount °API
756 82 IBP 82.3 1.8 0.9
1 756 122 2.6 2.6 0.644 122.3 4.4 3.1 88.2
2 756 167 2.3 4.9 0.683 167.3 6.7 5.5 75.7
3 756 212 5.0 9.9 0.725 212.3 11.7 9.2 63.7
4 756 257 7.9 17.8 0.751 257.3 19.6 15.7 56.9
5 756 302 6.2 24.0 0.772 302.4 25.8 22.7 51.8
6 756 347 4.9 28.9 0.791 347.4 30.7 28.3 47.4
7 756 392 4.6 33.5 0.808 392.4 35.3 33.0 43.6
8 756 437 5.2 38.7 0.825 437.4 40.5 37.9 40.0
9 756 482 4.9 43.6 0.837 482.4 45.4 43.0 37.6
10 756 527 6.2 49.8 0.852 527.4 51.6 48.5 34.6
11 40 392 4.3 54.1 0.867 584.0 55.9 53.8 31.7
12 40 437 5.2 59.3 0.872 635.0 61.1 58.5 30.8
13 40 482 5.3 64.6 0.890 685.5 66.4 63.8 27.5
14 40 527 3.2 67.8 0.897 735.7 69.6 68.0 26.2
15 40 572 5.4 73.2 0.915 785.4 75.0 72.3 23.1
Residuum 25.0 98.2 0.984 100.0 87.5 12.3
Total 98.2 0.858
Loss 1.8
Reported 0.854
Mid-Cumulative
Steps for this example

Crude Oil Assay – WTI (from OGJ article)
75
Steps

SAE 902098 Gasoline Blend Stock Analyses
76
Light Cat
Blending Cat Cracked Cat Cracked Cracked Light Heavy Full Range Light St C6 Light Mid Cut Heavy
Component Naptha #1 Naptha #2 Naptha Alkylate Alkylate Reformate Run Naptha Isomerate Reformate Reformate Reformate
Gravity, °API 52.1 51.9 66.8 72.3 55.8 44.2 81.8 83.0 72.0 32.8 29.8
Aromatics, vol% 35.2 35.9 17.6 0.5 1.0 61.1 2.2 1.6 4.8 94.2 93.8
Olefins, vol% 32.6 25.4 44.9 0.2 0.9 1.0 0.9 0.1 1.5 0.6 1.9
Saturates, vol% 32.2 38.8 37.4 99.3 98.1 37.9 96.9 98.3 93.7 5.1 4.2
Benzene, vol% 1.06 1.23 1.24 0.00 0.01 1.17 0.73 0.00 4.01 0.00 0.00
Bromine Number 57.1 41.7 91.4 2.3 0.3 1.2 0.5 3.8 3.1 0.6 0.9
RVP, psi 4.3 4.6 8.7 4.6 0.3 3.2 10.8 8.0 3.8 1.0 0.3
Distillation, °F
IBP 110 112 95 101 299 117 91 118 138 224 313
T05 143 142 117 144 318 168 106 131 169 231 326
T10 158 155 124 162 325 192 113 134 174 231 328
T20 174 171 130 181 332 224 117 135 179 231 331
T30 192 189 139 196 340 244 121 135 182 232 335
T40 215 212 149 205 345 258 126 136 185 233 339
T50 241 239 164 211 354 270 132 136 188 234 344
T60 270 269 181 215 362 280 139 137 190 235 350
T70 301 302 200 219 373 291 149 137 192 237 358
T80 336 337 224 225 391 304 163 138 194 240 370
T90 376 379 257 239 427 322 184 139 195 251 391
EP 431 434 337 315 517 393 258 146 218 316 485
RON 93.2 92.6 93.6 93.2 65.9 97.3 63.7 78.6 57.6 109.3 104.3
MON 81.0 82.1 79.4 91.2 74.5 86.7 61.2 80.5 58.5 100.4 92.4
(R+M)/2 87.1 87.4 86.5 92.2 70.2 92.0 62.4 79.5 58.0 104.9 98.4
Carbon, wt% 86.94 85.88 85.60 84.00 84.39 88.11 83.58 83.44 84.41 90.87 89.62
Hydrogen, wt% 13.00 13.56 14.20 16.09 15.54 11.60 16.29 16.49 15.54 9.32 10.34
Nitrogen, ppmw 46 37 27 0 0 0 0 0 0 0 0
Sulfur, ppmw 321 522 0 15 15 9 325 10 7 10 8
Heating Value,
BTU/lb (net) 17300 17300 18700 18400 18100 16800 18400 18500 18200 15500 17300
Table 7 Analyses of Blending Components

SAE 902098 Gasoline Analyses
77
Fuel A B C D E F G H I J K L M N O P Q R A Z ZZ
Code Avg Cert 2211 1122 2222 1111 2121 1221 2112 1212 2111 2122 1222 1211 2221 1121 1112 2212 M0 M85 M10
Gravity, °API 57.4 58.8 50.2 59.2 50.2 64.1 53.4 62.2 51.9 58.2 53.4 50.6 59.1 62.6 51.7 64.2 59.6 49.1 57.4 47.9 56.8
Aromatics, vol% 32.0 29.9 43.8 20.7 43.7 20.0 44.3 20.2 42.9 21.4 45.7 47.8 18.0 21.4 46.7 20.3 21.5 46.0 32.0 5.0 28.0
Olefins, vol% 9.2 4.6 3.3 22.3 17.2 3.2 17.4 20.2 4.1 4.0 4.9 17.7 21.8 5.7 19.3 18.3 4.8 4.0 9.2 1.0 6.8
Saturates, vol% 58.8 65.5 37.5 57.0 24.3 76.8 38.3 45.0 53.0 59.7 49.4 34.5 45.7 59.0 19.4 61.4 73.7 34.8 58.8 8.4 55.5
MTBE, vol% 0.00 0.00 15.40 0.00 14.80 0.00 0.00 14.60 0.00 14.90 0.00 0.00 14.50 13.90 14.60 0.00 0.00 15.20 0.00 0.00 0.00
Methanol, vol% 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 85.60 9.70
Benzene, vol% 1.53 0.52 1.33 1.49 1.38 1.52 1.42 1.52 1.30 1.28 1.45 1.42 1.51 1.44 1.38 1.53 1.47 1.41 1.53 0.42 1.16
Bromine Number 21.3 12.2 9.2 44.3 32.5 10.0 35.7 41.1 11.5 10.0 13.3 38.7 42.6 16.2 35.0 38.9 12.2 10.8 21.3 3.0 18.6
RVP, psi 8.7 8.7 8.7 8.5 8.7 8.8 8.8 8.5 8.9 8.6 8.8 8.5 8.7 8.8 8.6 8.5 8.6 8.4 8.7 8.8 12.0
Distillation, °F
IBP 91 87 89 87 90 89 92 93 87 89 90 89 91 93 92 90 92 89 91 110 89
T05 114 112 118 111 113 110 116 116 110 112 114 110 111 114 116 113 117 114 114 134 105
T10 128 127 136 128 128 125 130 125 127 125 127 127 125 124 130 126 134 129 128 141 113
T20 151 152 165 153 151 144 153 135 156 143 146 152 139 134 151 140 161 151 151 145 122
T30 174 180 185 176 172 162 175 143 182 159 166 178 152 142 168 155 186 170 174 146 129
T40 196 205 200 197 192 180 196 154 208 178 188 205 170 152 185 171 209 192 196 147 139
T50 218 220 213 218 220 197 214 168 239 208 208 236 193 164 204 190 234 225 218 147 202
T60 243 230 226 238 253 212 228 186 266 259 226 263 233 181 223 208 260 263 243 147 232
T70 267 242 236 265 281 227 240 214 291 294 238 294 283 211 237 227 289 293 267 147 259
T80 295 262 250 307 318 245 254 247 324 322 253 328 323 253 250 248 321 326 295 148 287
T90 330 300 288 357 357 279 286 286 353 356 294 357 356 292 283 284 357 354 330 148 324
EP 415 410 399 430 429 370 386 367 437 447 404 436 436 374 397 361 442 428 415 347 405
RON 92.0 96.7 100.0 93.7 98.9 90.5 96.9 95.4 97.1 92.7 93.5 97.1 96.6 91.5 100.4 92.7 90.2 99.4 92.0 107.1 95.7
MON 82.6 87.5 88.0 83.2 85.6 84.2 84.6 83.9 86.9 85.1 83.1 84.5 85.0 83.6 86.0 82.7 83.8 87.5 82.6 103.1 84.4
(R+M)/2 87.3 92.1 94.0 88.4 92.3 87.4 90.8 89.6 92.0 88.9 88.3 90.8 90.9 87.6 93.2 87.7 87.0 93.4 87.3 105.1 90.1
Carbon, wt% 86.74 86.64 85.34 86.29 85.09 85.05 87.79 83.53 87.71 83.51 87.88 87.87 83.65 83.36 85.44 86.11 85.85 85.50 86.74 44.25 81.48
Hydrogen, wt% 13.22 13.35 11.92 13.73 12.20 14.12 12.17 13.56 12.26 13.70 12.10 12.07 13.60 13.92 11.94 13.82 14.08 11.84 13.22 12.61 13.17
Nitrogen, ppmw 29 12 1 46 31 4 15 10 3 12 1 26 16 6 9 13 8 11 29 2 25
Sulfur, ppmw 339 119 284 316 267 290 317 312 261 297 318 266 301 294 288 333 310 279 339 27 242
Oxygen, wt% 0.00 0.00 2.72 0.00 2.69 0.00 0.00 2.88 0.00 2.76 0.00 0.00 2.67 2.68 2.60 0.00 0.00 2.63 0.00 43.13 5.33
Heating Value,
BTU/lb (net) 18300 18300 17500 18300 17800 18500 18100 17900 18200 17900 17500 17600 17700 18100 17100 18600 18100 17000 18300 9600 17400
Table 10 Blended Fuel Analyses

ASTM D 323 RVP Procedures
Procedure “A” (Atmospherically Stable Liquids)
78
Apparatus Liquid & vapor chambers. Vapor chamber 4.0 ± 0.2 times size of liquid chamber
Liquid Preparation 1 L sample container filled 70‐80% with test liquid sample. Sample container cooled
in a cold bath at 0 ‐ 1C (32 ‐ 34F). Sample container opened, allowing air to enter
container. Container shaken vigorously (to saturate the liquid with air) & returned to
cold bath.
Liquid Transfer The liquid chamber cooled in the same cold bath. Cold liquid sample transferred to
the cold liquid chamber, entirely filling liquid chamber.
Air Preparation Vapor chamber full of air is placed in a hot bath at 37.8 ± 0.1C (100 ± 0.2F).
Assembly Vapor chamber removed from hot bath & coupled to liquid chamber. The coupled
apparatus is inverted, shaken, & put into hot bath.
Pressure Measurement Apparatus should remain in hot bath for at least 5 minutes before the apparatus is
removed from bath, shaken, & returned to hot bath. Shaking procedure should be
repeated at least 5 times with no less than 2 minutes in between. Shaking procedure
should be repeated until 2 consecutive pressure readings indicate equilibrium has
occurred. Pressure measured as gauge but reported with reference to “gauge” or
“absolute”.

ASTM D 323 RVP Procedures
Procedure “C” (Volatile Liquids )
79
Liquid Preparation Sample container of about 0.5 L capacity cooled in a cold bath at 0 ‐ 4.5C (32 ‐ 40F).
This sample container is not opened & contacted with air.
Liquid Transfer Liquid chamber is cooled in the same cold bath. Cold liquid sample transferred to the
cold liquid chamber, similar to Procedure A. However, since this liquid is under
pressure, extra care must be taken to ensure that gas is not flashed off and lost and
that the liquid chamber is actually completely filled with the liquid.

ASTM D 56 Flash Point by Tag Closed Tester Flash
Points Below 60oC (140oF)
80
Apparatus Tag Close Tester — test cup, lid with ignition source, & liquid bath.
Preparation Transfers should not be made unless sample is at least 10C (18F) below the
expected flash point. Do not store samples in gas‐permeable containers since
volatile materials may diffuse through the walls of the enclosure. At least 50 mL
sample required for each test.
Manual Procedure 1. Temperature of liquid in bath shall be at least 10C (18F) below expected flash
point at the time of introduction of the sample into test cup. Measure 50 ± 0.5 mL
sample into cup, both sample & graduated cylinder being precooled, when
necessary, so that specimen temperature at time of measurement will be 27 ± 5C
(80 ± 10F) or at least 10C (18F) below the expected flash point, whichever is
lower.
2. Apply test flame —size of the small bead on the cover & operate by introducing
the ignition source into vapor space of cup & immediately up again. Full operation
should be 1 sec with equal time for introduction & return.
3. Adjust heat so temperature rise 1C (2F)/min ± 6 s. When temperature of
specimen in is 5C (10F) below its expected flash point, apply the ignition source.
Repeat application of ignition source after each 0.5C (1F) rise in temperature of
the specimen.

Linear Blending Rules
Values for individual blend
stocks averaged either with
volume fractions or mass
fractions
 Some properties blend best with
mole fractions, but molar
amounts not typically known
Units on the quality measure
may give an indication as to
volume or mass blending.
Volume blending
 Specific gravity (essentially mass
per unit volume)
 Aromatics & olefins content
(vol%)
Mass blending:
 Sulfur & nitrogen content (wt%
or ppm)
 Nickel & vanadium (ppm)
81
 



i i
mix i i
i
V X
X v X
V



 


 
 i oi i
i i
mix i i
i i oi
v X
m X
X w X
m v

How Do We Blend Specific Gravities?
Assume ideal liquid mixing — volumes are additive
 “Shrinkage” correlations available, mostly used for custody transfer
Liquid densities at fixed conditions blend linearly with volume
 Mass & volumes are additive
Can also blend with mass & molar amounts
 Volumes are additive
Density adjustments
 Corrections needed for temperature & pressure effects
82
 
    
 


, ,
, ,
i o i i o i
o mix i o i
i
V V
v
V V
  
   
 
, , , ,
1 i i i
o mix o i o mix o i
w x M
M

How Do We Blend API Gravities?
Specific gravity is blended & API gravity is back‐calculated.
 May have to calculate individual specific gravities from given API gravities
Example
 Incorrect value from direct volume blending of API gravities
83

Temperature Corrections to Specific Gravity
O’Donnell method1
API Volume Correction Tables
 Different 60 values depending on commodity type
• A Tables – Crude Oils
• B Tables – Refined Products
• D Tables – Lubricants
• C Tables – Individual & Special Applications
1Reported slope value is ‐0.00108 (g/cm3)2/oC, Hydrocarbon Processing, April 1980, pp 229‐231
84
 

    
2 2
0.000601 60
T o F
T
   
 
60 60
exp 60 1 0.8 60
T o F F
T T
 
 
        
 

What if we want to estimate volumetric shrinkage?
Method in Chapter 12.3 of API measurement manual
Example: Blend 95,000 bbl of 30.7oAPI (0.8724 specific gravity) crude oil with
5,000 bbl of 86.5oAPI (0.6491 specific gravity) natural gasoline
 By ideal mixing:
 With shrinkage:
85
   

     

0.819 2.28
8
4.86 10 100 where 100
L
L H
H L
V
S C C G G C
V V
  
     
      

100,000 bbl
0.6491 5000 0.8724 95000 141.5
0.8612 and 131.5 32.8
100000
mix H L
L L H H
mix mix
mix mix
V V V
V V
G
V
   
   

          

 
   
   
   
   
     
    
0.819 2.28
8
5000
100 5 4.86 10 5 100 5 86.5 30.7 0.0972
5000 95000
100 100 0.0972
100000 99,903 bbl
100 100
0.6491 5000 0.8724 95000 141.5
0.8621 and
99903
mix H L
L L H H
mix mix
mix
C S
S
V V V
V V
G
V
 

131.5 32.6
mix

How Do We Blend Yield Curves?
Amounts are added for
the same TBP
temperature ranges
 On a consistent
volume, mass, or mole
basis
 On an incremental or
cumulative basis
 Temperatures
“corrected” to 1 atm
basis
 Distillation type
corrected to TBP
86
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 250 500 750 1000 1250 1500 1750 2000
Temperature [°F]
Incremental
Amount
[vol%]
0
10
20
30
40
50
60
70
80
90
100
Cumulative
Amount
[vol%]
N'Kossa
Ratawi Crude Oil
Cumulative Amount

How Do We Blend Properties for Individual
Fractions?
Blend based on properties and amounts for the fraction in each
blend stock, not the overall amount of blend stock.
87

How Do We Correct Boiling Point for Pressure?
Equation form of Maxwell‐Bonnell charts (1955)
 Pvap units of mmHg, temperatures in units oR
88

 


    



10
3000.538 6.761560
0.002184346 for 1.7 mmHg
43 0.987672
2663.129 5.994296
log 0.001201343 0.002184346 for 1817 mmHg 1.7 mmHg
95.76 0.972546
2770.085 6.412631
0.001201
36 0.989679
vap
vap vap
X
X P
X
X
P X P
X
X
X







 


343 for 1817 mmHg vap
X P
 
  

     
   

 

 
10
1
0.0002867
& 2.5 12 log
760
1
748.1 0.0002867
vap
B B W
B
P
T
X T T f K
T
 

    
 

 
 

 
 

1 760 mmHg
659.67
Min 1,Max ,0 760 mmHg
200
vap
vap
B
P
f T
P

Pressure Correction Example
“Correct” a 437oF boiling point measured at 40 mmHg to the normal boiling
point (at 760 mmHg).
Using the 2nd of 3 equations:
With T=896.67oR determine T’B=1094.98
If we neglect the Watson K factor correction (i.e., assume KW = 12) then
TB = T’B & the normal boiling point is 635oF
89
 
 
 


  
 

10
10
10
0.972546log 40 5.994296
2663.129 5.994296
log 40
95.76 0.972546 95.76log 40 2663.129
0.001767618
X
X
X

 
  
 

 

 
1
0.0002867
437 459.67
0.001767618 1094.98
1
748.1 0.0002867
B
B
T
T

How Do We Interconvert D86 & TBP Temperatures?
Method from 1994 API Technical Data Book
 Consistent with the “API94” option in Aspen Plus
90
 
 
    
1.0258
TBP,50% D86,50% TBP,50% D86,50%
TBP D86 TBP D86
0.87180 ( & in °F)
( & in °F)
B
T T T T
T A T T T
Vol% A B
100% to 90%* 0.11798 1.6606
90% to 70% 3.0419 0.75497
70% to 50% 2.5282 0.82002
50% to 30% 3.0305 0.80076
30% to 10% 4.9004 0.71644
10% to 0%* 7.4012 0.60244
*Reported 100% & 0% give better trends as 99% & 1%.

Interconvert D86 & TBP Temperatures
91
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70
D86 Temperature Difference [°F]
TBP
Temperature
Difference
[°F]
0% to 10%
10% to 30%
90% to 100%
30% to 50%
50% to 70%
70% to 90%

How Do We Interconvert D86 & TBP Temperatures?
92
 
 
 
  
 
TBP D86
1/
TBP D86
TBP
D86
& in °R
b
b
T a T
T T
T
T
a
Vol% a b
0%* 0.9167 1.0019
10% 0.5277 1.0900
30% 0.7429 1.0425
50% 0.8920 1.0176
70% 0.8705 1.0226
90% 0.9490 1.0110
95% 0.8008 1.0355
Use with care – may give incorrect temperature vs. volume trends

How Do We Interconvert D1160 & TBP
Temperatures?
D1160 temperatures at 10 mm Hg are converted to TBP
temperatures at 10 mm Hg — graphical method to interconvert
 D1160 temperatures at 50% & higher equal to the TBP temperatures
 0% to 10%, 10% to 30%, & 30% to 50% D1160 temperature differences
converted to TBP temperature differences
93
       
        
2 3 4
1160 1160 1160 1160
TBP D D D D
T a T b T c T d T
Vol%
Distilled
Range
a B c d Max T
0% ‐ 10% 2.23652561 ‐1.39334703E‐2 3.6358409E‐5 1.433117E‐8 144F
10%‐30%
30%‐50%
1.35673984 ‐5.4126509E‐3 2.9883895E‐5 ‐6.007274E‐8 180F

Interconvert D1160 & TBP Temperatures
94
0
25
50
75
100
125
150
175
200
225
0 25 50 75 100 125 150 175 200 225
D1160 Temperature Difference [°F]
TBP
Temperature
Difference
[°F]
Note: ASTM D1160 & TBP 50% distillation
temperatures assumed equal at 10 mmHg
Based on API Figure 3A2.1
Subatmospheric Distillation &
True Boiling Point Distillation
Relationship
0% to 10%
10% to 30% & 30% to 50%
50% to 70% & 70% to 90%

How Do We Interconvert D2887 & TBP
Temperatures?
 D2887 essentially TBP on wt% basis, not vol%
95
 

    
TBP,50% D2887,50%
TBP D2887 TBP D2887
( & in °F)
B
T T
T A T T T
Vol% A B
100% to 95% 0.02172 1.9733
95% to 90% 0.97476 0.8723
90% to 70% 0.31531 1.2938
70% to 50% 0.19861 1.3975
50% to 30% 0.05342 1.6988
30% to 10% 0.011903 2.0253
10% to 0%* 0.15779 1.4296

D86 Conversion Example
96
Vol% D86 D86 T TBP T TBP
IBP 91 14.3
37 65.2
10 128 79.5
46 76.1
30 174 155.6
44 62.7
50 218 218.4
49 61.5
70 267 279.9
63 69.4
90 330 349.3
85 188.7
EP 415 538.0
Steps for this example

D‐86 vs TBP Temperatures
97
0
100
200
300
400
500
600
0 100 200 300 400 500
D86 Temperature [°F]
TBP
Temperature
[°F]
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90 100
Cumulative Yield [vol%]
Distillation
Tem
perature
[°F]
D86 Yield Curve
TBP Yield

How Do We Correlate Yield to Boiling Point?
Needed for interpolation, extrapolation, and smoothing of data
Traditional methods
 Electronic version of plotting cumulative yield data vs. boiling point temperature
on “probability paper”
• Guarantees an “S” shaped cumulative yield curve
• No specific 0% or 100% points
Distribution models
 Whitson method (1980)
• Probability distribution function.
• Can generate distribution from
a limited amount of C6+ data
 Riazi method (1989)
• Cumulative amount (Y)
• 0% point, no 100% point
• Essentially the same equation
form as Dhulesia’s equation (1984)
98
 
 

 

  
   
 
1
1 i
M M
p M
 
 
 
 
 
 
      
 
 

   
   
 
1
0 0
0 0
1
ln 1 exp
1
T
T
B
B
T T
T T
T T T T
A B
Y
T B Y A T

How Do We Use the Probability Form?
Distillation yield curves typically have an “S” shape
Traditional to linearize on “probability” graph paper
 Axis transformed using functions related to Gaussian distribution function
Functions available in Excel
 Transformed Yield: =NORMSINV( Pct_Yield/100 )
 From interpolated value: =NORMSDIST( Value ) * 100
Transformed 0% & 100% values undefined
 Typical to set IBP & EP to 1% & 99%
99

“Linearized” Distillation Yield Curves
100

Incremental vs. Cumulative Yield
Incremental yield can be calculated as the
difference in the cumulative yields at the
final & initial boiling points
 Values impacted by method chosen to
interpolate/extrapolate
101
     
,
i f f i
Y T T Y T Y T
  

How Do We Blend Distillation Curves?
Blend the distillation curves for all blend stocks & extract the
temperatures from the resulting curve
Steps
 Convert all of the starting distillation analyses to TBP basis (@ 1 atm)
 Pick a set of TBP temperatures for which the blend calculations will
proceed. Extract the yield values for at these selected temperature values
for all blend stocks.
• Use whatever temperatures seem reasonable to cover the span of all input
values
 Calculate a yield curve for the blend at the temperatures chosen in the
previous step
 Extract the temperature values for the specified yield values
 Convert to original distillation basis (if required)
102

Distillation Curve Blend Example
Steps
 Convert all D86 analyses to TBP
• Approximate IBP & EP as 1% & 99%
 Pick a set of TBP temperatures &
interpolate for appropriate yield values
 Volumetrically blend at each temperature for combined TBP curve
 Interpolate for appropriate TBP values at the standard volumetric yields
 Convert to D86 analysis
103
LSR
Mid Cut
Reformate
Vol% LSR
Mid Cut
Reformate
°F LSR
Mid Cut
Reformate
Blend Vol% TBP D86
°API 81.8 32.8 81.8 32.8 54.1
IBP 91 224 1 40.5 200.8 25 0.4 0.0 0.2 1 52.9 120.5
T10 113 231 10 88.1 224.7 50 1.7 0.0 0.9 10 101.0 142.8
T30 121 232 30 109.9 229.6 75 5.8 0.0 2.9 30 144.0 163.6
T50 132 234 50 130.5 234.8 100 19.3 0.0 9.6 50 218.0 217.7
T70 149 237 70 156.3 241.1 125 44.4 0.0 22.2 70 236.0 228.6
T90 184 251 90 200.9 263.4 150 65.4 0.0 32.7 90 258.7 242.9
EP 258 316 99 350.8 384.2 175 80.0 0.0 40.0 99 371.7 305.3
Fraction 50% 50% 200 89.7 0.9 45.3
225 92.6 11.0 51.8
250 94.8 79.6 87.2
275 96.4 91.7 94.0
300 97.6 94.5 96.0
325 98.4 96.5 97.5
350 99.0 97.9 98.4
375 99.4 98.8 99.1
400 99.6 99.3 99.5
Blend Stock Data D86 Converted to TBP Blend at Specified Yields
Blend at Selected Temperatures

How Do We Estimate Light Ends from Yield Curve?
Determine the incremental amount from the difference in
cumulative yields between adjacent pure component boiling
points
Steps
 Choose light‐ends components
• Typically methane, ethane, propane, iso & normal butane, iso & normal
pentane
 Determine boiling point ranges associated with pure component boiling
points
• Sometimes extend range to 0.5oC above the pure component boiling point
 Extrapolate distillation yield curve to find cumulative yields at the boiling
point ranges. Find differences to determine incremental amounts.
104

Light Ends Example
Steps
 Choose light‐ends components
 Determine boiling point ranges associated
with pure component boiling points. Use as
the Final Boiling Point for range.
 Extrapolate distillation yield curve to find
cumulative yields at all boiling point values.
 Calculate differences to determine
incremental amounts.
105
Initial Final
Cumulative
@ Initial
Cumulative
@ Final
Pure
Component
Initial Final
Cumulative
@ Initial
Cumulative
@ Final
Increment
Whole Crude Methane -258.73 N/A -258.73 0.0 0.02 0.02
Light Naphtha 55 175 1.7 5.6 Ethane -127.49 -258.73 -127.49 0.02 0.17 0.15
Medium Naphtha 175 300 5.6 15.3 Propane -43.75 -127.49 -43.75 0.17 0.53 0.36
Heavy Naphtha 300 400 15.3 21 i-Butane 10.78 -43.75 10.78 0.53 1.03 0.50
Kero 400 500 21 29.2 n-Butane 31.08 10.78 31.08 1.03 1.30 0.27
Atm Gas Oil 500 650 29.2 40.4 i-Pentane 82.12 31.08 82.12 1.30 2.27 0.97
Light VGO 650 850 40.4 57.3 n-Pentane 96.92 82.12 96.92 2.27 2.65 0.38
Heavy VGO 850 1050 57.3 71.5
Vacuum Resid 1050 End 71.5 100
Yield [vol%]
TBP [°F] TBP [°F]
Yield [vol%]
‐500
‐250
0
250
0.01 0.10 1.00 10.00 100.00
Cumulative Yield [vol%]
Boiling
Point
(°F)
C1
C2
C3
iC4
nC4
iC5
nC5

How Do We Estimate Other Properties of Fractions?
Properties inferred from measured trends
 Relative density / specific gravity / API gravity
 Sulfur content
 Carbon residue
Properties from correlations
 Molecular weight / molar mass
 Critical properties & accentric factor
 Heat of combustion (Btu/lb, liquid state @ 60oF)
106
   
   
2 3
LHV
2 3
HHV
ˆ 16792 54.5 0.217 0.0019
ˆ 17672 66.6 0.316 0.0014
H G G G
H G G G
 
     
1.26007 4.98308
20.486 exp 0.0001165 7.78712 0.0011582
B o B o B o
M T T T

What Happens When We Change Cut Points?
In general
 The amount can be calculated as the difference in cumulative yields between the
new initial & final boiling points
• Interpolate within the yield vs. temperature curve using the probability form
 The properties can be determined by interpolating the curve for the property vs.
the mid‐increment yield
• Linear interpolation usually sufficient
Special cases
 Slightly smaller than a given cut in the assay – find properties of the “excluded”
fraction & subtract contribution from the given cut
 Slightly larger than a given cut in the assay – find properties of the “included”
fraction & add contribution to the given cut
 Combination of two or more given cuts in the assay – find properties by adding all
contributions
107

Revised Cut Points – Example #1
What is the yield of the total gas oil (500 – 1050oF)? What are the properties?
 Add contributions for the Atm Gas Oil, Light VGO, & Heavy VGO
108
   
       
1050 500 85.8 39.5 46.3 vol%
GO
V Y F Y F
          
   
   
 14.6 0.8554 19.1 0.8909 12.6 0.9327
0.8911
46.3
i
i
GO
GO
V
V
 
 
           
        
   
  
   


14.6 0.8554 19.1 0.8909 12.6 0.9327
0.58 wt%
14.6 0.8554 19.1 0.8909 12.6 0.9327
0.27 0.57 0.91
i
i
GO
i
i
i
V
S
V
S

What is the yield of the HVGO if the cut range
is 850 – 1000oF? What are the properties?
 Determine amount & estimate properties of
1000 – 1050oF cut.
 Cumulative yield @ 1000oF from interpolation
of yield vs. temperature
 Properties from linear interpolation of mid‐
increment yield vs. property
 Remove contributions from the Heavy VGO in
the assay
109
 
  

 
   
1000 83.1 vol%
83.1 85.8
84.4
2
85.8 83.1 2.7 vol%
mid
Y F Y
V
 
 
   

84.4 vol% 16.5 0.9564
84.4 vol% 1.12 wt%
G
S
   
       
1000 500 83.1 73.2 9.9 vol%
GO
V Y F Y F
     
 


12.6 0.9327
9.9
2.7 0.9564
0.9262
GO
       
  
 

12.6 0.9327
0.86 wt%
0.91 2.7 0.9564 1.12
9.9 0.9262
GO
S

What is the yield of the Vac Resid if the cut
point is 1000oF+? What are the properties?
 Determine amount & estimate properties of
1000 – 1050oF cut.
 Cumulative yield @ 1000oF from interpolation
of yield vs. temperature
 Properties from linear interpolation of mid‐
increment yield vs. property
 Add contributions to the Vac Resid in the assay
110
 
  

 
   
1000 83.1 vol%
83.1 85.8
84.4
2
85.8 83.1 2.7 vol%
mid
Y F Y
V
 
 
   

84.4 vol% 16.5 0.9564
84.4 vol% 1.12 wt%
G
S
 
      
100 1000 100 83.1 16.9 vol%
GO
V Y F
     
 


14.2 1.0001
16.9
2.7 0.9564
0.9931
GO
       
  
 

14.2 1.0001
1.41 wt%
16.9 0.9931
1.46 2.7 0.9564 1.12
GO
S

Can We Estimate Gravity Curve When None Given?
Assume that all fractions have the same Watson K factor
Example – Estimate Ratawi
Watson K factor & gravity
curve based on overall
gravity & distillation
analysis
 Curve is estimate, points are
from the assay
111
Ratawi Crude Oil
0.60
0.70
0.80
0.90
1.00
1.10
1.20
0 10 20 30 40 50 60 70 80 90 100
Mid-Increment Yield [vol%]
Specific
Gravity
 
 

    
 

3
3
from
o
w o i oi i wi Bi
i Bi
K v v K T
v T

How Do We Blend Watson K Factor?
Best method
 Blend specific gravity
 Determine new average boiling point from blended yield curve
Approximate method
 Blend individual Watson K factors by weight
• Implies average boiling point from volumetric blend of cube root of boiling
point
112

 




i oi i
mix i i
i oi
v K
K w K
v

What is the Average Boiling Point for a Mixture?
5 types are defined in the API Technical Data Book
 Volume average boiling point
 Mass average boiling point
 Molar average boiling point
 Cubic average boiling point
 Mean average boiling point
Watson K‐factor is to use the Mean Average Boiling Point (MeABP)
113
 

  ,
1
n
b i b i
v
i
T v T
 

  ,
1
n
b i b i
w
i
T w T
 

  ,
1
n
b i b i
M
i
T xT
 

 
  
 

3
3
,
1
n
b i b i
cubic
i
T v T
 
   


2
b b
M cubic
b mean
T T
T

Estimate Average Boiling Points from Distillation
Curve
Procedure 2B1.1 of the API Technical Data Book using D86 distillation values
114
 
 
   
   
   
   
     
     
   




  
  
  
  
     
 
 
     
 
 

10 30 50 70 90
90 10
1
2
3
4
0.6667 0.25
1
0.6667 0.333
2
VABP
5
SL
90 10
WABP VABP
MABP VABP
CABP VABP
MeABP VABP
ln 3.062123 0.01829 VABP 32 4.45818 SL
ln 0.563793 0.007981 VABP 32 3.04729 SL
ln
T T T T T
T T
     
     
    
 
 
     
 
 
0.45 0.45
3
0.6667 0.333
4
0.23589 0.06906 VABP 32 1.8858 SL
ln 0.94402 0.00865 VABP 32 2.99791 SL

How Do We Blend Heating Values?
Heating Value
 Molar, mass, or liquid‐volume average (depending on units)
 Lower/net heating value (LHV) — water in gas state
 Higher/gross heating value (HHV) — water in liquid state
115
 
 
  ˆ ˆ
or
mix i i mix i i
H x H H w H
       

2 2 2 2 2
Fuel+ O CO g +H O g +N g +SO g
       
 

  

  
2 2
2 2 2 2 2
HHV LHV H O H O
Fuel+ O CO g +H O +N g +SO g
vap
ref
H H n H T

Vapor Pressure Calculations
Bubble Point – TVP (True Vapor Pressure)
 At 1 atm, could use ideal gas & liquid assumptions – molar blending
 Vapor pressure approximation using accentric factor
 Maxwell‐Bonnell relationship for petroleum fractions
 EOS (equation of state) calculations more rigorous
• Soave‐Redlich‐Kwong or Peng‐Robinson
116
 
1 1
vap
i
i i i i
P T
y x K x
P
 
   
 
 
  
 
   
  
   
 
 
10
7
log 1 1
3
vap
ci
i
i
ci
T
P
P T

How Do We Blend RVPs?
RVP is nearly equal to the True Vapor Pressure (TVP) at 100oF
For ideal gas & liquid mixtures, TVP blends linearly with molar
fraction
Approximate volumetric linear blending with “RVP Blending
Indices”
117
       
 
  
 
 
1/1.25
1.25 1.25 1.25
RVP RVP RVP RVP
i i
mix i mix i
v v
 
 
 
    
 
 
 


exp
TVP
vap
i
P
vap vap
i
i i i i i i i i
P
vap
i i
mix
v
y P x P dP y P x P
RT
x P

RVP & TVP – API Technical Data Book Methods
Intent is to estimate
true vapor pressures
(TVPs) from a
measured RVP
Can also estimate RVP
from any measured
vapor pressure value
 TVP could be
measured at any
temperature –
could use boiling
point
 Slope is of the
ASTM D86
distillation curve @
T10
118

Other Correlations
GPSA Fig. 6‐4 makes use of
Kremser relationship (1930)
for TVP @ 100oF:
TVP = 1.07 (RVP) + 0.6
119

Other correlations
Santa Barbara County APCD Rule 325, Attachment B, equation 25:
TVP = (RVP) exp( Co (IRTEMP – ITEMP) ) + CF
where: Co RVP dependent coefficient
ITEMP 1/(559.69 oR)
IRTEMP 1/(Ts + 559.69 oR)
Ts
oF temperature stored fluid
Based on API Figure 5B1.2
120

How Do We Blend Octane Numbers?
Octane numbers generally blend non‐linearly
 Interactions between components in mixture
Approximate linear blending with “Octane Blending Indices”
 Indices are fairly closely guarded
In this class we’ll generally assume linear blending with volume
121
   
   




i
mix i
i
mix i
RON v RON
MON v MON

Non‐Linear Octane Blending Formula
Developed by Ethyl Corporation using a set of 75 & 135 blends
122
   
 
 
   
 
       
     
   
 

   
 
      
   
   
 


  

 


2 2 2 2
1 2 3
2
2 2
2 2
1 2 3
100
"Road" Octane
2
Sensitivity
Volume Average i i
i
R R a RJ R J a O O a A A
A A
M M b MJ M J b O O b
R M
J R M
V X
X
V
Petroleum Refinery Process Economics, 2nd ed. ,
by Robert E. Maples, PennWell Corp., 2000
75 blends 135 blends
a 1 0.03224 0.03324
a 2 0.00101 0.00085
a 3 0 0
b 1 0.04450 0.04285
b 2 0.00081 0.00066
b 3 ‐0.00645 ‐0.00632

Gasoline Blending Sample Problem
What are the API gravity, RVP, & average octane number for a
33/67 blend of Light Straight Run Gasoline & Mid‐Cut Reformate?
123
Steps
for
this example

What is Driveability Index (DI)?
Oriented towards the auto industry
Need enough volatility to completely vaporize fuel in the cylinder
 Lowering RVP makes the fuel harder to vaporize
Empirical relationship between gasoline volatility & engine
performance (driveability & emissions)
DI = 1.5 T10 + 3 T50 + T90 + (2.4oF)(EtOH vol%)
The lower the DI, the better the performance
 Alkylates raise T50
 Ethanol raises RVP & depresses T50, but not the DI
124

How Can We Estimate Flash Point?
Related to volatility of mixture.
 Assume ideal gas since tests done at 1 atm.
Method of Lenoir
Method of Gmehling & Rasmussen
 Related to lower flammability limit
125

 

1
1.3
N
vap
i i i i
i
x M P
 

 
 
     

 

1 ,
25
1 with 25 0.182
vap
N
i i i
i i
i i c i
x P T
L L C
L H

How Can We Estimate Flash Point?
API Procedure 2B7.1 for closed cup test (using ASTM D 86 T10)
 1987 Version (units of oR)
 1997 Version (units of oF)
• Open Cup
• Closed Cup
 2016 API Data Book has
revised Procedure 2C1.1 using
IBP & T5
126
 
    10
10
1 2.84947
0.014568 0.001903ln
F
T
T T
 
10
0.68 109.6
F
T T
 
10
0.69 118.2
F
T T

How Do We Estimate & Blend Cetane Index?
Cetane index is an estimate of the cetane number based on
composition. It does not take into account effects of additives to
improve cetane number.
Estimation method outlined by ASTM D 976
Index = ‐420.34 + 0.016 G2 + 0.192 G log(T50) + 65.01[log(T50)]2 – 0.0001809 T50
2
where T50 is 50% point as determined by D 86 distillation [oF] &
G is the API gravity
 Four Variable methods outlined in ASTM D 4737
• Different correlations for 15 ppmw & 500 ppmw diesels
Cetane index can be linearly blended by volume (as an
approximation)
127

How Are Octane & Cetane Numbers Related?
In general compounds with high octane numbers have low cetane
numbers
Correlation developed from
gasoline samples
128
 
 
 
 
CN 60.96 0.56 MON
CN 68.54 0.61 RON
Bowden, Johnston, & Russell, “Octane‐Cetane Relationship”,
Final Report AFLRL No. 33, March 1974,
Prepared by U.S. Army Fuels & Lubricants Research Lab & Southwest Research Institute
0
5
10
15
20
25
70 80 90 100
Cetane
Number
(CN)
Octane Number (MON or RON)
RON Expression
MON Expression

How Do We Convert SUS viscosity?
129
0
50
100
150
200
250
300
350
400
450
500
0 20 40 60 80 100
Kinematic Viscosity [cSt]
SUS
Viscosity
210°F
0°F
 
  
 
 
     
  
 
      
 
 
2 3 5
1.0 0.03264
1.0 0.000061 100 4.6324
3930.2 262.7 23.97 10
SUS T

How do we adjust viscosity for temperature?
ASTM D341 for viscosities above 0.21 cSt
For viscosities greater than 2.0 cSt the equation is essentially:
130
 
   
 
 
 
 
 
 
   
  
        
   
   
  
  
  
  
       
log log log
0.7
exp 1.14883 2.65868
exp 0.0038138 12.5645
exp 5.46491 37.6289
exp 13.0458 74.6851
exp 37.4619 192.643
exp 80.4945 400.468
0.7 exp 0.7487 3.295 0.7 0.611
Z A B T
Z C D E F G H
C
D
E
F
G
H
Z Z    
 
  
 
2 3
9 0.7 0.3193 0.7
Z Z
 
   
    
log log 0.7 log
A B T

Viscosity vs. Temperature Example
Steps
 Calculate the Z & temperature terms
from the given data
• Convert temperatures to absolute basis
 Determine A & B parameters from data
• This case uses linear regression & all 4
points
 Use A & B parameters to find Z at other
temperatures
 Convert Z to cSt
• Approximate formula used here
°F cSt log(log(Z)) log(°R)
Est
log(log(Z))
Est cSt
Relative
Deviation
104 4,102 0.5579 563.67 0.5514 3,629 ‐12%
122 1,750 0.5110 581.67 0.5137 1,836 5%
212 115 0.3146 671.67 0.3253 130 13%
275 37.9 0.2005 734.67 0.1934 35.7 ‐6%
A: 1.732
B: ‐0.002094
r²: 0.997
By linear regression
131
0
1
10
100
1,000
10,000
100 200 300 400 500 600 700
Temperature [°F]
Viscosity
[cSt]

How Do We Blend Viscosities?
Viscosity blending has complicated composition effects
Simple viscosity blending equations are more appropriate for gas‐
phase viscosity – should not be used for blending liquid‐phase
petroleum fraction values
 Arrhenius
 Bingham
 Kendall & Monroe
132
   
  

ln ln
mix i i
v

 

1 i
mix i
v
 
 
  
 

3
1/3
ln
mix i i
x

How Do We Blend Viscosities?
Desire to blend viscosity with either volume or mass amounts
Linear blending with “Viscosity Blending Indices” of kinematic viscosity
May see an index based on log‐log terms with extra coefficients and/or natural‐
log terms. Give identical results.
For heavy fractions often mass blending is suggested with c of 0.8 to 1.0
 Refutas equation – mass blending
Other types of blending indices
 Chevron Method 2
133
 
   
 
        

log log log log where 0.7
mix c i i c c
v
       
 
     

VBN VBN where VBN 14.534 ln ln 0.8 10.975
i i
blend i i
w
 
 
 
 
   
 
     
  

ln ln
ln ln 1000
ln 1000 ln 1000 1
W
W
W
mix i
i mix
mix i
v

ASTM D 7152 Viscosity Blending
Procedure C when using viscosity values all at the same temperature
 “ASTM Blending Method” – volume blending
 “Modified ASTM Blending Method” – mass blending
Based on log‐log (MacCoull‐Walther‐Wright) transformation viscosity
 Developed for volume blending & kinematic viscosity but could be used for mass blending
• For base stock blends, no significant difference between volumetric & mass blending
• For fuel blends (chemically converted blend stocks), mass blending more accurate
 Exponential correction term insignificant above 2 cSt
 Extends the use of log‐log terms from down to 0.2 cSt.
134
 
 
 
        


 
 
      
 

2
10
2 3
0.7 exp 1.47 1.84 0.51
log log
10 0.7
exp 0.7487 3.295 0.6119 0.3193
WB
i i i i
i i
B i i
B
B B B B B
Z
W Z
W vW
Z
Z Z Z Z

1
10
100
1,000
10,000
100,000
0.1 1 10 100
Ratio Cutter:Resid [vol/vol]
Blend
Viscosity
[cSt]
Volume Average cSt
Log‐Log Blending Rule
Volume Average log(cSt)
Chevron Blending Indices
Viscosity Blending Example
Determine the amount of cutter stock needed to blend with 5,000 bpd 80,000
cSt vacuum resid to make a fuel oil with 180 cSt @ 122oF. The cutter stock has
8.0 cSt viscosity.
ASTM Blending Method & Chevron
Method 2 essentially the same results
135

Solid & Near‐Solid Formation:
Pour Point, Cloud Point, & Freezing Point
Estimates based on physical properties
 API Technical Data Book, Procedures 2C5.1, 2C2, & 2C6.1
 Good to about 7oF
136
 
      
, 2390.42 1826 122.49 0.135 MeABP
FPT R o W
T K
 
 
 
  

   
0.315
0.712 MeABP 0.133
5.49
8
, 3.85 10 MeABP 10 1.4
o
pour R
T
     
      
0.315
10 , 10
log 7.41 5.49log MeABP 0.712 MeABP 0.133
CPT R o
T

How are the Carbon Residues Related?
Carbon residue – coking tendency
 ASTM D 524 — Ramsbottom (RCR)
 ASTM D 189 — Conradson (CCR)
 ASTM D 4530 – Microcarbon (MCRT)
CCR & MCRT essentially the same
137
   
 
   
 
2
RCR exp 0.236 0.883ln CCR 0.0657ln CCR

New vanadium compounds identified in heavy
Venezuelan crude oil
138
“New Vanadium Compounds in Venezuela Heavy Crude Oil Detected by Positive‐ion
Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry”
Xu Zhao, Quan Shi, Murray R. Gray & Chunming Xu
Scientific Reports 4, Article number: 5373 (2014)
https://www.nature.com/articles/srep05373/figures/4

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