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Refinery Products

All refineries can produce a range of products:

Hydrogen
Ethylene and chemicals
LPG
Refinery Products Butanes
Motor Gasoline
Though
not every
Aviation Gasoline refinery
Naphtha
Refinery Jet Fuel produces
Crude Oil
Kerosene all of
Diesel these at
Heating oil once
Fuel Oil
Lube Oil
Asphalt
Coke

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Refinery Products (Cont.) Refinery Products (Cont.)

In other words, if the refinery makes anything that has the

Determines properties of gasoline
The type of The refinery
products configuration

The required How the refinery It can sell it as gasoline!

product processes are run
properties

Almost all refineries produce
Because oil is a complex mixture of molecules, you cannot  Light ends (Low boiling products)
specify a composition for any refinery product (except light
gases and chemicals)  Gasoline
 Jet fuel
 Kerosene
 Diesel
Instead, the products are specified by  Fuel oil
their properties

So let us have look at these in more detail.

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Refinery Products (Cont.) Refinery Products (Cont.)

Light Ends or Low boiling products:

Light Ends or Low boiling products:
C4H10:
 Compounds which are in the gas phase at ambient temperature and pressures: CH4,
 Used as components of gasoline.
C2H6, C3H8, C4H10 and their corresponding olefins.
 Used in LPG and other refinery processes.
CH4:
 Butane and propane mixture sold as a LPG.
 Used as a refinery fuel.
 n-butane has a lower vapor pressure than iso-butane and is usually preferred for blending
 Used as a feedstock for hydrogen production by pyrolytic cracking and reaction
into gasoline to regulate its vapor pressure and promote better starting in cold weather.
with steam.  n-butane has a RVP of 358 kPa and i-butane has RVP of 490 kPa.
C2H6:  i-butane is not a desirable compound for gasoline blending because its higher vapor
 Used as a refinery fuel. pressure permits a lesser amount to be incorporated into the gasoline.
 Feedstock for hydrogen and ethylene production.  n-butane used as feedstock for isomerization unit to form i-butane.
 C3H8:  i-butane used as a feedstock to alkylation unit where it is reacted with unsaturated

 Frequently used as a refinery fuel. compounds (propylene, butene and pentene) to form high octane isoparaffin compounds in

 Sold as a LPG (max. vapor press: 210 psig at 100 oF) the gasoline range.
 i-butane produced mainly from FCC and hydrocracking process.
 Propylene used for polypropylene (PP) production
 i-butane is converted to isobutylene which is reacted with methanol to yield methyl tertiary
butyl ether (MTBE). 6
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Refinery Products (Cont.) Refinery Products (Cont.)

Gasoline: (iii) FCC and Hydrocracking (HC) gasoline:
 Gasoline are complex mixture of hydrocarbons having typical boiling ranges between  Generally used directly as gasoline blending stocks.
38 and 205 oC (determined from ASTM).  Sometimes, Heavy FCC gasoline sent to reformer units for octane improvement
 Components are blended to promote high antiknock quality, ease of starting, quick while light gasoline is directly taken to gasoline blending stocks.
warm-up, low tendency to vapor lock and low engine deposits. (iv) Polymer gasoline:
Gasoline Blend stocks:  Manufactured by polymerizing olefinic hydrocarbons to produce higher molecular
(i) Light straight-run gasoline: weight olefins in the gasoline boiling range.
 Consists of C5 fraction.  RON of polymer gasoline is 96-97 and MON is 82-83; PON is 89; RVP is 0.64 bar.
 Straight-run gasoline has octane number of 40-60.
(ii) Reformate gasoline:
 C5+ gasoline product.
 Reformer increases the octane by converting low-octane paraffins to high octane isobutylene Di-isobutylene
aromatics. isobutylene
 Heavy naphtha and coker gasoline used as feed stock for reformer.
 When octane needs require, FCC and hydrocracked gasoline processed by the reformer
unit to increase the octane level.
 Reformate RON is 90-104 Propylene Propylene Dimer
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Refinery Products (Cont.) Refinery Products (Cont.)

(v) Alkylate gasoline: (v) Alkylate gasoline (cont.):

 Product of the reaction of iso-butane with propylene or butylene to produce
branched chain hydrocarbons.
 Properties of alkylate: RON = 90, MON = 89, PON = 90, RVP = 0.3-0.4 bar.
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 Refinery technology favors alkylation process rather than polymerization process
for the following reasons:
 Alkylation of a given quantity of olefins produces twice the volume of high octane
gasoline as can be produced by polymerization.
 Alkylation product is paraffinic rather than olefinic and olefins are highly
photoreactive and contribute to visual air pollution and ozone production.
 PON of alkylate is higher and sensitivity (RON-MON) is significantly lower than
that of polymer gasoline.
(vi) n-butane:
 Blended into gasoline to give the desired Reid vapor pressure.
 The RVP of gasoline is a compromise between a high RVP (to improve engine
starting characteristics) and low RVP (to prevent vapor lock and reduce
evaporation losses).
 RVP of gasoline: 49.6 kPa (summer) and 93.1 kPa (winter).

Refinery Products (Cont.) Refinery Products (Cont.)

(vi) n-butane:
 Tendency to vapor lock is directly related to the RVP of gasoline. To control this,  Sources of sulfur in gasoline:
the RVP of the gasoline should not exceed the following limit.

Temperature (oC) Max. allowable RVP (kPa)

15.6 87.6
21.1 75.8
26.7 64.8
32.2 55.2

Gasoline blend stock properties:

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Refinery Products (Cont.) Refinery Products (Cont.)

Octane Numbers for selected pure compounds:

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Refinery Products (Cont.) Refinery Products (Cont.)

Gasoline properties:
Gasoline properties:
 Many refinery processes exist to improve octane; motor gasoline has RON of 87-93  Octane number is influenced by different factors:

 In the past, octane was improved by adding tetra-ethyl lead (TEL) Variable Effect on octane
 More recently, octane has been increased by using more high octane streams from Altitude -3 RON per 1000 ft increase in altitude (Increasing altitude a fuel of
catalytic processes (“unleaded” gasoline) less octane is satisfactory; less evaporation loss)
 Octane is now often improved by adding oxygenates and their properties are listed Humidity -0.5 RON per 10% increase in relative humidity at 70 0F (less
below: octane fuel required for high humidity conditions)
Engine speed -1 RON per 300 rpm increase (high speed engine requires low
octane fuel)
Air temperature +1 RON per 11 0C rise (cold countries require less RON fuel)

Coolant temperature +1 RON per 10 0F increase (For every 10 0F increase in coolant

temperature, engine demands an increase of 1 RON in quality of
fuel as essential)
 10% MTBE: increase 4.3 RON and 3.4 MON for reformat gasoline, 2.3 RON and 1.4
MON for cracked gasoline Combustion chamber +1 to 2 RON per 1000 miles up to 6000 miles
deposits
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Refinery Products (Cont.) Refinery Products (Cont.)

Worldwide gasoline quality:
Gasoline Quality Requirements (Euro Norms):

India Property Euro-I Euro-II Euro-III Euro-IV Euro-V

Euro South New South (Year (Year 1996) (Year 2000) (Year 2005) (Year 2009)
Attributes Unit (BS Japan China Taiwan
III Korea Zealand Africa
III) 1992)
RON 95 95 95 95 95
RON Min. 91 91/95 89/96 91/94 91/95 90/93/95 92/95/98 95/97
MON 85 85 85 85 85
ppm
Sulfur 150 150 100 130 350/150 800 80/120/180 1000/1500 Sulfur, ppm 500 500 150 50 10
min
(max)
Vol%
Aromatics 42 42 - 30 or 35 48/42 40 ** - Benzene, 5.0 5.0 1.0+ 1.0 1.0
max
%vol. (max)
Vol%
Olefins 21 21/28 - 23 or 18 20 or 25 35 ** -
max Aromatic, - - 42 35 35
%vol. (max)
70-sum,
RVP kPa 35-60 60&70 44-78 45 kPa min 88 (win) 59/59/61 45-75
96-win Olefin, %vol. - - 18 18 18
(max)
Lead, g/lit 0.013 0.013 0.005 0.005 0.005

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Refinery Products (Cont.) Refinery Products (Cont.)

Gasoline Quality Requirements (Indian Norms):
Typical Process Units & Gasoline Blending Components in Indian Refineries:
Property Bharat Stage-II Bharat Stage-III Bharat Stage-IV Bharat Stage-VI
(Target Year: (Target Year: (Target Year: (Target Year:
S. Process Gasoline Remarks
2001 - selected 2005 - selected 2010 - selected 2020 - nationwide)
cities & 2005 - cities & 2010 - cities & 2017 - No Unit Component
nationwide) nationwide) nationwide) 1 Catalytic Reformate High RON, Low Sulfur, High Benzene
Density at 15 oC, 710 - 770 720 - 775 720 - 775 720 - 775 Reforming and Aromatics
Kg/m3 2 FCC FCC Gasoline High RON, Low MON, High Sulfur,
RON, min 88 91 91 91 High Olefins
MON, min 84 (Antiknock 81 81 81 3 Crude Light naphtha Low RON, Low Sulfur
Index) distillation
Sulfur, ppm (max) 500 150 50 10
4 HCU Light/ Heavy Low Sulfur, Low RON
Benzene, %vol. 3 (Metros), 5 (rest 1.0 1.0 1.0 Naphtha
(max) of India)
5 DCU, VBU Cracked Naphtha Low RON, High Olefins, Diolefins,
Aromatic, %vol. - 42 35 35 high sulfur
(max)
Olefin, %vol. (max) - 21 21 21
Lead, g/lit 0.013 0.005 0.005 0.005
RVP @ 37.8 oC, 35 - 60 60 60 60
20
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Refinery Products (Cont.) Refinery Products (Cont.)

Aviation Gasoline:
 Narrow boiling range; Low vapor pressure; Sulfur is very low.
Kerosene:

 Basically consists of aromatics and highly branched paraffins to get high octane  API gravity: 41.5-43.
number.  Flash point: above 42 oC (approximately 50 oC)
 Cracked products in aviation gasoline are not permitted due to their chemical behavior  Small amount of naphtha is required in kerosene to produce good burning.
of giving inimical deposits.
 Smoke point of Indian kerosene is 18 mm.

Jet Fuel:  Sulfur content: 0.13 wt.%
High smoke point is essential for clean combustion

Diesel Fuel:
 Cetane Number (ASTM D-613): The percentage of pure cetane in a blend of cetane
and α-methylnaphthalene which matches the given quality of a diesel fuel sample.
 Higher the cetane number means shorter ignition delay and less CO emission.
 Cetane number increases with increase in carbon number of molecules.
 Cetane number increasing order: n-paraffins > olefins > iso-paraffins >
aromatics (please check with next slide!!!)
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Unsaturated compounds are responsible for gum formation

Refinery Products (Cont.) Refinery Products (Cont.)

Cetane numbers for selected pure compounds:
Properties of diesel blend stocks :

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Refinery Products (Cont.) Refinery Products (Cont.)

Worldwide diesel quality:
Diesel Fuel:

Two types of diesel fuel.
New India
Europe Australia No.1 Diesel or High Speed Diesel (HSD):
Attributes zealand Japan
(Euro-IV) (2002) Bharat II Bharat III Bharat IV Bharat VI
(2004)  Above 1000 rpm; load & speed vary
Cetane  Examples.: Engines used for road transport (buses and trucks) and diesel
54 49 - 45 48 51 51 51
number, min locomotives.
Density @ 820 -  Cetane No.> 50
845 820 - 860 860 820 - 860 820 - 845 820 - 845 820 - 845
15 oC, Kg/m3 860
 Pour point of Indian Diesel: 18 (summer), 6 (winter) and 0 oC (depends upon the
Kinematic
climatic conditions)
Viscosity @ - 1.5 - 4.5 2.0 - 4.5 2.7 2.0 - 5.0 2.0 - 5.0 2.0 - 4.5 2.0 - 4.5
40oC, cSt  Flash Point: 50-55 oC.
Total sulfur,  Diesel Index (DI): 45-55 [DI = oAPI Х Aniline Point (oF)/100]
50 & 10 3000 500 50/10 500 350 50 10
mg/Kg (max) No.2 Diesel or Low Speed Diesel (LSD):
35#
Flash point, oC 61* 61.5* 35# 35# 35#  Below 300 rpm; for heavy loads at constant speed.
/66*
Polyaromatic  Example: Propulsion engines in marine vessels and engines used in electric power
Hydrocarbons 11 - - - - 11 11 11 generation.
(PAH), %wt.
 Flash point: 49-50 oC (min)
* Pensky Martens Closed Cup 25  Contains cracked stocks. 26
# Abel

Refinery Products (Cont.) Refinery Products (Cont.)

Typical Process Units & HSD Blending Components in Indian Refineries:
Atmospheric Gas Oil (AGO):
 Feed stock for catalytic cracking unit.

S. No. Process Unit HSD Component Remarks  As such not sold in the market

1 FCC/RFCC TCO Low Cetane
VGO:

2 Crude SRGO Crude Specific  Feed stock for catalytic cracking unit.
3 HCU Gas Oil High Cetane, Low Sulfur
Lube Oil:
4 DCU, VBU Kero/Gas Oil Low Cetane  100 grades of lube oils available

Residue:
 Heavy liquid fuels and solids (fuel oil, coke, asphalt)

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