Estimation of Refinery

Stream Properties
UNIT I
 Topics to be covered
TBP, EFV, ASTM distillation curves and their relevance

Conversion of ASTM data to TBP data

Average temperatures and characterization factor

Pseudocomponent concept

Calculation of molecular weight, viscosity, enthalpy, blend properties

Outcome:
Appreciate the crude oil quality and price
Need for analysis of crude oil properties
Complexity of crude oils and its fractions Thermodynamic properties
- Enthalpy
Design and operation of refinery processing equipment like - Heat capacity
- Compressibility factors
◦ fractionation towers - Equilibrium K-values
◦ pumps - Flash curves
Transport properties
◦ heat exchangers - Viscosity
- Thermal conductivity
- Diffusivity
Physical properties
- Densities
- Volumes
Characterization of Petroleum Fractions:
Basic input data
Specific Gravity

Boiling Point curve (ASTM, TBP or EFV)

Kinematic Viscosity

Refractive index

Molecular weight
Specific Gravity

Both densities of oil and water are at the same standard temperature

and pressure conditions, which are 1 atm (14.7 psia) and 15.6 0C 60 F)
API gravity

Heavy oils have low API and light oils have high API gravities

Density measurements are done by

◦ Pycnometer
◦ Mettler/Parr densitometer
Boiling Point Curves: Distillation types
ASTM TBP

Single stage 15 stages

No reflux Reflux ratio of 5

Degree of fractionation lower Degree of fractionation higher

IBP is higher and FBP is lower IBP is lower and FBP is higher

Simple, requires less sample Complicated

 ASTM distillation
ASTM distillation is carried out in a relatively simple
apparatus consisting of a flask holding the sample
connected to an inclined condenser, which condensed
the rising vapours.

The fractions distilled are collected in a graduated

cylinder. The temperature of the rising vapours is
recorded at specific interval of the collected distillates.

This is essentially a batch distillation with one

equilibrium stage and no reflux and minimum
separation of the components of the fractions.
 TBP distillation
It is performed in columns with 15 theoretical plates
or equilibrium stages and a reflux ratio of 5.

Rising vapours are condensed and

Operation is at 760 mm Hg for boiling points below

400 C. For higher boiling point fractions, the
distillation is conducted at reduced pressures as low
as 0.5 mm Hg.
Significance of curves
Conversion between ASTM and TBP
Distillation
TBP distillation is both tedious and time-consuming

Two methods used

◦ Riazi and Daubert or API method
◦ Daubert method
 Riazi and Daubert (API Method)

where a and b are constants

Temperatures are in Rankin

 Daubert Method

The symbols T and T0 stands for ASTM D86 and TBP temperatures,respectively, both in F.

The subscripts 0 and f stand for the initial and final temperatures, respectively.

Ai and Bi are constants

Constants for Daubert Method
Calculations
T (ASTM) (0F) Ti Ti’ T’ (TBP) (0F)

T0 T1 = T10 - T0 T1’ = A1 (T1)B1 T0’ = T10’- T1’

T10 T2 = T30 – T10 T2’ = A2 (T2)B2 T10’ = T30’- T2’
T30 T3 = T50 – T30 T3’ = A3 (T3)B3 T30’ = T50’- T3’
T50 T4 = T50 – T50 = 0 T4’ = A4 (T4)B4 = 0 T50’ = A4(T50)B4
T70 T5 = T70 – T50 T5’ = A5 (T5)B5 T70’ = T50’+ T5’
T90 T6 = T90 – T70 T6’ = A6 (T6)B6 T90’ = T70’+ T6’
T95 T7 = T95 – T90 T7’ = A7 (T7)B7 T95’ = T90’+ T7’
Problem
Solution
Average boiling points
Volume Average Boiling Point (VABP)

Mean Average Boiling Point (MeABP)

Volume Average Boiling Point (VABP)
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.

All temperatures are in 0F

Mean Average Boiling Point (MeABP)
where MeABP is in 0F

where MeABP is in degrees Rankin

Problem
Calculate the MeABP of the petroleum fraction of the previous example. If the
API gravity of this fraction is 62, calculate the Watson’s characterization factor.

Answer: VABP = 224.5 F, MeABP = 206.1 F, and K = 11.94

 Problems 1 2 3 4 5


IBP, F 60.7 165.7 166.4 61.0 330.8

Homework problems 10 vol%, F

20 vol%, F
73.2

84.3
179.0 187.6 78.6

193.0 205.9 93.6

346.3

362.3

Calculate the MeABP of 30 vol%, F 99.1 207.0 222.4 106.1 378.0

the petroleum fraction. 40 vol%, F 108.3 221.1 237.9 117.0 393.5

Also calculate the 50 vol%, F 122.5 235.5 253.2 126.8 408.6

Watson’s characterization 70 vol%, F 142.3 265.6 283.6 143.7 438.0

80 vol%, F 150.6 284.2 299.0 151.2 452.2

factor.
90 vol%, F 158.0 306.1 314.5 158.4 466.2

95 vol%, F 161.5 317.8 322.3 161.7 473.1

EP, F 164.7 328.7 329.2 164.7 479.3

API 38 28 42 60 60
Pseudo components
Hence petroleum fractions are characterized as discrete
Cuts and Pseudo-components
Actual components of crude oil are not known.

The petroleum fractions are ‘‘cuts’’ from the crude oil with specific boiling point
range and with special properties such as API gravity and viscosity.

Each of these cuts can be further defined by dividing them into narrow boiling
fractions, called pseudo- (not real) components.

For these pseudo-components, the average boiling point can be estimated as

either mid-boiling point or mid-percentage boiling point.
Pseudo components
Each pseudo-component is characterized by an average normal
boiling point, specific gravity and molecular weight.
First two properties are found by experimentation and MW can be found by
correlation
Using these, the thermodynamic and thermophysical properties like enthalpy,
entropy and transport properties like viscosity, thermal conductivity and
diffusivity can be found
From these, the percentage of paraffins, naphthenes and aromatics can be found.
Breakup of TBP curve into pseudo
components
TBP cut point ranges are used to define pseudo-components with

the average temperature of the cut or the mid point NBP.

If the petroleum fraction contains components lighter than pentanes, the

composition of the lighter ends has to be available experimentally through
chromatographic analysis of the vapours.

Otherwise the lighter ends are lumped with the lightest pseudo-component.
 General Guidelines for determining the
pseudo components
100C for light fractions with BP less than 2000C

150C for fractions with BP between 200-4000C

200C for fractions with BP between 400-6000C

300C for fractions with BP beyond 6000C

Problem
Divide the TBP curve of the petroleum cut as calculated from API method in
previous example into 20 pseudo-components. Calculate the liquid volume
percentage of each pseudo-component
Solution
TBP curve is extrapolated to the final point of the distillation (100%) by fitting
the curve to a suitable polynomial function and extrapolating the results
Procedure
The FPB of the cut is 218.2 0C and the IBP = -5.40C

Each pseudo cut has an interval of [218.2 – (-5.4] / 20 = 11.2 0C

The curve can be cut as follows:

11.2 C
The FBP of the first cut is IBP + 11.2 = 5.8 0C

Average BP of the first pseudo component is (-5.4 + 5.8)/2 = 0.20C 2.84 %

Vol % of 2.84 is read from the TBP curve.

Similarly the second cut has FBP of 170C and the end vol % of 6.19

Vol % if this cut is 6.19*2.84 = 3.36

Avg BP of the second cut is (17+5.8)/2 = 11.4 0C

Pseudo components generated
Thermophysical
properties calculation
Molecular Weight
Pedersen formula
Problem
Calculate the molecular weight for the cut with NBP of 216.4 C and K = 11.94.

Answer = 170.8
Kinematic Viscosity

where v100 and v210 are the kinematic viscosities at 100 and 210 F, in centistokes.
Refractive Index
 Refractive Index
where a, b, c, d, e, and f are the constants
varying with molecular weight range

n is the refractive index at 20 C

I is the Huang characterization parameter at 20 C

Tb is the mean average boiling point, in deg

Rankin

M is the molecular weight of petroleum fractions

SG is the specific gravity, 60 F/60 F

Problem
Calculate the kinematic viscosities and the refractive index for oil which has a
MeABP of 320 C and API gravity of 34.

Answer = 1.481
Molecular type composition (P, N, A)
For heavy fractions (M > 200)

where a, b, c, d, e, f, g, h, and i are the constants varying with molecular weight range

xp, xn, and xa are the mole fraction of paraffins, naphthenes, and aromatics, respectively

Ri is the refractive intercept given by

n is the refractive index

d is the density of liquid

Molecular type composition (P, N, A)
VGC is the viscosity gravity constant

V is Saybolt Universal viscosity at 100 F or 210 F in SUS

SG is the specific gravity at 60 F

Molecular type composition (P, N, A)
Relation between Saybolt Universal Viscosity and kinematic viscosity
Molecular type composition (P, N, A)
For light fractions M  200, the viscosity gravity function is
Molecular type composition (P, N, A)
Problem
Calculate the P, N and A composition for the oil in the previous example