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=
u u u
Equation of State:
Partial differentiation of EOS:
with the mixing rules for a mixture and used for
) , , , , , , ( ........ , , , ,
bi ai ci ci ci i i ij i ii
T P x f a b a b a O O u e
(
+
+
+
+
2 2 2 / 1 2
2 / 1
) (
2
) (
) (
) /( ) ( 2
) 1 (
b
b
T
a
b
RT
T b
b ab a x
b
b
b
RT
i
k ki i
k
k
u u
u
u
u u
u
u u
u
0 ) ( and 0 ) (
2
2
= =
c c
T T
P P
ou
o
ou
o
0867 . 0 and 4278 . 0
a
= O = O
b
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applying the pseudocritical rules to the critical region:
93 , 0 >
R
T
) ( ) (
) ( ) (
'
'
R CM CT CM
CM
R CM CT CM
CM
T D
T D T T T T
u u u u + =
+ =
Further, with adjustments to SRK and PR applied in PRO/II we get
the BIPs between the components:
n
CMj CMi
CMj CMi
ij
k
(
(
+
=
2 / ) (
1
3 / 1
'
3 / 1
'
3 / 1
'
3 / 1
'
u u
u u
3 = n
(the best fit with experimental data)
Model Basis: Chueh and Prausnitz
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Notation
factor ..acentric ..........
EOS Kwong Redlich in parameter ess dimensionl .... ,
phase liquid in ffraction ....mole x.........
mixture of volume critical true .........
mixture of volume ical pseudocrit corrected .......
mixture of volume ical pseudocrit ........
phase liquid in k component of me molar volu partial ..........
mixture liquid or liquid of lume ..molar vo ..........
mixture liquid of volume ..total V.........
re temperatu reduced .......... T
ure ..temperat T.........
pressure ..total P.........
parameters n interactio for s BIP' ......... k
region critical the o function t correction )... D(T
EOS Kwong Redlich in nstants b.......co a,
a
CT
'
CM
R
ij
R
e
u
u
u
u
u
b
CM
k
O O
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PRO/II PFD- one stage
Typical one stage liquid liquid extraction unit:
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Pseudo component feed Vacuum Residue (VR)
kg/kg 9669 . 0
15
= d
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Pseudo component properties
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PRO/II- K-value Fill Options
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EOS for Fill Options
The following EOS are awailable for the Fill Option:
- Modified Chueh Prausnitz Hydrocarbon Fill -
Soave Redlich Kwong
SRK Panagiotopoulos-Reid
SRK Modified Panagiotopoulos-Reid
SRK SIMSCI
Peng Robinson
PR Panagiotopoulos-Reid
PR Modified Panagiotopoulos-Reid
Predictive Peng Robinson 78
Tacite
The best fit with practical results we achieved with the
SRK Modified Panagiotopoulos Reid thermodynamic !
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BIPs calculation
BIPs calculated from the output report:
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Stream list
DAO: 28.5 %, Asphalt : 71.5 %
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VR-DAO-Asphalt TBP
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VR-DAO-Asphalt distribution
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Property list
As shown in the property list special data as S, V, Ni, Fe, N and CCR
can be controlled in the DAO, Asphalt via a distribution in the feed (VR):
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Bench scale tests
The theoretical results were compared to bench scale tests in a autoclave:
Conditions: subcritical pressure from 30 to 35 bar and
temperature about 50C
Solvent: Propane (100%)
Autoclave
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Bench scale tests
Results: DAO and Asphalt from the bench scale unit
DAO..Deasphalted oil
AS..Asphalt (Pitch)
Asphalt DAO
*SRK -Mod Panag. -Reid
**PR -Mod Panag. -Reid
The SRK Modified Panagiotopoulos -Reid method gives the best fit to the practical results !
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Study of thermodynamic models
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Solvent impact
The choise of the solvent or solvent mixture is very important !
Asphaltenes
Resins
Oils
C
r
u
d
e
O
i
l
A
m
o
s
p
h
e
r
i
c
R
e
s
i
d
u
e
V
a
c
u
u
m
R
e
s
i
d
u
e
P
r
o
p
a
n
e
P
r
e
c
i
p
i
t
a
t
e
P
e
n
t
a
n
e
P
r
e
c
i
p
i
t
a
t
e
H
e
p
t
a
n
e
P
r
e
c
i
p
i
t
a
t
e
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Simulation studies of Solvent mixtures
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Ternary plots -Temperature influence-
Ternary plot from literature:
1
2
3
Solvent to Feed ratio
(tie lines):
10,5
23,0
38,0
Binodal curves
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Ternary plot Pressure influence -
Binodal curves
Solvent to Feed ratio
(tie lines):
10,5
23,0
38,0
1
2
3
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PRO/II simulation of multiple stage extraction
Heater on stage 1 to precipitate Asphalt
Controller for precipitation
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Ternary plot Pressure influence -
The number of trays are not so important !
For the design the
HTU, NTU concept
must be applied !
HTUHeight of Transfer Unit
NTUNumber of Transfer Unit
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The Solvent Deasphalting (SDA) is a key technology processing heavy
residues to valuable oils (DAO, Deasphalted Oil) and asphalt (Pitch) for the
Bitumen production. The process will be more and more interesting also in
fuel oil refineries as a Bottom to Barrel technology with low costs.
The calculation of the extraction process with NPB components is difficult
because of the lack of BIPs between the components. Other ways to build
up the data from the UNIFAC model are not applicable.
The model from CHUEH and PAUSNITZ, published in the AIChE Houston
Meeting in 1967 is applicable to estimate the BIPs between the NBP
components and the solvents, finally to calculate the extraction of the SDA
for high pressure.
Summary
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Summary
The model application in the PRO/II simulation program under the
Equation of State (EOS) with the VLE K values Fill Option is the basis
for the complete process simulation of the whole SDA process.
Experimental results have shown that the model can be applied to design
the SDA process with different solvents (Propane, Butane etc.) and
solvent mixtures for the sub- and supercritical extraction processes.
Further investigation should be done to apply the model also to other
extraction technologies e.g. solvent extraction with furfural or NMP.
Thank you for your attention !