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TRAINING COURSE

Refinery Amine, Sour Water &


Sulphur Recovery Unit (SRU)
HYSYS Simulation
Prepared By:
Tahir Syed, Process Engineer
https://www.linkedin.com/in/tahirsyed2/
hussaintahir123@yahoo.com
Introduction
Light Ends and Sour Water are produced from Refinery
Separation Units (Crude/Vacuum Distillation, and other
fractionators) & Reaction Units (FCC, Hydrocracker, Reformer,
Coker, Hydro-treater, etc.) are treated by Amine and Sour Water
Stripper Unit respectively
Treated light ends are recycled back to the process while treated
sour water is used for desalting and can also be upgraded to Boiler
Feed-water quality or sent to wastewater treatment.
 The light ends from both the SWS and Amine unit are sent to
SRU for sulphur recovery and to reduce sulphur emissions.
 This area in the refinery is as exciting as working on Separation
and Reaction units and developing working simulation skills is
worthwhile for new design, operations troubleshooting & revamps.
Table of Contents
Amine Unit Simulation Sulphur Recovery Unit Simulation
Amine Data SRU Problem Statement
Amine Problem Solution SRU Process Flow Diagram
Amine Unit PFD SRU Simulation Results
Amine Stream Table Claus Plant Reactions
Amine Unit HYSYS Simulation Steps SRU Simulation Steps
Combustion Air to Furnace
Sour Water Stripper Unit Simulation SRU Plant Configuration
SWS Data Sulphur Recovery Efficiency
SWS Process Flow Diagram Waste Heat Boiler
SWS Stream Table SWS Feed Lineup
SWS Unit HYSYS Simulation Steps SRU Simulations-Detailed
Sulphur Species
Combined Amine, SWS, SRU Simulation
Simulation Examples Reference
The data source is from the book “Fundamentals of Petroleum
Refining”. The problems are solved using UNISIM but we can
emulate the steps to develop this simulation in HYSYS.

• Amine Unit Simulation - DEA Example E15.6 – Page 387


• SWS Unit Simulation - Example E17.14 - Page 451
• SRU Unit Simulation - Example E15.11 - Page 393

Proposed steps to solve the problems are discussed in this


presentation. Also, Youtube links are included to develop step by step
simulation. For SRU, Example E15.11 we discuss a solution using
Conversion Reactors as well as HYSYS SRU Template. For combined
Amine, SWS, SRU simulation we use both the Conversion Reactors
and HYSYS SRU Template.
HYSYS Simulation Tutorial
Yobutube Links
Amine Unit:
• https://youtu.be/B3xwOh2UA0w

Sour Water Stripper Unit:


• https://youtu.be/vMXlrlxqVPg

Sulphur Recovery Unit:


• https://youtu.be/rQkbhA_x-Fg
Amine Unit Simulation
Amine Unit Data
Amine Problem Solution
Amine Circulation Rate

Let's suppose we have 1233 Kgmole/h acid gas


coming to the DEA unit (as in example problem)
having a total of 160.3 kgmole/h of Acid gas
(H2S+CO2). As per GPSA Fig 21-4, the acid gas pick
up, mol/mol amine, normal range is (0.20–0.80). We
take .305 mole acid gas per mole amine so 100% DEA
amount will be 160/.305=525.25 kgmoles/h. Divide
this by the DEA strength i.e., 28%. It gives 1876
kgmoles/h amine circulation rate. Typical lean
loading (H2S+CO2) is 0.01 for regenerated DEA.
Amine Unit PFD
Amine (DEA) Unit HYSYS
Flowsheet
Amine Stream Table
SWS Unit Simulation
SWS Data
SWS Process Flow Diagram
SWS Unit HYSYS Flowsheet
SWS Stream Table
SRU Unit Simulation
This simulation will be done busing Conversion
Reactor as required by SRU Unit Simulation -
Example E15.11 - Page 393
and also by using HYSYS SRU Template as well as
GPSA Databook.
SRU Problem Statement
SRU Process Flow Diagram
SRU HYSYS Flowsheet
Conversion Reactors
SRU HYSYS Flowsheet
HYSYS Template
SRU Simulation Results
SRU Plant Configuration

• Plant configuration in Example E15.11 is according to the FIG.


22-6 of GPSA Data-book which suggests for 20-55% H2S in the
acid gas feed, the process scheme to be a Straight-through or
straight-through with acid gas and/or air preheat. In this case air
is preheated to 118 degC as there is 40.2 Mole% H2S in the
feed to Claus Plant in Example E15.11.
Sulphur Recovery Efficiency
• The table E15.11 shows 2516 kgmoles/h total sulphur
production which also contains around 506 kgmoles of water
which gives around 2010 kgmoles/h of Sulphur. Please note
that there is 2010 kgmoles/h in the feed as H2S. The book has
rightly mentioned 2516 kgmoles/h because that is sulphur to
be handled in sulphur degassing, granulation, etc. Also, the
book has mentioned that all H2S and SO2 has to be converted
so a figure closer to 2010 kgmoles/h is fine. Generally, we are
okay with 95% sulphur recovery so we can tweak conversion
in the converters accordingly.
Combustion Air to Furnace

The amount of H2S in feed is 2010 kgmoles/h.


Therefore, oxygen required for 1/3 rd H2S combustion to
SO2 =(1/3)*(3/2)*2010=1005 kgmoles/h, then air
=1005/.21= 4786 kgmoles/hr, so Nitrogen is 4786-
1005=3781 kgmoles/h. Similarly, oxygen required for the
combustion of Ammonia and Hydrocarbons will also be
estimated as needed. In this project, hydrocarbons
getting destructed in the Incinerator and not in the
furnace. Refer to GPSA Section 22-Sulphur Recovery,
Example 22-1 for hydrocarbon combustion air
requirement calculation.
Waste Heat Boiler

• Waste Heat Boiler downstream front end furnace can


be designed for HP, MP or LP Steam by modifying shell
side outlet pressure. Resulting temperature can be
verified from Steam Tables. Steam Produced can be
used in SWS, Amine Re-boilers and SRU Pre-
Converter Re-Heaters, Power generation (in large
plants) and other users. Total boiler feed water
requirements and steam generation / consumption can
be estimated by this simulation.
Claus Plant Reactions
Using HYSYS Conversion Reactors
SRU HYSYS Simulation Steps
using Conversion Reactors
1. Enter the Properties Environment.
2. Add Feed Stream Components As Per Table E15.11, Page
395, Fundamentals of Petroleum Refining. Select
S1_Vapor and S_Amorphous for Sulphur. “S1 Vapor”
component will be used in the thermal stage reactions
while S_Amorphous will be used for Catalytic stages.
Alternatively, “S1 Vapor” can be tried for both thermal &
catalytic stages.
3. Select Peng Robinson as the Fluid Package.
SRU HYSYS Simulation Steps
using Conversion Reactors
4. Add Furnace or Thermal Stage Reactions 15.21
and 15.22 as one set. Rank 15.21 as 1 and 15.22 as
rank 0. Enter conversion (Co) = 100.
5. Add Converter or Catalytic Stage reaction (15.23)
as a separate set. Enter conversion (Co) = 100.
Note: Tweak Converter/Furnace reaction conversion
given above to match the results in the
presentation.
SRU HYSYS Simulation Steps
using Conversion Reactors
6. Enter the Simulation Environment.
7. Activate Standard HYSYS Object Palette.
8. Set up Feed and Air Streams as per given data.
9. Add Furnace as a Conversion Reactor. Attach Air and Feed
Streams. Select Set 1 for Reactions.
10. Connect the effluent stream from the Furnace to the tube
side of the waste heat boiler which is modeled as a Shell and
Tube Heat Exchanger with Boiler feed-water stream on the
shell side.
SRU HYSYS Simulation Steps
using Conversion Reactors
11. Route the cooled stream from the Waste Heat Boiler.
Cool the gases in the WHB between 300 to 330 degC
12. Flash it in 2-phase separation vertical vessel.
Send vapor to Shell & Tube HX with boiler feed water on
shell side to condense sulphur at 135 degC. This should
recover 201 kgmole/hr sulphur.
13. It will then be flashed again to separate sulphur and
vapor phase.
14. The vapor phase will be reheated to the required
temperature as per mentioned in the table E15.11 before
being fed to the Catalytic converters.
SRU HYSYS Simulation Steps
using Conversion Reactors
15. Add Catalytic Converter as a Conversion Reactor
and select Reaction 15.23. Also add an Energy
stream and outlet temperature of 171 deg C.
16. Tweak conversion to match the outlet Sulphur
stream as per table E15.11.
17. Add subsequent Catalytic Converters and Heater
same as above.
18. Sum up bottom streams from the three
converters and from sulphur condenser to find total
Sulphur produced (2516 kgmoles/hr i.e. 2010
kgmoles/hr sulphur+506 kgmoles/hr water).
SWS Feed Lineup

• Sour Water Stripper gases having NH3 can also be


lined up by adding an additional reaction to
Furnace reaction set as 2 NH3 + 3/2 O2 → N2 + 3
H2O and couple of other reactions. Ideally,
ammonia must be fully destroyed in the furnace but
an outlet temp of around 1250 deg C has to be
maintained. Furthermore, combustion air
requirements will be recalculated for NH3, H2S,
Fuel Gas, etc.
• Use References on Slide: 30 to identify the
reactions.
• Watch Youtube Video: The Experts Network:
Processing Ammonia in Sulphur Plants.
Link: https://youtu.be/Mu1zEYsxSfA
Comments
(1) While SRU simulation was conducted using the
SRU Unit Simulation - Example E15.11 - Page 393
data, the amount of sulphur condensed from the
1st condenser was 200 kgmoles/hr.
(2) The same data was used to solve the above
problem by using HYSYS/SULSIM template which
yielded about 900 kgmoles/hr.
(3) Therefore, I tried to understand the reasons and
found that there are additional reactions taking
place in Claus Front End furnace.
(4) An effort was made to develop detailed simulation
as presented in the following slides using
additional reactions.
SRU Simulations-Detailed
(1) Add more reactions to the reaction furnace as mentioned in
"Kinetic modeling of a modified Claus Reaction Furnace" thesis
by Aaron Pollock Ellsworth. Also, there are other useful theses
available on this link, including the one by Hawboldt, Kelly Anne
N., . These theses discuss furnace reactions related to
Amine/SWS SRU feeds. The link is prism.ucalgary.ca,
University of Calgary, Prism Library. These reactions will be
added as Conversion reactions to the Furnace reaction set and
conversion will be adjusted to match Sulsim template results.
(2) SulphurPro simulator manual at ogtrt.com.
(3) GPSA Section 22 for Sulphur Species formation. COS, CS2
formation and destruction. The GPSA problem 22-1 can be
solved by using DESIGN II simulation package as well, both for 3
and 8 Sulphur species. There is a solved example for each case
included in the DESIGN II library (winsim.com).
Sulphur Species
• GPSA Section 22 has a worked example which takes
into account Sulphur allotropes (S2, S3......S8) formed
in the reaction furnace/converters. We can use GPSA
example to estimate the Sulphur allotropes. Their
molecular weights are in the order of 32, 64,
96.....Refer to GPSA Fig. 22-21 for Distribution of
Sulfur Vapor Species based on temperature.
HYSYS SRU Templates

• Very robust SRU templates (SULSIM) are available


with HYSYS using Sulphur Recovery fluid package
and a dedicated model palette as well as other
features. The template “3 Stage Claus Unit with
Incinerator” can be used to check Example E15.11
simulation. There is another template for Sour Water
Stripper Gas. Also, GPSA Example 22-1 is a handy
solution.
HYSYS Conversion Reactors in
Sulphur Recovery Units (SRU)
Simulation
Introduction

• The Conversion Reactors provide flexibility to the process


engineer to alter the conversion of a particular reaction and
note the impact on the outlet conditions.
• It is highly useful when we have reactor outlet stream analysis
(e.g. from the field). We can adjust Conversion to verify the field
process parameters as appropriate. However, conversion
values should be realistic and verified.
• GPSA problem 22-1/HYSYS Sulsim templates can help in
estimating the outlet temperature and stream composition while
adding reactions to the Front End Furnace.
• Furthermore, Conversion reactors can be applied in other parts
of an SRU.
SRU Flow Diagram
SRU Flow Diagram
Conversion Reactors in SRU

The Conversion Reactors can be used to model the


following units to develop a comprehensive SRU HYSYS
simulation model:

• Reaction Furnace
• Waste Heat Boiler Outlet Stream
• Sulphur Condensers
• Gas Re-Heaters for Claus Converters feed
• Claus Converters
• Incinerator

A brief description of the reaction sets applicable to each of


the above is presented in the following slides.
Conversion Reactors Tutorial

• A video tutorial “Aspen HYSYS Lecture 08 Conversion Reactor”. The


youtube link is: https://youtu.be/3F1b0_Vik1g

• As mentioned in the video, add an energy stream to the conversion


reactors where ever fixing of the outlet temperature is required. It
will help in fixing outlet temperature in Converters at 171 degC. It will
also help Waste Heat Boiler outlet stream Sulphur species conversion
and condensation at 135 degC, etc., as mentioned above). The
temperature will be decreased from 371 degC to 135.1 degC in first
conversion reactor then from 135.1 degC to 135 degC in next
conversion reactor.
Reaction Furnace

The following are the two main reactions:


• 2H2S + O2 2S + 2H2O
• 2H2S + O2 2SO2 + 2H2O

• Refer to the following theses which discuss furnace reactions related


to Amine/SWS SRU feeds which have to be added as Conversion
reactions to the Furnace reaction set:

• "Kinetic modeling of a Modified Claus Reaction Furnace" thesis by


Aaron Pollock (pdf pages 98, 132, 133).
• “Kinetic modeling of key reactions in the Modified Claus Plant Front
End Furnace” thesis by Kelly Hawboldt (pdf pages 28, 29).

• The link is prism.ucalgary.ca, University of Calgary, Prism Library.


Reaction Furnace

• The solution of GPSA problem 22-1 is a handy tool to find both


Sulphur produced in the Furnace (as S2 vapor) and the outlet
temperature. Follow GPSA FIG. 22-27 “Equilibrium Constant for
Claus Reaction”, a and b.
• The conversion of various reactions will have to be adjusted in
the simulation to match the sulphur recovery, outlet temperature
etc., as calculated above.
• Also, follow GPSA FIG. 22-7 “Potential COS and CS2
Formation in Claus Furnaces” to adjust the conversion of COS
and CS2 forming reactions in the Reaction Furnace.
• In case we also have Sour Water Stripper gas then more
reactions will have to be added to the reaction set and
temperature will be adjusted to approx. 1250 degC.
Waste Heat Boiler Outlet Stream

• The Reaction Furnace produces Sulphur mainly in the “S2 vapor”


form. The furnace outlet stream will be cooled in the Waste Heat
Boiler to 370 deg C.
• GPSA FIG. 22-21 “Distribution of Sulfur Vapor Species” can be used
to estimate the conversion of S2 to S6 and S8 vapors respectively at
370 deg C or other outlet temperature as required. Add an energy
stream to this conversion reactor.
• I have prepared a spreadsheet based on GPSA solution to determine
the conversion of S2 to S6 and S8 respectively. Email me at
hussaintahir123@yahoo.com and I will send you a copy of the
spreadsheet. The following reaction set will be defined for this
conversion reactor:
S2 S6 (100% Conversion)
S2 S8 (100% Conversion)
• Some S2 vapor will remain in the feed to Sulphur Condensers.
• Other sulphur species have been ignored for simplicity.
Sulphur Condensers

• The condenser can be modeled as a conversion reactor


where the process gas will be cooled to 135 deg C.
• The following reactions will be defined to convert S2, S6 and
S8 vapor to SLiq (100% Conversion):
• S2 SLiq
• S6 SLiq
• S8 SLiq
• The vapor stream will be then sent to the Catalytic
Converter.
• This process will apply to other condensers downstream
using considering sulphur species existing at that
temperature.
• An energy stream will be added to this conversion reactor
also and the outlet temperature of 135 degC will be
specified.
Gas Re-Heaters

• If fuel gas or Acid gas is used as a fuel to pre-heat Claus


Converters feed then a conversion reactor will produce the
effluent to be used in shell & tube exchanger.
Claus Converters

The main reaction is:


• 2H2S + SO2 3S + 2H2O

• Please follow GPSA FIG. 22-7 FIG. 22-10 “Hydrolysis of COS


and CS2 with Activated Alumina Catalyst in Sulfur Converter” to
adjust the conversion of COS and CS2 to H2S in the Catalytic
Converter. A separate Reaction set for first Converter can be
defined.
• We will add two more reactions for COS and CS2 hydrolysis to
the 1st converter reaction set as following:
• COS + H2O  CO2 + H2S
• CS2 + 2H2O  CO2 +2 H2S
• Refer to GPSA FIG. 22-2 “Theoretical Equilibrium Percent
Conversion of Hydrogen Sulfide to Sulfur in Sulfur Converter“
Incinerator

• It can also be defined as a Conversion reactor. The reaction set will


include reactions for the 100% oxidation of H2S, COS, CS2,
Hydrocarbons, etc.
• Reaction sets used for Front End Furnace can be defined here as well.
• An estimate of incinerator inlet and outlet stream compositions can
be made by using Sulsim. The conversion values can be adjusted
accordingly for this conversion reactor.
• A video tutorial (not in English), “#13 Aspen HYSYS - Conversion
Reactor _ Combustion of Methane _ Set _ BAHASA INDONESIA” can
be followed to develop the simulation. The youtube link is:
https://www.youtube.com/watch?v=fLrkUd0dTpM
GPSA Reference Figures

• GPSA FIG. 22-2 Theoretical Equilibrium Percent Conversion of


Hydrogen Sulfide to Sulfur (Converters)
• GPSA FIG. 22-7 Potential COS and CS2 Formation in Claus
Furnaces”
• GPSA FIG. 22-10 “Hydrolysis of COS and CS2 with Activated
Alumina Catalyst in Sulfur Converter”
• GPSA FIG. 22-27 “Equilibrium Constant for Claus Reaction”, a
and b
• GPSA FIG. 22-21 “Distribution of Sulfur Vapor Species”
Refinery Amine, Sour Water &
Sulphur Recovery Unit (SRU) Process
Simulation
Develop your Own HYSYS
Template
Combined Amine, SWS, SRU
Simulation

Amine (DEA) Unit


Sulphur
Recovery Unit
(SRU)
Sour Water
Stripper (SWS)
Unit
Combined PFD

Typical Operating Conditions on the


following slide
Typical Operating Conditions
Notes
Proposed Steps for
Template Development
• Start with HYSYS DEA Unit Template.
• Add “Peng Robinson” Fluid Package for SRU and
“Sour PR” for Sour Water Stripper (SWS). DEA
template already has “Acid Gas-Chemical Solvents”
package. So, there will be three thermodynamic
packages in combined simulation.
• Add SRU Furnace as mentioned before.
• Add reaction set as mentioned before.
• Use GPSA Example 22-1 Data to develop SRU furnace
and match Furnace outlet temperature and Sulphur
production/other components. Adjust Conversion of
various reactions in reaction set accordingly.
Proposed Steps for
Template Development
• Once SRU Furnace is calibrated with GPSA example data
feed the acid gas stream from the upstream DEA unit to
SRU Furnace and keep on adding rest of the process as
mentioned before.
• Replicate SWS template available in HYSYS.
• Feed SWS gas to the SRU as well and adjust furnace
conversion and outlet temperature.
• Develop two cases for SRU Reaction Furnace. One with
two reactions and the other with additional reactions.
Develop a separate case for SWS gas lineup.
DISCLAIMER
• This presentation is intended for personal learning of process
simulation only. A thorough review with technology suppliers
on case by case basis is recommended for practical
applications, equipment selection, operations troubleshooting,
etc.
Thank you

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