Petroleum Refinery Engineering

PP-414

Dr. SAUD HASHMI

Associate Professor

Department of Polymer & Petrochemical

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 Talk outline

Part 1: Refinery Feedstock & Its Specification.

Part 2: Major Refinery Products & Specification?

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 Refinery Property Estimation

The following list summarizes the refinery process and product properties required
for process design calculations:

1. True boiling point curve (always given) of crude and intermediate/product streams
2. Volume (Mean) average boiling point (VABP)
3. Mean average boiling point (MEABP)
4. Weight average boiling point (WABP)
5. Molal average boiling point (MABP)
6. Characterization factor (K)
7. Vapor pressure (VP) at any temperature
8. Viscosity at any temperature
9. Average sulfur content (wt %)
10. Degree API
11. Enthalpy (Btu/lb)
12. ASTM conversion to TBP and vice‐versa
13. Viscosity of a mixture using viscosity index
14. Flash point of a mixture using flash point index
15. Pour point of a mixture using pour point index
16. Equilibrium flash vaporization curve
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 Physical properties of feedstock's and products
True Boiling Point Distillation (TBP Distillation)

The boiling point distribution of crude oil (boiling point versus volume or mass percent
distilled) is obtained through a batch distillation test ASTM 2892. The distillation
apparatus has 15–18 theoretical plates with a 5:1 reflux ratio. For boiling points below
340 C (644F) the distillation is performed at atmospheric pressure. The residue is
distilled under vacuum (1–10 mm Hg). The boiling points under vacuum are
converted to normal boiling points. The distillation continues to a normal boiling point
of 535C (995F). This test allows for the collection of sample cuts at different boiling
point ranges. These cuts can be subjected to physical and chemical measurements.
.
ASTM Distillation (an Engler Distillation)

The distillation of petroleum cuts is done in a simple distillation apparatus which does
not have a fractionation column. For light cuts (gasoline, kerosene, diesel and heating
oil) the distillation is run at atmospheric pressure under ASTM D86 test. For heavier
fractions an ASTM D1160 test at reduced pressure is employed.
The temperature of the vapor at which the first drop of condensate drips from the
condenser is referred as “IBP” initial boiling point. The vapor temperature is also
recorded at each successive 10% is collected. When 95% has been distilled the
maximum temperature is recorded as “End Point” EBP.
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 Physical properties of feedstocks and products
Simulated Distillation by Gas Chromatography
The boiling point distribution of the whole crude oil can be determined by an injection
of the sample in a gas chromatograph which separates the hydrocarbons in boiling
point order. The retention time is related to then boiling point through a calibration
curve. The results of this test are comparable to the true boiling point tests. In
addition, the boiling point distribution of light and heavy petroleum cuts can also be
done by gas chromatography. One of the standards methods of measurements is
ASTM D5307.

API Gravity
API = (141.5/SG 60oF) – 131.5 The purpose of this equation was to extend the range
of the specific gravity scale. Crude oil SG changes, although small, may be
Important.
Crude Oils oAPI = 10 – 50
Higher oAPI, more paraffinic crude, higher yields of gasoline.
Lower oAPI, more aromatic crude, lower yields of gasoline.

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 ASTM Methods for Products Property Evaluation

Salt Content
Measured by ASTM – 3230 (lb NaCl/1000 bbl)
Desalting is necessary because NaCl content > 10 lbs/1000 bbl leads to corrosion
Metals
Measured by EPA Method 3040. These include Ni, V, Ag, Hg, Na, and Ca. Metals
can cause catalyst deactivation and corrosion.
Sediment and Water
Measured by ASTM D – 96 These inorganic particles can lead to operational
problems.
Acidity : Measured by ASTM – 664
Pour Point
Measured by ASTM D-97 – temperature at which oil ceases to flow. Diesel may
contain waxes, smaller than candle wax, which could solidify in cold weather.

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 ASTM Methods for Products Property Evaluation

Flash Point
Temperatures above which the oil will spontaneously combust. Fractions in vacuum
tower are the least combustible. They are the heaviest.

Vapor Pressure
Measured by ASTM D-323 Also know as Reid vapor pressure (RVP). True vapor
pressure is usually 5-9% > RVP

Carbon Residue
The solid residue (%wt) remaining after heating to coking temperatures (700-800oC)
ASTM D-524 Ramsbottom Carbon
ASTM D-189 Conradson Carbon
CCR incr. then Asphaltene incr.

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 Base of crude oil

1. (Mallison classification according to residuum) a material left behind after

distillation of fractions.

Residue > 50% paraffins Paraffinc base

Residue < 20% paraffins Asphaltic base
Residue 20-50% paraffins Mixed base

2. The U .S. Bureau of Mines designated base of crude oil.

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 Refinery Products
4. Characterization Factor

The most widely used index is characterization factor (Watson, Nelson and Murphy).
It was originally defined as:
In which:

TB is the average molal / Mean boiling point (R)

S is the specific gravity at 60 F
It has since related to viscosity, aniline, temperature, molecular weight, critical
temperature, percentage of hydrocarbon etc.
K ≥ 12.15 (Paraffinic Base)
K< 11.5 (Aromatic Base)
K between 11.5-12.15 (Napthenic Base)
5. Correlation Index (C .I)
Like (C.F) related to boiling point and gravity
C.I for Parafine =0 C.I for Benzene =100
C.I =0-15 Parafine C.I =15-50 either Naphtenes or mix (Parafine Naphtenes)
C.I = above 50 Aromatic Department of Polymer & Petrochemical
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 Evaluation Of Oil Stock
Characterization Factors
There are several correlations between yield and
the aromaticity and paraffinicity of crude oils,
but the two most widely used are the UOP or
Watson ‘‘characterization factor’’ (KW) and the
U.S. Bureau of Mines ‘‘correlation index’’ (CI).
This method is for calculating the UOP
Characterization Factor of petroleum oils from
API gravity and distillation data.
The UOP Characterization Factor, commonly
called KUOP, is indicative of the general origin
and nature of a petroleum stock.
 Evaluation Of Oil Stock
Watson characterization factor:

SG: Specific Gravity at 15C (60 F)

Tb: mean average boiling point (R) (MeABP)
The Watson characterization factor ranges from less than 10
for highly aromatic materials to almost 15 for highly paraffinic
compounds.
Crude oils show a narrower range of KW and vary from 10.5
for a highly naphthenic crude to 12.9 for a paraffinic base
crude.
 Evaluation Of Oil Stock
Mean Average Boiling Point (R) (MeABP)
Given the ASTM D86 distillation the VABP can be calculated as the
average of the five boiling temperatures at 10, 30, 50, 70 and 90 percent
distilled.

Where all temperatures are in F

The MeABP is calculated using the following equation:

 Calculation of Kw
Calculate the MeABP of the petroleum fraction . If the
API gravity of this fraction is 62, calculate the Watson’s
characterization factor.
UOP characterization factor:
Kuop has the same expression as Kw, but Tb transfer to
Volume average boiling point (VABP)
Additional notes related to the application of the above
characterization factors:
• Aromatics would have lower KUOP
• The use of boiling point indicates a relationship to the
interactive forces between the molecules.
• The use of specific gravity relates to how tightly the
molecules are packed (i.e. density)
 CH-406 : Evaluation Of Oil Stock
correlation index (CI).
The correlation index is useful in evaluating
individual fractions from crude oils. The CI scale is
based upon straight-chain paraffins having a CI
value of 0 and benzene having a CI value of 100.
The CI values are not quantitative, but the lower the
CI value, the greater the concentrations of paraffin
hydrocarbons in the fraction; and the higher the CI
value, the greater the concentrations of naphthenes
and aromatics.
 6. Viscosity Index: (V. I)

A series of numbers ranging from 0-100 which indicate the rate of change of
viscosity with temperature.
Paraffinic base V.I =100
Naphthenic base V.I = 40

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