EDL Anlagenbau Gesellschaft mbH

Process Simulation of Solvent Deasphalting Plants

with PRO/II based on Thermodynamic Equilibrium Data
"VLE K -Values - Fill Options"

Moscow, 28-30 March 2012

EDL Anlagenbau Gesellschaft mbH

Introduction

SDA, the Solvent Deasphalting technology is actually one of the

most interesting „Bottom to Barrel“ technology for heavy residues
in modern refineries

?
• Large price differences between light sweet crudes and heavy sour crudes
created strong incentives for bottom processing tecchnologies

• Old fashion technology SDA in the lube oil refinery

will be more and more also applied in fuel oil refineries, too

• The SDA technology is the lowest investment cost variant compared to

Gasification, Visbreaker, Hydrocracker, Coker et al

• In the best case both products DAO as well as Pitch can be converted in
further process steps to valuble products, no further residues will be available

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Integration of SDA in modern Refinery

Lube Oil Refinery Bright Stock

FCC -Plant
Crude Fuel Oil Refinery
ADU Hydrocracker

DAO

AR
VDU
SDA

Asphalt (Pitch)
Bitumen plant
ADU…Atmospheric Distillation Unit VR
VDU…Vacuum Distillation Unit
SDA…Solvent Deasphalting
AR…..Atmospheric Residue
VR…..Vacuum Residue

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Typical SDA

a typical SDA plant is a PDA, e.g.

- Propane Deasphalting Plant -

The plant normally consists of the following parts:

• Propane Extraction
• DAO Train
• Asphalt Train
• Propane Condensation and Recovery
• Pressure Relieve -, Slop - and Flushing system

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SDA simulation and design

The simulation and design of a SDA , especially the

liquid –liqud extraction process is a challenging task !

?
• the feed, Vacuum Residue can only be simulated with pseudo
components e.g. it is impossible to use components from the data base
with a defined structure
• the pseudo components have no structure to produce BIPs from the
UNIFAC –Model to build activity coefficients between the components
• the liquid –liquid extraction process for the SDA is based on the different
solubilities between the solvent and the hydrocarbons
• BIPs are necessary to calculate the equilibria in the two liquid phases,
the DAO and the Asphalt phase

BIP… Binary Interaction Parameters

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Model Basis: „Chueh and Prausnitz“
The BIPs can be calculated based on a publication from Chueh and Prausnitz
(1967) for an EOS (Equation of State) via the partial molar volumes of the
multicomponent liquid mixture:

Equation of State:
RT a
P  0.5
  b T  (  b)

Partial differentiation of EOS:

2( xi aki )  abk /(  b)
RT bk
(1  ) i

P  2P k 
 b  b  (  b)T 1/ 2
( )T  0 and ( 2 )T  0
 c
 c RT a  2  b 

(  b) 2 T 1/ 2  2 (  b) 2 

with the mixing rules for a mixture and used for a  0.4278 and b  0.0867

a, b, aii , bi , aij ........ f ( xi , i ,ci , Pci , Tci , ai , bi )

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Model Basis: „Chueh and Prausnitz“

applying the pseudocritical rules to the critical region: TR  0,93

T 'CM  TCM  (TCT  TCM ) D(TR )

 'CM  CM  (CT  CM ) D(TR )

Further, with adjustments to SRK and PR applied in PRO/II we get

the BIP„s between the components:

n
   ' 1/ 3  ' 1/ 3
kij  1   ' 1/ 3 
CMi CMj

 ( CMi   CMj ) / 2 
' 1/ 3

n3 (the best fit with experimental data)

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Notation

a, b.......constants in Redlich Kwong EOS

D(TR )...correction function to the critical region
k ij .........BIP's for interaction parameters
P...........total pressure
T...........temperature
TR ..........reduced temperature
V......... ..total volume of liquid mixture
............molar vo lume of liquid or liquid mixture
 k ..........partial molar volu me of component k in liquid phase
CM ........pseudocritical volume of mixture
 'CM .......corrected pseudocritical volume of mixture
CT .........true critical volume of mixture
x......... ....mole ffraction in liquid phase
 a ,  b ....dimensionl ess parameter in Redlich Kwong EOS
............acentric factor
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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)

d15  0.9669 kg/kg

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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:

Autoclave

Conditions: subcritical pressure from 30 to 35 bar and

temperature about 50°C
Solvent: Propane (100%)
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Bench scale tests
Results: DAO and Asphalt from the bench scale unit

Asphalt DAO

DAO…..Deasphalted oil
AS……..Asphalt (Pitch)

*…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

Crude Oil

Amospheric Residue

Vacuum Residue

Propane Precipitate
Oils

Pentane Precipitate

Heptane Precipitate
Resins

Asphaltenes

The choise of the solvent or solvent mixture is very important !

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Simulation studies of Solvent mixtures

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Ternary plots -Temperature influence-

Binodal curves
Ternary plot from literature:

Solvent to Feed ratio

(tie lines):
1…0,5
2…3,0
3…8,0

1
2 3

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Ternary plot – Pressure influence -

Binodal curves
Solvent to Feed ratio
(tie lines):
1…0,5
2…3,0
3…8,0

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 !

HTU…Height of Transfer Unit

NTU…Number of Transfer Unit

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Summary

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.

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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 !

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