5.1 Feed Analysis: 5 Physical Properties Estimation

Physical Properties Estimation 14
CHAPTER
5
Physical
Properties
Estimation
5.1 Feed Analysis

The composition of a petroleum fraction is expressed in terms of its ASTM D-86 distillation
analysis. The engine waste oil having boiling point range 130-550°C. . The distillation analysis
and other properties of the feed stream have been taken from the book “waste engine oil re-
refining and energy recovery by Francois Audibert”. They are listed in the table given below
Table 5.1 Feed Analysis

ASTM D-86 Analysis
Volume % Temperature Other Properties
Recovered (°C)
IBP 130 API Gravity, 60 °F 26.4
5 175 Water(Weight%) 10
10 232 Sulfur (Weight %) 1.2
50 404 Density (kg per cubic
meter) 885.4
90 516
95 532 Flow rate (Kg per
5140
EP 550 hour)
5.2 Conversion of ASTM D-86 Analysis to TBP Analysis

The usual way of representing the composition of a petroleum fraction is ASTM D-86
analysis. It gives % volume recovered as a function of temperature in a distillation that is
performed without reflux. A more precise way is the TBP analysis that is performed in a tray
column with large number of theoretical stages and high reflux ratio. Sufficient time is provided
to achieve the equilibrium. The TBP analysis is required to estimate the composition of the feed
in terms of pseudo-components.
ASTM D-86 analysis is converted to TBP analysis based on the empirical equations
given in procedure API 3A1.1( from API Technical data hand book seventh edition).But we use
Hysis in which ASTM D-86 directly converted into TBP in oil manager.
Fig 5.1
5.3 Physical Properties

5.3.1 Volumetric Average Boiling Point (VABP)
The volumetric average boiling point of the whole Diesel feed is determined by using the
ASTM D-86 analysis according to the procedure API 2B1.1(from API Technical data hand book
seventh edition). The equation is
T10  T30  T50  T70  T90

VAPB 
5
5.3.2 Characterization Factor (Kw)
The characterization factor is a simple way of expressing the composition of a petroleum

fraction in terms of the types of molecules present in it. For the waste oil feed, it is given by
Kw 
 VABP  3
where S is the standard specific gravity (60 °F / 60 °F).
5.3.3 Standard Specific Gravity and API Gravity

Standard specific gravity (60 °F / 60 °F) is estimated for each feed component from the
definition of the characterization factor. The equation is
1
(TBP ) 3
S
Kw
The API gravity is determined from the defining equation
141.5
API   131.5
S
5.3.4 Molecular Weight (M)

Molecular weight is required for conversion of weight-based analysis to mole-based
analysis, which is then used in the hydrotreating profile. Approximate molecular weight of each
feed component is estimated using the standard specific gravity and TBP according to the
procedure API 2B2.1(from API Technical data hand book seventh edition).
5.3.5 Critical Temperature (Tpc) and Pressure (Ppc)

Since each of the feed components is itself an undefined petroleum fraction, so it will
have a critical temperature and a critical pressure. These values are important for estimation of
other properties like acentric factor.
Using the API gravity and the characterization factor, Tpc is estimated using the procedure
API 4D3.1. Similarly, Ppc is estimated using the procedure API 4D4.1 (from API Technical data
hand book seventh edition).
5.3.6 Vapor Pressure (P*)

Vapor pressure is estimated using the procedure API 5A1.19. First of all, an empirical
factor X is determined using the TBP of the feed component and the temperature of interest.
Then the vapor pressure is determined as an empirical function of X depending upon the range of
the vapor pressure encountered.
5.3.7 Acentric Factor (ω)

It is important for correlating a number of thermodynamic properties. It is estimated from
the defining equation
   log  Pr *   1.000
where Pr* = reduced vapor pressure = Pr/Ppc
Pr = vapor pressure at T = 0.7Tpc
5.3.8 Enthalpy (H)

Procedure API 7B4.7 is used for the estimation of enthalpies of the feed components at
the temperature of the interest. First of all, liquid state enthalpy of each feed component is
determined at Tr=0.8 as a function of empirical constants A 1, A2 and A3. Each of these empirical
constants is a function of standard specific gravity and characterization factor of the feed
components.
Next step is to calculate the standard enthalpy for each pseudo-component at any given
temperature. Again empirical constants B1, B2 and B3 are determined as functions of standard
specific gravity and characterization factor. The relation for the enthalpy at any given
temperature takes into consideration these 3 empirical constants as well as the liquid state
enthalpy at Tr=0.8, temperature of interest, critical temperature, molecular weight and the
acentric factor.
5.3.9 Density (ρ)

The density of a feed component in liquid state at any given temperature is estimated by
using the modified Rackett equation given in procedure API 6A3.6 (from API Technical data
hand book seventh edition).
The equation is
1  RTpc  [1(1Tr )2 / 7 ]
  Z RA
  Ppc 
where ZRA is an empirically derived constant.
The first step is to calculate the value of this empirical constant. This is done at the
reference state of 60 °C where the specific gravity is already known. Then this value is used in
the same relation to calculate the density at any given temperature.
5.3.10 Viscosity (μ)

The kinematic viscosity of a liquid petroleum fraction at 100 °F is determined according
to the procedure API 11A4.2. The equation is
100  ref  cor
Both the terms on the R.H.S. of this equation are functions of TBP of a pseudo-component.
The reduced viscosity of low-molecular-weight fractions is determined by using the

procedure API 11A5.1. The parameters considered here are a simple fluid viscosity term (as a
function of Tr and Pr), a correction term for molecular acentricity (as a function of Tr and Pr), and
the acentric factor. First of all, reduced viscosity is calculated at 37.8°C (100°F) and also at the
given temperature, and then these values are used for the calculation of actual viscosity at the
given temperature.
The kinematic viscosity of high-molecular weight fractions at any given temperature and
low pressure is determined by procedure API 11A4.1. The relation is
s
 559.67 
  B   0.86960
 T  459.67 
The two empirical constants here are functions of reference kinematic viscosity at 37.8°C
(100°F). The next step is to correct this empirically determined value for the effect of pressure.
This is done according to the procedure API 11A5.5(from API Technical data hand book
seventh edition).
5.3.11 Specific Heat (Cp)

The specific heat of liquid petroleum fractions at low pressure is determined using the
procedure API 7D2.2. The equation is
c p  A1  A2T  A3T 2
The empirical constants A1, A2 and A3 are functions of standard specific gravity and
characterization factor. The value determined by this equation is then corrected for the effect of
pressure using the procedure API 7D3.1 (from API Technical data hand book seventh
edition).
. The equation is
 ~0 ~ 
c p  c 0p 
R  cp  cp 
M  R 
 
 
The term within the parentheses is known as the dimensionless effect of pressure on specific
heat. It is actually a combined effect of dimensionless effect of pressure on the specific heat of a
simple (ideal) fluid and the correction term for molecular acentricity. These two terms are
determined as a function of Tr and Pr using the tables 7D3.2 and 7D3.3 in procedure API 7D3.1,
respectively.
The heat capacity of petroleum fraction vapors is determined using the procedure API
7D4.2 in a similar way. The pressure correction term from procedure API 7D3.1 is also included
here.
5.3.12 Vapor-Liquid Equilibrium Constant (K)

The equilibrium constant K is important for calculations of vapor and liquid composition
and flow rates in the separators and distillation column. The K-values for light fractions (TBP <
200 °F) at any given temperature and pressure are determined using the figure API 8A 1.17.
Figure API 8A1.18 is used for determination of the K-values of higher fractions. The K-values
for H2S and water in petroleum fractions are determined from figure API 8C1.3. The K-value for
hydrogen gas in petroleum fractions is determined using figure API 8B1.2. The additional
parameter here is the average boiling point of gas-free liquid.
Since it is very difficult to estimate the physical properties from these empirical co-relations so,
for our simplicity we take these properties from hysys.
References:
1. API Technical Data Handbook,7th Ed. , American Petroleum Institute Publishing,1997

5.1 Feed Analysis: 5 Physical Properties Estimation

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Physical Properties Estimation 14

5.1 Feed Analysis

Table 5.1 Feed Analysis

5.2 Conversion of ASTM D-86 Analysis to TBP Analysis

5.3 Physical Properties

T10  T30  T50  T70  T90

5.3.2 Characterization Factor (Kw)

The characterization factor is a simple way of expressing the composition of a petroleum

where S is the standard specific gravity (60 °F / 60 °F).

5.3.3 Standard Specific Gravity and API Gravity

The API gravity is determined from the defining equation

5.3.4 Molecular Weight (M)

5.3.5 Critical Temperature (Tpc) and Pressure (Ppc)

5.3.6 Vapor Pressure (P*)

5.3.7 Acentric Factor (ω)

where Pr* = reduced vapor pressure = Pr/Ppc

Pr = vapor pressure at T = 0.7Tpc

5.3.8 Enthalpy (H)

5.3.9 Density (ρ)

where ZRA is an empirically derived constant.

5.3.10 Viscosity (μ)

100  ref  cor

The reduced viscosity of low-molecular-weight fractions is determined by using the

5.3.11 Specific Heat (Cp)

5.3.12 Vapor-Liquid Equilibrium Constant (K)

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