Petroleum Refining Chapter 5: Refinery Feeds and Products

Refinery Feeds and Products

Refinery Feeds
1. Kuwait crude mix: (To all refineries)
Crude
%
API
Kuwait Export Crude
95
31.4
Ratawi
4.24
23.5
Brugan
0.76
23.4
Total
100
31
From the divided area between Kuwait and Saudi Arabia.

Sulfur, wt%
2.56
3.77
3.32
2.62

2. Eocene: (To MAA Refinery)

3. Natural Gas: (To all refineries)
Destination
Source
MAA
KOC west fields
SHB
MAB

Burgan gas

Description
Sour gas
Sour condensate
Sour gas

Flow Rate
210 MMSCFD
40 MBPSD
48.7 MMSCFD
39 MMSCFD

Refinery Products

There are 2000 products (Refineries & Petrochemical plants)

Storage is expensive & limited products must be sold or used.
The price of refinery products is influenced by
1. Location
2. Demand
3. Availability
4. Combustion characteristics
5. API
6. Sulfur content
7. Prices of competing fuels
Usually the lowest value of a HC product is determined by its heating value or fuel oil
equivalent (FOE).
Combustion characteristics are determined by octane number for gasoline and cetane
number for Diesel.
Example of refinery products are shown below

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Table 5.1. Refinery Main Products and their uses.

Products
Main Use
1.
Fuel Gas (mainly C1 & C2)
Used within the refinery for to fuel heaters, boilers,
etc.
2.
LPG (mainly C3 & C4)
For export and local consumption
3.
Gasoline
Motor, Aviation, tractor, marine
4.
KNG (Kuwait Natural Gasoline)
Motor
5.
Kerosene
Aviation Turbine Kerosene (ATK)
Illuminating Kerosene (IK)
Dual Purpose Kerosene (DPK)
Gas turbine or jet fuel (JP5/8/9)
6.
Diesel
HSD (Auto Engines)
Marine Diesel Oil (Slow Engines)
Low Pour Point Diesel
7.
EGO (Export GO)
(Heavier than diesel) used for fuel or further
processing
8.
Heating oil
Heating
9.
Fuel oil
LSFO low sulfur fuel oil (for water desalination
& power and plants)
HSFO - High sulfur fuel (Bitumen)
LFO (Bunker/Cargo)
14.
Sulfur
Sulfuric acid, matches, etc.
15.
Coke (carbon)
Aluminum and other industries
16.
Asphalts
Roads
17.
Oils and waxes
Lubricating oils
White oils
Transformer & cable oils
Greases
Waxes
18.
Chemicals, Solvents, misc.
Many industries

Table 5.2. Applicable ASTM Specifications for Petroleum Products

Specification for
Specification Number
1. LPG
D1835
2. Automotive Gasoline
D439
3. Aviation Gasoline
D910
4. Aviation Turbine Fuels
D1655
5. Fuel Oil no. 1 to 6
D396
6. Diesel Fuel Oil
D975
7. Gas Turbine Fuel Oil
D2880

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Petroleum Refining Chapter 5: Refinery Feeds and Products

Table 5.3. Kuwait Refineries Feeds and Products.

MAA refinery
SHB refinery
MAB refinery
(400 MBPD)
(200 MBPD)
(265 MPD)
Product
BPD
Product
BPD
Product
BPD
Propane
Butane
Pentane
LPG
LPG
KNG (Kuwait Natural
Gasoline)
MoGas (96 unleaded,
Gasoline
90, 95 , 98 Leaded)
light Naphtha
Naphtha
lt Naphtha
Naphtha
PCN
Hvy Naphtha
PCN
PCN
Alkylate
ATK
Kerosene
ATK
DPK
ILL Kerosene
JP8
Kerosene
High Speed Diesel (HSD)
Diesel
HSD 20P/30P
Marine Diesel Oil
Marine Diesel
Marine Diesel
Low Pour Point
Oil
Diesel
Export GO
EGO (Export
GO)
VGO
CGO
LSFO
Fuel Oil
Fuel Oil
LFO (Bunker)
HFO (Bunker/Cargo)
Bitumen
Sulfur
Sulfur
Sulfur
228.3
Bitumen
Coke
710.6

M tons/yr

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Physical and Chemical Properties of Refinery Products

Low Boiling Products

Compounds that are in gas phase at ambient T & P.

Examples; methane, ethane, propane, butane, and their olefins.
Require a gas plant in the refinery
Gas quantity is expressed in
1. Weight basis: (lb or kg)
2. Volumetric basis: scf (standard cubic feet) or Nm (normal cubic meters)
3. Heating Value: (bbls FOE based on a lower heating value LHV of 6.05 MMBtu
or 6.38X106 KJ).
Standard conditions 60 F & 14.7 psia
Example 5.1:
Calculate the mass flow rate and the fuel oil equivalent (FOE) for a gas stream flowing at
10 MMSCFH. The laboratory analysis of the gas is given below,
Vol %
C1
70
C2
25
C3
5
Solution:
For a gas at standard conditions (ideal), the volume percent is equal to the mole percent.
mole %
MW
heating value (Btu/scf)
C1
70
16
909.4
C2
25
30
1618.7
C3
5
44
2314.9
PV = nRT
n = PV/RT = (14.71E+7)/(10.73(60+460)) = 26,346 lbmol/hr
or simply divide by 379.5 such that 1E+7/379.5 = 26,350 lbmole/hr
Mole average the MW of gas = 0.716 + 0.2530 + 0.0544
= 20.9 lbm/lbmol
gas mass flow = 26,35020.9 = 550,712 lbm/hr
Vol. average heating value = 0.7909.4 + 0.251618.7 + 0.052314.9
= 1157 Btu/scf
Gas heating value = (1E+7) SCFH (1157) Btu/scf = 1.157E+10 Btu/hr
FOE = (1.157E+10) Btu/hr / (6 MMBtu/bbl) = 1930 bbl/hr = 46,300 BPD
Table 5.4: Properties of Hydrocarbons and common gases1
Compound

MW

Methane
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane
n-Hexane

16.043
30.070
44.097
58.123
58.123
72.150
72.150
86.177

Heating Value
60F, 1 atm (Btu/scf)
Net
Gross
909.4
1010.0
1618.7
1769.6
2314.9
2516.1
3000.4
3251.9
3010.8
3262.3
3699.0
4000.9
3706.9
4008.9
4403.8
4755.9

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Petroleum Refining Chapter 5: Refinery Feeds and Products

n-Heptane
100.204
5100.8
n-Octane
114.231
5796.1
n-Decane
142.285
7189.6
Hydrogen sulfide
34.080
586.8
Nitrogen
28.013
Oxygen
31.999
Carbon Dioxide
44.010
Water
18.0153
Air
28.9625
1
Source GPSA Engineering Data Book, 10th ed., 1987.

5502.5
6248.9
7742.9
637.1
-

1. Methane (C1)
Use: - Refinery fuel (burned in heaters).
- Feedstock to the H2 production unit.
2. Ethane (C2)
Use: - Refinery fuel.
- Feedstock to H2 production unit.
- Feedstock to produce ethylene (petrochemical plant).
3. Propane (C3)
Use: - Refinery fuel
- Sold as LPG
- Propylene is sometimes separated for sale to petrochemical plants for
polypropylene manufacture.
4. n-Butane (n-C4):
Use: - Sold as LPG
- Feedstock to isomerization units producing isobutane.
- Blending into Gasoline (increase octane number1).
Price of gasoline > LPG
It is better to blend n-C4 into gasoline than sell it as LPG
It has high Octane Number (in the 90s)
VP (n-C4) < VP (i-C4) << VP (C3)
RVP 52
RVP 71
RVP 210
(unitpsig)

Preferred for blending into gasoline

(1) Regulate its vapor pressure
without exceeding the RVP specification
(2) Promote better start in cold weather.
of the gasoline product.

Refiners put as much n-C4 in their gasoline as vapor pressure limitations permit.
RVP spec is less for summer because (too high RVP leads to)
- Vapor lock (engine stalls; does not start).
- HC emissions (pollution & losses).
- Explosive.
- Storage tank rupture or leakage (hazard).
need to optimize RVP = 7.2 psig (summer)
= 13.5 psig (winter)

A costly alternative is higher severity catalytic processes such as reforming, alkylation, and
isomerization which reduces catalyst life.

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

5. Iso-butane (i-C4)
i-C4 can also be blended into gasoline, but its relatively higher RVP permits a lesser
amount to be incorporated into gasoline than n-butane.
Has greatest value when used as feedstock to alkylation unit.

Propene
i-C4 + Butenes
Pentenes

alkylation

iso-paraffins (high octane)

in the gasoline boiling range .

LPG
Liquefied petroleum gas contains mostly C3 and C4 with various ratios.
Produced from almost all processing units with naphtha stabilizers or debutanizers.
Gasoline
Motor gasoline is the principal product of refineries.
It consists of a complex mixture of HCs with typical ASTM BP range from 100 to
400 F.
API survey shows
- 40 types of gasoline exist
(variations in octane number, API, IBP, FBP, ).
- 90 % of gasoline in US used as motor fuel.
Gasoline Types:
- leaded
- unleaded
Grades
Kuwait UAE KSA USA
Regular
87
Premium
91
89
Super Premium
95
92/93
Utra
98
99
Regular Leaded Gasoline in US is now used only for:
- Farm equipment.
- Pre 1972 automobiles.
The difference is in Antiknock performance
Octane Number
Is a measure of the degree of knocking of (gasoline).
It compares the degree of combustion of gasoline to that of a mixture of n-heptane
(zero octane) and iso-octane (100 octane) expressed as V% iso-octane (2,2,4trimethylpentane) .
Most common lab tests for determination of octane number:
(a) Motor method (MON)
Represent performance on the highway or heavy load conditions (high speed).
(b) Research method (RON)
Represent performance during city driving (low speed and acceleration is
relatively frequent)
Both use same test engine but operate under different conditions. MON at high
engine speed and RON at low engine speed.
(c) Posted octane number (PON) PON RON MON
2
Sensitivity of the fuel
Sensitivity = (RON MON)

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Petroleum Refining Chapter 5: Refinery Feeds and Products

The sensitivity of the performance of the fuel to the two types of driving conditions
(Low Sensitivity fuels are better; equal performance is all conditions is desirable).
For all gasoline, octane numbers average about two numbers lower for the higher
elevations of the rocky-mountain states
Less n-C4 can be blended because of the lower pressure at high elevations (so the
final RVP of the blend is constant).
Gasoline blending streams
1.
Light straight run (LSR) gasoline (C5 180/190/200 F).
2.
Reformate (Catalytic Reformer gasoline).
3.
Alkylate (Alkylation unit gasoline)
4.
Catalytic Cracker gasoline.
5.
Hydrocracker gasoline.
6.
Polymer gasoline. (polymerizing olefins to produce higher MW olefins in the
gasoline boiling range)
7.
n-C4 RVP & ON
Octane Improvers (oxygenates)
1.
TEL (Tetra ethyl lead ) (pollutant)
2.
MTBE (methyl tertiary butyl ether)
3.
ETBE (ethyl tertiary butyl ether)
4.
TAME (tertiary amyl methyl ether)
5.
Ethanol
Table 5.1: Oxygenates and octane improvers of gasoline.

Methanol

Ethanol
(ethyl alcohol)

TBA
MTBE
(t-Butyl Alcohol) (tert-butyl methyl ether)
tert-Butanol

ETBE
TAME
ethyl tert-butyl ether tert-amyl methyl ether

TEL
(Tetraethyl lead)

Motor Gasoline Blending

1.
Promote high antiknock quality (high ON).
2.
Ease at starting.
3.
Quick warm up.
4.
Reduce vapor-lock.
5.
Reduce engine deposits.
Other additives (antiknock chemicals)
1. Antioxidants.
2. Metal deactivators.
3. Anti-stall agents.

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Environmental restrictions
Limit sulfur & total aromatics content of diesel.
On gasoline limit.
1. Sulfur (< 300 ppm or .03 wt %)
2. Total aromatics
3. Olefins2
4. RVP
5. Min. O2 content (for areas of CO2 problem)
6. Specific compounds (e.g. Benzene, xylenes)
This lead to the concept of Reformulated gasoline (a fuel for spark ignition engines
which is at least as clean burning as high methanol content fuels).
Gasoline Specifications
Properties of gasoline that have the greatest effect on engine performance:
1. RVP (govern ease of starting an engine).
2. BP. Range (IBP govern ease of starting).
3. Anti Knock Characteristics (Octane number).
The boiling range governs
- Ease of starting
- Rate of acceleration
- Mileage economy
- Tendency toward vapor lock
- Engine warm-up time3
Warm-up time is expressed in terms the distance operated to develop full power
without excessive use of the choke (3-7 km warm-up is considered satisfactory).
Reid Vapor Pressure
Vapor lock is directly related to RVP of the gasoline
The RVP should not exceed the following limits.
Ambient temp (F)
60
70
80
90

Max allowable RVP (psia)

12.7
11.0
9.4
8.0

As T increases, max allowable RVP is decreased. Why?

Effect of Altitude on Gasoline

1. Losses by evaporation.
2. Octane requirement. ( 3 units lower per 1000 ft of elevation)
In practice; the spark is advanced at higher elevation to improve engine
performance (2 units lower per 5000 ft elevation)

React with compounds in the atmosphere producing visual pollutants.

Controlled by the vol. % distilled @ 158 F and the 90% ASTM distillation temperature.

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Petroleum Refining Chapter 5: Refinery Feeds and Products

Effect of hydrotreating on gasoline

Hydrotreating the FCC Naphtha (gasoline) saturates the olefins and lowers ON by 23).
Table 5.5. Effects of variables on octane requirements1.
Variable
Effect on Octane Requirement
Altitude
-3 RON per 1,000 ft increase in altitude.
Humidity
-1 RON per 20% increase in relative humidity @ 70 F
Engine speed
-1 RON per 300 rpm increase
Air temperature
+1 RON per 20 F rise
Spark advance
+1.5 RON per 1 advance
Coolant temperature
+1 RON per 10 F
Combustion chamber deposits
+1 to 2 RON per 1,000 miles up to 6,000 miles
1
Source 'Petroleum Refining Engineering', Gary & Handwerk, 1991.

Distillate Fuels

Divided into Three types:

- Jet (turbine) fuels

- Diesel fuels
- Heating Oils (fuels)
They are blended from a variety of refinery steams to meet the desired spec.
Heating oils rank second after gasoline in refinery production
However, recently restricted by:
1.
Environmental regulations on fuel emissions which caused some users to
convert to natural gas & LPG.
2.
Expansion of air & truck travel, which increased diesel & jet fuel demands.

1. Jet Fuels (Turbine Fuels)

In the kerosene boiling range
Must be clean burning.

- Commercial aviation
- Military air crafts
Limiting specifications for jet fuels in general are:
- Freezing point (- 40 C)
- Flash point (110-150 F)
- Distillation
- Smoke point
- Aromatics content
Main difference is in freezing point - 40 to -50 C max.

Naphtha Jet Fuel

Produced primarily for the military
Wide-boiling-range stock (extends through the gasoline & kerosene boiling ranges)
More volatile & has more safety problems in handling.
Used in national emergency when kerosene type is not enough.
Kerosene Jet Fuel
More safe in handling

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

Commercial aviation
Narrow-boiling-range stock (350-550 F) kerosene range.

Table 5.6. US military jet fuel and related specifications.1

Specification
AN-F-32
MIL-F-5616
AN-F-34
AN-F-58
MIL-F-5624
MIL-T-5624
MIL-T-5624
MIL-F-25524
MIL-F-25656
MIL-T-38219
MIL-T-83133

MIL-F-5161
MIL-F-5572
MIL-I-25017
MIL-F-25558
MIL-P-25576
MIL-I-27686
MIL-F-81912
MIL-F-82522

MIL-I-85470
MIL-P-87107
MIL-P-87107
1

First
Issued
1944
1950
1945
1947
1950
1950
1950

Grade

Type

Use

JP-1

Very low-freeze kerosene

Obsolete

JP-2
JP-3

Wide cut (RVP max 2 psi)

Wide cut (RVP 3 to 7 psi)

Obsolete
Obsolete

Wide cut RVP 2 to 3 psi)

High-flash kerosene
Thermally stable kerosene
Light kerosene(thermally stable)
Low-volatility kerosene
(special properties)
kerosene (Jet A-1 type)

Air force standard

Naval carrier aircraft
Flight test fuel supersonic bombers
(obsolete)
Very high performance aircraft

1956
1965

JP-4
JP-5
JP-TS
JP-6
JP-7

1976

JP-8

Avgas

RJ-1
RP-1
FSII
RJ-4
RJ-5
RJ-6
FSII
JP-9
JP-10

RELATED SPECIFICATIONS
Referee JP-4 and JP-5
Aviation gasoline(several grades)
Chemical materials
High-density kerosene
Narrow-cut kerosene
Ethylene glycol mono-methyl ether
high flash, narrow-cut kerosene
T-H, dimethyl cyclopentadienes
T-H Norbornadiene dimer
63% RJ-5, 37% JP-10
di-EGME
blend of MCH, JP-10, and RJ-5
T-H dicyclopentadiene

Air force standard

Ground test fuels (obsolete)

Military standard (see Table 1)
Fuel soluble corrosion inhibitor
Air force ramjet fuel
Rocket fuel
Fuel system icing inhibitor
Missile fuel (navy)
Ramjet fuel (navy)
Missile fuel
Missile fuel system icing inhibitor
Missile fuel
Propellant/fuel component

Source 'ASTM manual on significance of tests on for petroleum refining' George V. Dyroff.
2. Diesel Fuels
2.1. Automotive Diesel Fuels
Types
No.1 Diesel Fuel (Super-diesel)
- Used in high speed in automobiles (trucks, busses)
- Usually made from virgin (CDU) stocks
- Have cetane number (45-50 min)
- BP range 360 600 F
No.2 Diesel Fuel
- Lower cetane number (40 min)
- Has a wider BP range 360 650 F
- Usually contains cracked stocks

Important Properties
1. Ignition quality (cetane number or index)
2. Volatility (Flash point)

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Petroleum Refining Chapter 5: Refinery Feeds and Products

3.
4.
5.
6.

Viscosity
Sulfur content
% Aromatics
Cloud point

Diesel Ignition Properties (Cetane number)

- Very similar to the octane number.
- Compares the degree of combustion of diesel fuel to that of a mixture of
cetane (C16H34, high-ignition quality) and alpha-methyl-naphthalene (C11
H10, low ignition quality) expressed as V% cetane.

Cetane
-methylnaphthalene
Lower S & aromatics content, lowers the particulate emissions from diesel engines.

2.2. Railroad Diesel Fuels

Used for railroads
Similar to the heavier automotive diesel fuels, except,
- Have higher BP ranges (up to 750 F end point)
- Lower cetane numbers (30 min.)
3. Heating oils
Its consumption ranks very high from Petroleum product, but has recently decreased
in favor of LPG.
Types:
No.1 Fuel Oil: (V. similar to Kerosene, with higher pour and end points)
No.2 Fuel Oils: (Similar to No.2 diesel fuel).
Limiting Specs are: 1. Distillation
2. Pour point
3. Flash point
4. Sulfur content
4. Residual Fuel Oils
Composed of the heaviest parts of the crude, generally, the vacuum unit fractionating
tower bottoms.
Types:
HSFO: Sells for very low price (70% of the crude oil).
LSFO: Heavy fuels oils with very low sulfur (price of crude).
Critical Specs are
1. Viscosity
2. Sulfur Content (Generally governed by the locality in which it is burned, i.e.
Africa, America).

No. 1 6 fuel oils

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Copyrights 2001-2015, Dr. Tareq Albahri, Chem. Eng. Dept., Kuwait University

The heaviest part of petroleum; Tar, pitch, asphalt and bitumen are often used
interchangeably although they are different
1. Tar

A viscous black liquid

Derived from the destructive distillation of organic matter.
Tar is predominantly composed of bitumen (Contains less bitumen than asphalt
does).
Is considered toxic and carcinogenic because of its high benzene contents.
Coal and petroleum tar has pungent or repulsive odor
Tar is used in treatment of the
skin-disease psoriasis. It is also a
general disinfectant. Petroleum
tar was also used in ancient
Egyptian mummification. Tar was
a vital component of the first
sealed roads. It was also used as
seal for roofing shingles and to
seal the hulls of ships and boats.

Tar
2. Asphalt
Asphalt is composed almost entirely of bitumen (Contains more bitumen than Tar
does).
Asphalt is a sticky, black and highly viscous liquid or semi-solid that is present in
most crude petroleum.
Asphalt can be separated from the other components in crude oil by processing of the
Vacuum Residue in a deasphalting unit, which uses either propane or butane in a
supercritical extraction. Further processing is possible by "blowing" the product:
namely reacting it with oxygen. This makes the product harder and more viscous.
The structure is most commonly modeled as a colloid, with asphaltenes as the
dispersed phase and maltenes as the continuous phase.
Uses; There are two forms commonly used in construction: rolled asphalt and mastic
asphalt.
In the ancient times used for mortar between bricks and stones, ship caulking,
waterproofing, and mummification.
Rolled asphalt concrete; The largest use of asphalt is for making asphalt concrete for
road surfaces and accounts for approximately 80% of the asphalt consumed in the

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Petroleum Refining Chapter 5: Refinery Feeds and Products

United States. Roofing shingles account for most of the remaining 20% asphalt
consumption. Other uses include cattle sprays, fence post treatments, and
waterproofing for fabrics.
Mastic asphalt; Mastic asphalt is a type of asphalt which differs from dense graded
asphalt (asphalt concrete) in that it has a higher bitumen (binder) content, usually
around 7-10% of the whole aggregate mix, as opposed to roller asphalt, which has
only around 5% added bitumen.
Base layer of asphalt concrete in a road under
construction.

3. Bitumen
Bitumen is sometimes referred to as Asphalt
A mixture of organic liquids that are highly viscous, black, sticky, and composed
primarily of highly condensed polycyclic aromatic hydrocarbons.
The residual (bottom) fraction obtained by fractional distillation of crude oil; It is the
heaviest fraction and the one with the highest boiling point.
Bitumen is primarily used for paving roads and waterproofing products, including the
use of bitumen in the production of roofing felt, sealing flat roofs, waterproof boats,
and even as a coating for buildings.
4. Pitch

Is a highly viscous liquid which appears solid

Can be shattered with a hard impact
Flows at room temperature but extremely slowly
Uses: Pitch was traditionally used to help caulk the seams of wooden sailing
vessels

5. Coke
The heaviest refinery product
Is a solid with little volatile HC amount
The volatile matter is removed by calcination

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