Sulfinol D Evaluation.

ECCN EAR 99
PDVSA Cardon Refinery

Sulfinol Evaluation
Confidential Technical Note

PDVSA Cardon Refinery
Sulfinol Evaluation
Confidential Technical Note
by
C.J. Taylor
ECCN EAR 99
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writing with the copyright owner. Copyright is vested in Shell Global Solutions (US) Inc.
Shell Global Solutions (US) Inc., 20082009. All rights reserved.
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Shell Global Solutions 3 CONFIDENTIAL - ECCN EAR 99
Table of Contents
Summary 4
1. Introduction 5
2. Design Basis 6
2.1 Sour Gas 6
2.2 Lean Solvent Composition 6
2.3 Treated Gas Specifications 7
2.4 Other Design Criteria 7
2.5 Future Case Conditions 8
3. Process Description 9
3.1 The Sulfinol Process 9
3.2 General Process Description 9
4. Evaluation 10
4.1 Design Case Conditions 10
4.2 Test Run Conditions 10
4.2.1 Feed Gas CO2 Composition 11
4.2.2 Feed Gas Temperature 11
4.2.3 Lean Solvent Temperature 11
4.2.4 Lean Solvent Composition 12
4.2.4.1 DIPA-oxazolidone Formation 13
4.2.5 CO2 Lean Solvent Loading 13
4.2.6 Test Run Case Summary 14
4.3 Future Case Conditions 15
4.3.1 CO2 Lean Loading 15
4.3.2 Circulation Rate 15
4.3.3 Reboiler Duty 15
4.3.4 Solutions for Improving Regeneration of Solvent 16
4.3.5 Absorber Column Tray by Tray Data 16
5. Process Conditions and Heat Exchanger Information 18
6. Sensitivity Analysis 19
6.1 Gas Inlet Temperature 19
6.2 Lean Solvent Inlet Temperature 20
7. Conclusion 21
8. Appendix A Process Flow Diagram (PFD) 22
Bibliographic Information 24
Summary
Shell Global Solutions (US) Inc. is pleased to provide the technical information on the Sulfinol
process. Information including a key process information, heat exchanger duty estimates, tray
by tray data, and two sensitivity analysis is provided for PDVSAs Cardon Refinery Study.
The CO2 removal section of HMU at the PDVSA Cardon Refinery was identified as a bottleneck
on PDVSAs last maximum capacity test run. Operationally, the Sulfinol unit was not able to
maintain the treated gas in specification of 0.05 mol % CO2. The lean Sulfinol flowrate was
increased from 7,400 ton/day to 9,600 ton/day by putting the spare circulation pump (PT-2202)
in service. However, the treated gas measured concentration of CO2 was 0.432 mol %.
The following three cases were evaluated for this study:
1. DesignCase
2. TestRunCase
3. FutureCase
The purpose of this study is to identify reasons as to why the Sulfinol unit during the test run
wasnt meeting the treated gas specification and to determine the required circulation rate to
achieve the treated gas specification when the Sulfinol unit is operated at the original design
conditions with new feed gas conditions.
The evaluation of the design case validated the models accuracy to match the actual operating
data for treated gas CO2 concentration.
The evaluation of the test run case determined that the additional CO2 concentration in the feed
gas was the major contributor to the increased CO2 concentration in the treated gas. The
increased solvent circulation rate of 9,600 ton/day should have been adequate to remove the
additional CO2 from the sour gas. However, it was determined that the low water content in the
lean solvent and the insufficient reboiler duty were the main causes as to why 9,600 ton/day of
solvent was not able to treated the sour gas to the desired treated gas requirement of 0.05 mol
% CO2. The reboiler duty was inadequate to regenerate the solvent to the required CO2 lean
loading to achieve the desired CO2 specification in the treated gas.
The lean loading for the test run was estimated to be 3,600 ppmw based on the reboiler duty
(steam rate) to regenerate the solvent. Shells recommended maximum CO2 lean loading is
2000 ppmw to avoid corrosion in the reboiler and lean solvent piping.
The evaluation of the future case demonstrated that the required lean solvent circulation is
9,000 ton/day. This higher circulation resulted in a higher reboiler duty (14.2 E6 kcal/hr) than
the existing reboiler design duty (11.7 E6 kcal/hr), and was therefore deemed inadequate. The
sensitivity analysis for the feed gas temperature showed no sensitivity on the required circulation
rate. The sensitivity analysis for the lean solvent temperature demonstrated 50 C is the most
optimum lean solvent temperature, which meets the CO2 specification in the treated gas without
the column temperature exceeding Shells maximum temperature constraint in the absorber.
When the lean solvent temperature is increased above 50 C, the CO2 specification can be met
with lower circulation rate, however the temperatures inside the column exceed the maximum
column temperature of 80 C which can result in corrosion of carbon steel material.
1. Introduction
on PDVSAs last maximum capacity test run. The conditions of the feed to the absorber C-2202
during this test are shown on Table 2-1 and Table 2-2. Operationally, the absorber was not able
to maintain the treated gas in specification of 0.05 mol % CO2. The lean Sulfinol flowrate was
increased from 7,400 ton/day to 9,600 ton/day by putting a spare circulation pump (PT-2202) in
service. However, the treated gas measured concentration of CO2 was 0.432 mol %.
The following three cases were evaluated for this study:
1. DesignCase
2. TestRunCase
3. FutureCase
The purpose of this study is to identify reasons as to why the Sulfinol unit during the test run
wasnt meeting the treated gas specification and to determine the required circulation rate to
achieve the treated gas specification when the Sulfinol unit is operated at the original design
conditions with new feed gas conditions (Future Case). The future case with new feed gas
conditions are shown in Table 2-5.
Tray by tray data was tabulated for the new feed gas conditions case to enable PDVSA to rate
the existing column to determine the feasibility of the existing amine contactor for the new
design conditions. Process conditions and heat exchanger information was provided for the 2
cases evaluated for this study.
A sensitivity study of the effect of gas inlet temperature and lean solvent inlet temperature were
evaluated in order to meet the CO2 design specifications.
2. Design Basis
The sour gas properties, treated gas specifications, and lean solvent data were received on
Monday, September 27th from Jos Ramrez of PDVSA.
2.1 Sour Gas
The process data of the sour gas to the absorber C-2202 for the test run and design conditions
are provided in Table 2-1. The lean solvent flowrate and inlet solvent temperature for the test
run and design conditions are also provided in Table 2-1.
Table 2-1: Sour Gas Feed Properties
Test run Conditions Design Contions

Absorber C-2202 Gas inlet Absorber C-2202 Gas inlet
Dry Gas Flowrate (t/d) 460 Flowrate (t/d) 460
H2O steam (t/d) 12.4 H2O steam (t/d) 4.2
Pressure (kgf/cm2 gauge) 15.3 Pressure (kgf/cm2) 16.6
Temperature (C) 67.5 Temperature (C) 45
Composition (mol %, dry basis) Composition (mol %, dry basis)
CO2 22.66 CO2 19.81
H2 75.15 H2 76.41
N2 0.158 N2 0.18
C1 1.987 C1 2.4
CO 0.04 CO 1.2
Sulfinol section Sulfinol Section
Lean sulfinol flowrate (t/d) 9600 Lean sulfinol flowrate (t/d) 7400
Inlet temp. of sulfinol (C) 52 Inlet temp. of sulfinol (C) 45
2.2 Lean Solvent Composition
The lean solvent composition for the test run and design conditions are provided in Table 2-2.
Table 2-2: Lean Solvent Composition
Test run Design

Water (wt %) 11 15
Dipa (wt %) 43.07 45
Sulfolane (wt %) 41.29 40
Oxaxolidone (wt %) 10.43 -
BL (wt %) 37.9 40-45
BT (wt %) 37.9 43-48
Note 1: The test run solvent composition was reported to be 105.79 %wt. Email
correspondence with Jos Ramrez of PDVSA confirmed his confidence in the DIPA, Sulfolane
and Oxazolidone values. The resulting water content on a 100 % basis would result in a water
concentration of 5.21 % wt. This low of water concentration is far below the recommended
minimum water concentration of 15 wt %.
2.3 Treated Gas Specifications
The following treating gas requirements for the C-2202 column are reported in Table 2-3.
Table 2-3: Treated Gas Specifications
Parameter All Cases Units

CO2 0.05 mol%
2.4 Other Design Criteria
The following is a list of additional design data used for developing this report.
Table 2-4: Additional Design Parameters
Test Run Design

Parameter Conditions Conditions Units
Utilities
Design air temperature 30 30 C
Reboiler heat duty (Note 1) 10.4 E+6 11.2 E+6 kcal/hr
Lean solvent
Lean Solvent Loading (Note 2) 0.025 0.003 mol/mol
Lean Solvent Loading (Note 2,3) 3600 450 ppmw
Absorber Column
Maximum temperature of solvent (Note 4) 80 80 C
Notes:
1. Thedesignreboilerdutyasspecifiedonthedatasheetwas11.7E+6kcal/hr.
2. TheleanloadingisnotmeasuredattheCardonRefinery,therefore,forthisstudythe
leanloadingswereestimatedbasedonthereboilerdutiesforthetestrunanddesign
conditions.
3. ShellsrecommendedmaximumCO2leanloadingis2000ppmwtoavoidcorrosionin
thereboilerandleansolventpiping.
4. SulfinolSolventtemperaturesinsidethecolumngreaterthan80Ccanresultin
corrosionofcarbonsteelmaterial.

2.5 Future Case Conditions
Table 2-5 provides the flow rate, temperature, pressure, and composition of the sour feed gas
and the lean Sulfinol temperature for the future case. The solvent composition for the future
Sour Gas case will be the design conditions specified in Table 2-2.
Table 2-5: Future Case: Sour Gas Feed Properties and Lean Solvent Conditions
Study Conditions
Absorber C-2202 Gas inlet
Dry Gas Flowrate (t/d) 460
H2O steam (t/d) 5.4
Pressure (kgf/cm2 gauge) 15.3
Temperature (C) 45
Composition (mol %, dry basis)
CO2 22.66
H2 75.15
N2 0.158
C1 1.987
CO 0.04
Sulfinol section
Lean sulfinol flowrate (t/d) Resulting
Inlet temp. of sulfinol (C) 45
3. Process Description
3.1 The Sulfinol Process
The Shell Sulfinol process is a regenerative amine based process for the removal of hydrogen
sulphide, carbon dioxide, carbonyl sulphide, mercaptans and organic sulphides/disulphides from
gas streams. The process was specifically developed for the treatment of gas streams at
elevated pressures. Sulfinol solvent is a mixture of water, amine (DIPA or MDEA) and
Sulfolane. A formulation with DIPA had been selected for this application.
The addition of Sulfolane increases the physical solubility of the acid gas contaminants (H2S and
CO2) in the solvent and improves the efficiency of the absorption process. The physical solubility
of the mercaptans and the organic sulphides/disulphide is also increased to a level whereby
these contaminants can be removed to low levels.
3.2 General Process Description
The process flow diagram defining the operation of the Sulfinol unit is shown in Appendix A.
Feed to the main absorber should pass through a feed gas conditioning system. This system
should exclude pipe scale, liquid hydrocarbons, corrosion inhibitors, and catalyst fines as these
will accumulate in the closed loop system and can lead to operating problems, like foaming.
Care should also be taken to exclude oxygen, such as from vapour recovery units, as it leads to
enhanced degradation.
The removal of the acidic components (CO2, H2S, COS, and mercaptans) from the gas phase
takes place in an absorber column, filled with trays or packing, where the gas stream is
contacted with the Sulfinol solvent counter-currently. The lean solvent is supplied to the
absorber under flow and temperature control. The temperature of the lean solvent is kept
sufficiently high to avoid condensation of hydrocarbons in the column. If hydrocarbons are
allowed to condense in the absorber, severe foaming of the solvent can occur. Rich solvent from
the absorber flows to a Lean-Rich heat exchanger where it is heated by hot lean solvent coming
from the regenerator bottom.
The heated rich solvent is introduced to the top of the stripping section of a regenerator, filled
with trays or packing, where the acid gases are stripped from the solvent by contacting the
solvent counter currently with stripping steam. The stripping steam is generated at the bottom of
the regenerator in the reboiler. Acid gas leaving the stripping section of the regenerator is
washed in the water wash section of the regenerator and is then routed to the regenerator
overhead condenser. The cooled acid gas along with condensed water flows to the reflux
accumulator, where the acid gas and water are separated. The condensed water is mixed with
the make-up water and returned under flow control to the regenerator as reflux via the reflux
pump. The acid gas product from the reflux vessel is routed to a downstream processing unit
(e.g., acid gas injection).
Lean Sulfinol solvent from the bottom of the regenerator is pumped back to the absorber via
lean-rich exchanger, solvent cooler. A slipstream of the lean Sulfinol solvent after lean-rich
exchanger is routed to the series of filters (mechanical filter, activated carbon filter followed by
after carbon filter). Suspended solids are considered to be a major cause of foaming in
absorbers and regenerators. This mechanical filtration can be supplemented by filtration through
an active carbon bed to remove surface-active contaminants.
4. Evaluation
4.1 Design Case Conditions
The design case was modeled to confirm the plant would meet the treated gas specification of
0.05 mol % CO2 under the design conditions. Without knowing the exact CO2 lean loading of
the plant, the treated gas CO2 concentration was determined for various CO2 lean loadings to
show the sensitivity on the lean loading of the CO2 removal. Figure 4-1 shows the lean loading
required to meet the treated gas specification is ~ 750 ppmw for the design circulation of 7,600
ton/day.
CO2inTreatedGasvsEstimatedCO2LeanLoading
0.35
Design
0.30
Measured
CO2intreatedGas(mol%)
0.25
0.20
0.15
0.10
0.05
0.00
1,000 2,000 3,000 4,000 5,000
EstimatedCO2LeanLoading(ppmw)
Figure 4-1: Effect of Lean Loading
The reboiler duty for the design case was measured to be 11.2 E 6 kcal/hr (Table 2-4). The
estimated lean loading for this reboiler duty at the design conditions is 450 ppmw. The
estimated lean loading is less than the required lean loading (750 ppmw) which explains why
the CO2 in the treated gas was below the 0.05 mol % CO2. Our model predicted a 0.047 mol
% CO2 concentration in the treated gas with the loan loading of 450 ppmw, which validates
that the model accurately predicts the CO2 concentration in the treated gas for the design
conditions.
4.2 Test Run Conditions
on PDVSAs last maximum capacity test run. Operationally, the absorber was not able to
maintain the treated gas specification of 0.05 mol % CO2. The lean Sulfinol flowrate was
increased from 7,400 ton/day to 9,600 ton/day by putting the spare circulation pump (PT-2202)
in service in attempt to lower the treated gas CO2 concentration. However, the treated gas CO2
concentration was measured to be 0.432 mol %.
The major differences between the test run conditions and the design conditions were the feed
gas CO2 composition, feed gas temperature, lean solvent flow, lean solvent temperature, lean
solvent composition, and the CO2 lean solvent loadings. These changes were investigated to
determine the major causes of the increased CO2 concentration.
4.2.1 Feed Gas CO2 Composition
The feed gas CO2 composition increased from 19.81 mol % to 22.66 mol % between the design
case and the test case. The test case CO2 concentration increased by ~ 15 %, which results in
approximately 15 % additional moles of CO2 which needed to be absorbed by the solvent. The
30 % increased in lean Sulfinol circulation using the spare circulation pump should have been
enough solvent to handle the additional CO2 load on the solvent. It was determined that the
additional CO2 concentration was a major contributor to the increased CO2 concentration in the
treated gas, but the solvent circulation rate of 9,600 ton/day should have been adequate.
Therefore, the reason as to why the solvent circulation rate of 9,600 ton/day yielded the higher
CO2 concentration in the treated gas was investigated.
4.2.2 Feed Gas Temperature
The feed gas temperature was increased from 45 C to 67.5 C between the design case and
the test case. While, the feed gas temperature was increased by 22.5 C, the impact to the
treated gas CO2 concentration is negligible. This is a result of the treated gas temperature
entering the column very quickly coming to thermal equilibrium with the rich solvent temperature
leaving the column. The temperature profile of the bottom ten trays of the column for the test
run conditions was predicted by our model and reported in Table 4-1. As shown in Table 4-1, the
rich solvent temperature leaving the column is ~ 80 C and in the first two trays the temperature
of the gas increases to ~ 80 C. Above tray two, the gas temperature closely matches the
solvent temperature throughout the column. Therefore, the increased feed gas temperature of
the test case was determined not to be a major reason why the solvent circulation rate of 9,600
ton/day yielded the higher CO2 concentration in the treated gas.
Table 4-1: Temperature Profile in Column (Bottom 10 Trays)
Solvent Temperature Gas Temperature

Trays Deg C Deg C
1 78.5 67.5
2 79.5 79.5
3 76.8 76.8
4 73.3 73.3
5 69.7 69.7
6 66.3 66.3
7 63.2 63.2
8 60.5 60.5
9 58.3 58.3
10 56.5 56.5
4.2.3 Lean Solvent Temperature
The lean solvent temperature increased from 45 C to 52 C between the design case and the
test case. While the lean solvent temperature was increased by 7 C, the impact on treated gas
CO2 concentration is minimal. The optimum lean solvent temperature for CO2 removal is
between 45 C and 50 C. However, due to the exothermic reactions associated CO2

absorption, it is important to keep the temperature of the solvent in the absorber below 80 C to
avoid corrosion associated with high temperature in absorber columns made of carbon steel
material. The higher lean solvent temperature results in higher solvent temperatures throughout
the column, which could result in increased corrosion rates. The lean solvent temperature
sensitivity reported in Section 6.2 demonstrates the circulation rate to meet the treated gas
specification is optimal at 50 C. Therefore, it was determined that the test run conditions lean
solvent temperature of 52 C was not a major reason why the solvent circulation rate of 9,600
ton/day yielded the higher CO2 concentration in the treated gas.
4.2.4 Lean Solvent Composition
The lean solvent composition changed severely from the design conditions during the test run.
While, the DIPA and Sulfolane concentration remained fairly constant, the water concentration
was significantly decreased and there was a substantial formation of DIPA-oxazolidone. The
water concentration in Sulfinol solvent is critical for CO2 removal. Figure 4-2 shows the CO2
concentration in the treated gas increases substantially as the water concentration is decreased
below 10 wt %. Therefore, the lower water content of the solvent during the test run can explain
the high CO2 concentration (0.432 mol %) measured during the test run. The decreased water
concentration in the test case was determined to be a major reason why the solvent circulation
rate of 9,600 ton/day yielded the higher CO2 concentration in the treated gas.
The recommended minimum for water concentration is 15 wt %, as the absorption of CO2

becomes significantly worse below 15 %. It should be noted that the water concentration below
15 %wt is outside the scope of the operating data which our Sulfinol model is based upon;
therefore the results are less conclusive than the data inside the operating data window.
CO2inTreatedGasvsWaterConcentration
0.70
3600ppmwCO2
9,600T/DCirculation
0.60
Measured
0.50
0.40
0.30
0.20
0.10
0.00
5 7 9 11 13 15 17
WaterConcentration(wt%)
Figure 4-2: Effect of Water Concentration

4.2.4.1 DIPA-oxazolidone Formation
DIPA-oxazolidone is the principle degradation products in systems with CO2 and DIPA it is
formed from a reaction with carbamate and CO2, carbamate is the primary product formed in
the reaction between DIPA and CO2:
CO2 + 2R2NH = R2NCOO- + R2NH2+ = DIPA-oxazolidone + R2NH + H2O
Where R2NH is DIPA, R2NCOO- is carbamate
DIPA-oxazolidone can be tolerated up to around 10% wt of the total solvent inventory.

Concentrations greater than 10% wt are not recommended due to the following reasons:
DIPAoxazolidone is effectively a waste product that decreases the concentration of

DIPAavailableforacidcomponentremoval
DIPAoxazolidoneincreasestheviscosityofthesolventtherebydecreasingheattransfer
andpumpingefficiency
The rate of DIPA-oxazolidone formation is enhanced by high CO2 partial pressures above the
solvent, high temperatures and large residence times.
The DIPA-oxazolidone essentially ties up the good amine (DIPA) and doesnt allow for CO2
removal. The DIPA-oxazolidone does have some physical solvent nature and acts similar to
sulfolane. For modeling purposes, the DIPA-oxazolidone is considered to be sulfolane.
Reclamation of the Sulfinol should be utilized when the concentration of DIPA-oxazolidone

exceeds 10 wt %. For DIPA-oxazolidone concentration less than 10 %, the water and DIPA
concentration shall be maintained, while allowing the Sulfolane concentration to deviate.
4.2.5 CO2 Lean Solvent Loading
The lean loading is not measured at the Cardon Refinery; therefore the CO2 lean loadings were
estimated based on the reboiler duties for the test run conditions. Figure 4-3 shows the effect of
lean loading on the estimated CO2 concentration in the treated gas for the test-run conditions.
This figure clearly shows that as the CO2 lean loading increases, the CO2 in the treated gas
increases considerably. Therefore, it was concluded that lean loading is a major reason for the
increased CO2 concentration in the treated gas.
The reboiler duty for the plant during the test run conditions was measured to be 10.4 E6 kcal/hr
(Table 2-4). The lean loading for the test run was estimated to be 3,600 ppmw based on the
reboiler duty (steam rate) to regenerate the solvent. It should be noted that Shells
recommended maximum CO2 lean loading is 2000 ppmw to avoid corrosion in the reboiler and
lean solvent piping.
The reboiler duty (steam rate) for the test run case was significantly lower than Shells
recommended reboiler duty for this higher circulation rate. A general rule of thumb for Sulfinol-D
solvent is to use between 70 80 kg steam/ ton of solvent. Therefore, the desired reboiler duty
for 9,600 ton/day of solvent would be 14 16 E+6 kcal/hr.
CO2inTreatedGasvsEstimatedCO2LeanLoading
0.200
0.180
9,600T/DCirculationRate
0.160
0.140
0.120
0.100
0.080
0.060
0.040
0.020
0.000
2,000 4,000 6,000 8,000 10,000 12,000
EstimatedCO2LeanLoading(ppmw)
Figure 4-3: Effect of Lean Loading
Using the estimated lean loading of 3,600 ppmw, the CO2 in the treated gas was estimated to
be 0.06 mol % (Figure 4-3). It should be noted that Figure 4-3, assumed a water concentration
in the solvent of 11 wt % as per the test-run conditions design basis as originally reported.
However, if the concentration of water in the solvent was lower than reported (See Note 1 of
Table 2-2), the curve in Figure 4-3 would be shifted upwards, as a result of the effect of water
concentration as shown in Figure 4-2.
4.2.6 Test Run Case Summary
It was determined that the additional CO2 concentration in the feed gas was the major
contributor to the increased CO2 concentration in the treated gas. The increased solvent
circulation rate of 9,600 ton/day should have been adequate to remove the additional CO2 from
the sour gas. However, it was determined that the low water content in the lean solvent and the
insufficient reboiler duty were the main reasons as to why 9,600 ton/day of solvent was not able
to treated the sour gas to the desired treated gas requirement of 0.05 mol % CO2. The low
water content of the solvent was not suitable for the solvent to absorb the CO2 from the sour
gas. The reboiler duty was inadequate to regenerate the solvent to the required CO2 lean
loading to achieve the desired CO2 specification in the treated gas. If the reboiler duty was
increased to 14 - 16 E6 kcal/hr and the solvent composition was maintained at the design
conditions, the treated gas concentration should be below the 0.05 mol % CO2 specification.
4.3 Future Case Conditions
The future case was modeled to determine the circulation required to meet the treated gas
composition of CO2 to be less than 0.05 mol %.
4.3.1 CO2 Lean Loading
In order to predict the circulation required to meet the treated gas specification, an assumption
of the CO2 lean loading has to be made. Shells assumption of the CO2 lean loading for the
future case is 450 ppmw. This assumption was established based on the lean solvent loading
estimated by our model for the design case conditions and reboiler estimate. This assumption
could be validated by PDVSA if a lean loading measurement was taken.
4.3.2 Circulation Rate
Using a CO2 lean loading of 450 ppmw, the required lean solvent circulation rate was estimated
to 9,000 T/D to meet the treated gas CO2 specification. If the CO2 lean loading is determined to
be higher than the assumed lean loading of 450 ppmw, Table 4-2 provides the solvent
circulation rate required to achieve the 0.05 mol % CO2 concentration in the treated gas.
4.3.3 Reboiler Duty
Using a circulation rate of 9,000 ton/day, the required reboiler duty to achieve the assumed CO2
lean loading of 450 ppmw is 14.2 E+6 kcal/hr. The maximum duty available was established by
the design reboiler duty as specified on the datasheet of 11.7 E+6 kcal/hr. As this required
reboiler duty is more than the maximum duty of the reboiler, the reboiler was assumed to be
inadequate.
If the CO2 lean loading is determined to be higher than the assumed lean loading of 450 ppmw,
Table 4-2 provides the required reboiler duty to achieve the respective lean loadings for the
given circulation rates in order to meet the 0.05 mol % CO2 concentration in the treated gas.
Table 4-2: Circulation Rate Required and Reboiler Duties for Various CO2 Lean Loadings
Lean Solvent Loading Solvent Circulation Rate Reboiler Duty

ppmw CO2 Ton/Day E+6 kcal/hr
450 9,000 14.2
1000 9,200 14.5
1500 9,600 15.1
2000 10,000 15.7
4.3.4 Solutions for Improving Regeneration of Solvent
There are a few suggestions for improving the regeneration of the solvent.
1. Investigateoptionstoincreasereboilerduty
2. InjectLPsteamintothebottomofthecolumntoimproveregenerationofthesolvent
anddecreasetheCO2leanloading.

ThesesuggestionscanbeevaluatedbyShellGlobalSolutions(US)inthefutureifdesired.Ifyou
haveanyquestionsregardinganyofthesesolutions,wewouldbegladtodiscussfurther.
4.3.5 Absorber Column Tray by Tray Data
Tray by tray data was tabulated for the new feed gas conditions case to enable PDVSA to rate
the existing column to determine the feasibility of the existing amine contactor for the future
design conditions.
Table 4-3: Tray by Tray Data for Sulfinol Absorber

GAS GAS LIQUID LIQUID LIQUID LIQUID LIQUID
TRAY TL TG PRESS. SOLVENT GAS VISC TRAY DENSITY DENSITY VISC COND. SURFT HEAT CAP.
C C BARA KG/H KG/H CP KG/M3 KG/M3 CP W/M/K mN/M KJ/KG/K
Bottom 45 0.0162 7.191
1 73.6 72.4 15.98 391200 17450 1 6.108 1105.7 6.38 0.207 37.95 2.72
2 72.0 72.0 15.96 389400 15390 2 5.55 1103.1 6.30 0.207 38.10 2.70
3 68.5 68.6 15.94 387300 13350 3 5.007 1102.1 6.65 0.207 38.41 2.68
4 64.8 65.0 15.92 385300 11390 4 4.449 1101.1 7.13 0.207 38.72 2.67
5 61.3 61.5 15.90 383300 9594 5 3.892 1099.9 7.66 0.206 39.03 2.66
6 58.1 58.3 15.87 381500 8014 6 3.365 1098.7 8.23 0.206 39.31 2.65
7 55.3 55.5 15.85 380000 6697 7 2.896 1097.5 8.79 0.206 39.55 2.65
8 53.0 53.2 15.83 378600 5657 8 2.505 1096.4 9.30 0.206 39.74 2.65
9 51.3 51.4 15.81 377600 4875 9 2.197 1095.4 9.74 0.206 39.90 2.65
10 50.0 50.1 15.79 376800 4311 10 1.968 1094.6 10.09 0.206 40.01 2.64
11 49.1 49.1 15.77 376300 3919 11 1.804 1093.9 10.33 0.206 40.09 2.64
12 48.4 48.5 15.75 375900 3652 12 1.69 1093.5 10.51 0.205 40.14 2.64
13 48.0 48.1 15.72 375600 3473 13 1.613 1093.2 10.64 0.205 40.18 2.64
14 47.8 47.8 15.70 375400 3355 14 1.561 1093.0 10.71 0.205 40.20 2.64
15 47.6 47.6 15.68 375300 3278 15 1.526 1092.8 10.77 0.205 40.22 2.64
16 47.5 47.5 15.66 375200 3228 16 1.502 1092.7 10.80 0.205 40.23 2.64
17 47.4 47.4 15.64 375200 3195 17 1.486 1092.7 10.82 0.205 40.24 2.64
18 47.3 47.3 15.62 375100 3174 18 1.475 1092.6 10.83 0.205 40.24 2.64
19 47.3 47.3 15.60 375100 3160 19 1.467 1092.6 10.84 0.205 40.24 2.64
20 47.3 47.3 15.57 375100 3151 20 1.461 1092.6 10.85 0.205 40.24 2.64
21 47.3 47.3 15.55 375100 3146 21 1.457 1092.6 10.85 0.205 40.25 2.64
22 47.3 47.3 15.53 375100 3142 22 1.453 1092.5 10.85 0.205 40.25 2.64
23 47.3 47.3 15.51 375100 3139 23 1.45 1092.5 10.85 0.205 40.25 2.64
24 47.3 47.3 15.49 375100 3138 24 1.448 1092.5 10.85 0.205 40.25 2.64
25 47.3 47.3 15.47 375100 3137 25 1.445 1092.5 10.85 0.205 40.25 2.64
26 47.3 47.3 15.45 375100 3136 26 1.443 1092.5 10.85 0.205 40.25 2.64
27 47.3 47.3 15.42 375100 3136 27 1.441 1092.5 10.85 0.205 40.25 2.64
28 47.3 47.3 15.40 375100 3135 28 1.439 1092.5 10.85 0.205 40.25 2.64
29 47.3 47.3 15.38 375100 3135 29 1.436 1092.5 10.85 0.205 40.25 2.64
30 47.3 47.3 15.36 375100 3134 30 1.434 1092.5 10.85 0.205 40.25 2.64
31 47.3 47.3 15.34 375100 3133 31 1.432 1092.5 10.85 0.205 40.25 2.64
32 47.3 47.3 15.32 375100 3132 32 1.43 1092.5 10.85 0.205 40.25 2.64
33 47.3 47.3 15.30 375100 3131 33 1.427 1092.5 10.85 0.205 40.25 2.64
34 47.3 47.3 15.27 375100 3130 34 1.425 1092.5 10.85 0.205 40.25 2.64
35 47.3 47.3 15.25 375100 3128 35 1.423 1092.5 10.85 0.205 40.25 2.64
36 47.3 47.3 15.23 375100 3125 36 1.42 1092.5 10.85 0.205 40.25 2.64
Top 45.0 0.0067 1094.4 12.07 0.205 40.44 2.63
Table 4-4: Tray by Tray Data for Sulfinol Regenerator

FAT GAS GAS GAS LIQUID LIQUID LIQUID LIQUID LIQUID
TRAY TL TG PRESSURE SOLVENT TOTAL VISC DENSITY DENSITY VISC COND. SURFT HEAT CAP.
C C BARA KG/HR KG/HR CP KG/M3 KG/M3 CP W/M/K mN/M KJ/KG/K
Bottom 135.4 0.010 0.94

1 125 125.2 1.75 400100 25310 0.96 1017.6 0.75 0.23 34.70 3.05
2 124.6 124.6 1.73 400100 25160 0.95 1018.1 0.76 0.23 34.74 3.04
3 124.3 124.3 1.72 400000 24990 0.95 1018.6 0.77 0.23 34.76 3.04
4 123.9 123.9 1.70 399800 24750 0.94 1019.2 0.78 0.23 34.79 3.04
5 123.3 123.3 1.68 399600 24410 0.95 1020.3 0.80 0.23 34.82 3.04
6 122.3 122.4 1.67 399200 23920 0.96 1022.3 0.83 0.23 34.86 3.03
7 120.8 120.9 1.65 398800 23180 1.00 1025.8 0.88 0.23 34.92 3.03
8 118.5 118.5 1.64 398000 21980 1.06 1031.7 0.99 0.22 35.02 3.02
9 115.0 115.0 1.62 396800 20310 1.18 1040.4 1.18 0.22 35.16 3.00
10 110.4 110.4 1.61 395100 18880 1.35 1051.7 1.49 0.22 35.36 2.98
11 98.2 111.3 1.61 8697 25068 1.47 961.1 0.29 0.68 60.00 4.21
12 45.4 98.2 1.60 7962 24333 1.57 990.0 0.59 0.64 68.78 4.18
Top 45.0 0.015
Notes:
1. Theregeneratorwasmodelledat10strippingtraysand2refluxtrays.
5. Process Conditions and Heat Exchanger Information
Table 5-1: Process Conditions and Heat Exchanger Information
Process Conditions Units Test Run Design Future

Treated Gas CO2 mol % 0.42 0.05 0.05
Circulation T/D 9,600 7,400 9,000
DIPA concentration wt % 43 45 45
Sulfolance concentration wt % 46 40 40
Water concentration wt % 11 15 15
CO2 Lean Amine Loading mol/mol 0.025 0.003 0.003
CO2 Lean Amine Loading ppmw 3562 447 447
CO2 Rich Amine Loading mol/mol 0.31 0.33 0.29
CO2 Rich Amine Loading ppmw 11100 16523 14472
Reflux rate T/D 41 46 100
Heat Exchangers
Condenser E6 kcal/hr 1.1 1.2 2.6
Reboiler E6 kcal/hr 10.4 11.2 14.2
L/R Exchanger E6 kcal/hr 9.0 9.7 12.1
Amine Cooler (air) E6 kcal/hr 9.2 9.9 11.7
6. Sensitivity Analysis
A sensitivity study was performed to evaluate the effect of gas inlet temperature and lean
solvent inlet temperature on the circulation rate required to meet the CO2 design specifications
for the future case.
6.1 Gas Inlet Temperature
The sensitivity analysis performed on the gas inlet temperature demonstrated that the circulation
rate to achieve the 0.05 mol % CO2 specification in the treated gas was insensitive to the feed
gas temperature. This is because the treated gas temperature entering the column very quickly
comes to thermal equilibrium with the rich solvent temperature leaving the column. Table 6-1
shows that for both the inlet gas temperatures (65 C, 35 C), the gas leaving the Tray 1 is ~ 72
C, which matches the rich solvent temperature for Tray 1 and the remainder of the column.
Therefore, the increased feed gas temperature is not a sensitive parameter for determining the
required circulation rate to meet the specification of 0.05 mol % CO2 concentration in the treated
gas.
Table 6-1: Temperature Profiles in Column (Bottom 10 Trays)
Solvent Gas Solvent Gas

Temperature Temperature Temperature Temperature
Trays Deg C Deg C Trays Deg C Deg C
65.0 35.0
1 72.8 72.8 1 71.3 71.3
2 71.4 71.4 2 71.3 71.3
3 69.2 69.2 3 69.2 69.2
4 66.9 66.9 4 67.0 67.0
5 64.7 64.7 5 64.7 64.7
6 62.5 62.5 6 62.5 62.5
7 60.3 60.3 7 60.4 60.4
8 58.3 58.3 8 58.4 58.4
9 56.4 56.4 9 56.5 56.5
10 54.7 54.7 10 54.7 54.7
6.2 Lean Solvent Inlet Temperature
The sensitivity analysis performed on the lean solvent inlet temperature demonstrated that the
circulation rate to achieve the 0.05 mol % CO2 specification in the treated gas was sensitive to
the feed gas temperature as shown in Table 6-2. As the temperature of the lean solvent is
increased, the kinetics of the reaction for CO2 absorption increase, and therefore the CO2
removal is improved and the required circulation rate is decreased. However, at higher lean
solvent temperatures, the temperature of the solvent in the column begin to exceed the
maximum acceptable temperature ( 80 C ) for Sulfinol solvent to avoid corrosion of the carbon
steel in the column. If the absorber is stainless steel or clad with stainless steel then the
maximum temperature conditions can be relaxed. If it is desired to operate the column at higher
temperatures, it is recommended to change the absorber metallurgy to stainless steel of clad
with stainless steel to avoid corrosion.
Table 6-2 illustrates that 50 C is the most optimum lean solvent temperature, which meets both
the CO2 specification and the maximum temperature constraint. When the lean solvent
temperature is increased to 55 C, the CO2 specification can be met with 7,300 ton/day solvent,
however the maximum column temperature is 88 C. Therefore, the circulation rate needed to
be increased to 9,600 ton/day in order to lower the column temperature below. Similarly, at 60
C lean solvent temperature, the circulation rate was increased to meet the maximum
temperature constraint.
Table 6-2: Sensitivity of Lean Solvent Temperature
Lean Solvent Circulation Max Temperature CO2 in Treated

Temperature Rate in Column Gas (Actual)
C T/D C mol %
35 13,000 54 0.05
40 10,700 63 0.05
45 9,000 72 0.05
50 8,200 80 0.05
55 7,300 88 0.05
55 9,600 80 < 0.05
60 7,200 94 0.05
60 11,500 80 < 0.05
7. Conclusion
The evaluation of the design case validated the models accuracy to match the actual operating
data for treated gas CO2 concentration.
The evaluation of the test run case determined that the additional CO2 concentration in the feed
gas was the major contributor to the increased CO2 concentration in the treated gas. The
increased solvent circulation rate of 9,600 ton/day should have been adequate to remove the
additional CO2 from the sour gas. However, it was determined that the low water content in the
lean solvent and the insufficient reboiler duty were the main causes as to why 9,600 ton/day of
solvent was not able to treated the sour gas to the desired treated gas requirement of 0.05 mol
% CO2. The reboiler duty was inadequate to regenerate the solvent to the required CO2 lean
loading to achieve the desired CO2 specification in the treated gas.
The lean loading for the test run was estimated to be 3,600 ppmw based on the reboiler duty
(steam rate) to regenerate the solvent. Shells recommended maximum CO2 lean loading is
2000 ppmw to avoid corrosion in the reboiler and lean solvent piping.
The evaluation of the future case demonstrated that the required lean solvent circulation is
9,000 ton/day. This higher circulation resulted in a higher reboiler duty (14.2 E6 kcal/hr) than
the existing reboiler design duty (11.7 E6 kcal/hr), and was therefore deemed inadequate. The
sensitivity analysis for the feed gas temperature showed no sensitivity on the required circulation
rate. The sensitivity analysis for the lean solvent temperature demonstrated 50 C is the most
optimum lean solvent temperature, which meets the CO2 specification in the treated gas without
the column temperature exceeding Shells maximum temperature constraint in the absorber.
When the lean solvent temperature is increased above 50 C, the CO2 specification can be met
with lower circulation rate, however the temperatures inside the column exceed the maximum
column temperature of 80 C which can result in corrosion of carbon steel material.
8. Appendix A Process Flow Diagram (PFD)

5
V-1002
E-1003
FC
2
6 V-1004 Water
LC
MU
P-1001 E-1001 13
C-1001 C-1002
P-1003
1 S-1001/3
LC
11
Feed V-1001
12 E-1004
Gas
10
7 E-1002
P-1002
CASE Test Run (low water) #N/A
Stream <1> <2> <5> <13>
Temperature degC 67.5 52 45 45
Pressure bara 16.0 15.473 1.64 1.64 Process Flow Diagram / H&MB
Flow kg/s 5.5 0.9 4.6 0.0 ACID GAS REMOVAL
MolWt 12.0 2.6 41.6 18.0 PDVSA Cardon ReF
H2S mol% 0.0000 0 0.0000 PDVSA Cardon ReF
CO2 mol% 22.2661 0.2576 91.6836
Rev 1 Date Oct/2010 by SGSI BV
File C:\Users\craig.j.taylor\Desktop\[AMEST.xlsm]PFD 5
Figure A-1: Sulfinol Process Flow Diagram

Bibliographic Information
This report has been classified as Restricted and is subject to US Export Control regulations and
has been classified as ECCN EAR 99.
Report Number : NA
Title : PDVSA Cardon Refinery Sulfinol Evaluation
Subtitle : Confidential Technical Note
Author(s) : C. Taylor PTU/TDUA
Reviewed by : A. Joura PTU/TDUA
Approved by : J. Critchfield PTU/TDUA
Content Owner : C. Taylor PTU/TDUA
Issue Date : 2010-22-10
Activity Code : 00000000
Project Number : 00000000
Sponsor :
Keywords : PDVSA Cardon Refinery, Sulfinol,
Electronic file :
Issuing Company : Shell Global Solutions (US) Inc.
Westhollow Technology Center, P.O. Box 4327,
Houston, TX 77210, USA.
Tel. +1 281 544 8844

Sulfinol D Evaluation.

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Sulfinol D Evaluation.

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ECCN EAR 99

PDVSA Cardon Refinery

Confidential Technical Note

Shell Global Solutions (US) Inc., 20082009. All rights reserved.

The following three cases were evaluated for this study:

The following three cases were evaluated for this study:

2.1 Sour Gas

Table 2-1: Sour Gas Feed Properties

Test run Conditions Design Contions

2.2 Lean Solvent Composition

Table 2-2: Lean Solvent Composition

Test run Design

2.3 Treated Gas Specifications

Table 2-3: Treated Gas Specifications

Parameter All Cases Units

2.4 Other Design Criteria

Table 2-4: Additional Design Parameters

Test Run Design

2.5 Future Case Conditions

3.2 General Process Description

Figure 4-1: Effect of Lean Loading

4.2 Test Run Conditions

4.2.1 Feed Gas CO2 Composition

4.2.2 Feed Gas Temperature

Table 4-1: Temperature Profile in Column (Bottom 10 Trays)

Solvent Temperature Gas Temperature

4.2.3 Lean Solvent Temperature

between 45 C and 50 C. However, due to the exothermic reactions associated CO2

4.2.4 Lean Solvent Composition

The recommended minimum for water concentration is 15 wt %, as the absorption of CO2

Figure 4-2: Effect of Water Concentration

4.2.4.1 DIPA-oxazolidone Formation

CO2 + 2R2NH = R2NCOO- + R2NH2+ = DIPA-oxazolidone + R2NH + H2O

Where R2NH is DIPA, R2NCOO- is carbamate

DIPA-oxazolidone can be tolerated up to around 10% wt of the total solvent inventory.

DIPAoxazolidone is effectively a waste product that decreases the concentration of

Reclamation of the Sulfinol should be utilized when the concentration of DIPA-oxazolidone

4.2.5 CO2 Lean Solvent Loading

Figure 4-3: Effect of Lean Loading

4.2.6 Test Run Case Summary

4.3 Future Case Conditions

4.3.1 CO2 Lean Loading

4.3.2 Circulation Rate

4.3.3 Reboiler Duty

Lean Solvent Loading Solvent Circulation Rate Reboiler Duty

4.3.4 Solutions for Improving Regeneration of Solvent

4.3.5 Absorber Column Tray by Tray Data

Table 4-3: Tray by Tray Data for Sulfinol Absorber

Table 4-4: Tray by Tray Data for Sulfinol Regenerator

Bottom 135.4 0.010 0.94

5. Process Conditions and Heat Exchanger Information

Table 5-1: Process Conditions and Heat Exchanger Information

Process Conditions Units Test Run Design Future

6.1 Gas Inlet Temperature

Table 6-1: Temperature Profiles in Column (Bottom 10 Trays)

Solvent Gas Solvent Gas

6.2 Lean Solvent Inlet Temperature

Table 6-2: Sensitivity of Lean Solvent Temperature

Lean Solvent Circulation Max Temperature CO2 in Treated

8. Appendix A Process Flow Diagram (PFD)

Figure A-1: Sulfinol Process Flow Diagram

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