Project/Grant Name: Amine Unit Emissions Method Analysis

Proposal for Grant Activities (PGA)/PCR No. 582-18-82006-04

Grant Number: 582-17-72921
Tracking No. 2018-247

Final Report

Prepared and Submitted by:

Vincent M. Torres, PE
Principal Investigator
Center for Energy & Environmental Resources

Eric Chen, Ph.D.

Research Associate
McKetta Department of Chemical Engineering

The University of Texas at Austin

Austin, Texas

August 30, 2019

Table of Contents
Executive Summary ............................................................................................................... iii
1 Introduction ...................................................................................................................... 4
2 Technical Approach ........................................................................................................... 4
2.1 Overview ............................................................................................................................................................................ 4
2.2 Amine Units Emissions Methods Selection ......................................................................................................... 6
2.3 Data Collected .................................................................................................................................................................. 6
2.4 Description and Summary of Assessment of Available Data Sets ............................................................. 7
3 Amine Units Emissions Methods Estimates ..................................................................... 10
3.1 Technical Approach .................................................................................................................................................... 10
3.2 AMINECalc v1.0 Limitations ................................................................................................................................... 10
3.3 ProMax and HYSYS Process Simulators ............................................................................................................. 11
3.4 Gas Sample Analysis Speciation Format ............................................................................................................ 11
3.5 Saturated Sour Gas Composition Input .............................................................................................................. 12
3.6 Amine Unit Operating Conditions and Configuration .................................................................................. 12
3.7 ProMax and HYSYS Process Configuration Specifications ......................................................................... 13
3.8 Approach Used in Process Simulation of Amine Units ................................................................................ 13
4 Analysis and Discussion of Amine Units Emissions Methods Estimates ............................ 13
4.1 Case Study 1A - S7-V2 (O) Amine Unit ............................................................................................................... 13
4.1.1 Data Set Analysis ...................................................................................................................................................... 14
4.1.2 Laboratory Gas Analysis ........................................................................................................................................ 15
4.1.3 AMINECalc Simulation ........................................................................................................................................... 17
4.1.4 ProMax Simulation Parameters ......................................................................................................................... 19
4.1.5 HYSYS Simulation Parameters ........................................................................................................................... 19
4.1.6 Absorber Analysis ..................................................................................................................................................... 20
4.1.7 Rich Amine Flash Analysis .................................................................................................................................... 22
4.1.8 Regenerator Analysis .............................................................................................................................................. 22
4.2 Case Study 1B - Hypothetical S7-V2 (O) Amine Unit Simulation ............................................................ 25
4.2.1 Absorber Analysis ..................................................................................................................................................... 27
4.2.2 Rich Amine Flash Analysis .................................................................................................................................... 29
4.2.3 Regenerator Analysis .............................................................................................................................................. 31
4.2.4 VOC Rich Flash and Acid Gas Analysis ............................................................................................................. 35
4.2.5 BTEX Rich Flash and Acid Gas Analysis .......................................................................................................... 36
5 Conclusions ..................................................................................................................... 37
6 Recommendations .......................................................................................................... 37
References............................................................................................................................ 39
Appendix .............................................................................................................................. 40

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 Executive Summary
Recent research indicates conventional software programs may not accurately estimate VOC
(specifically benzene, toluene, ethylbenzene, and xylene) emissions from amine units. From data
the TCEQ has evaluated, it appears that measurement data in conjunction with process simulator
results calculated more VOC emissions from amine units than were previously estimated using
traditional software such as the American Petroleum Institute's (API) AmineCalc.

The purpose of this study was to evaluate methods (including publicly available direct
measurement data, models and process simulators) for estimating volatile organic compounds
(VOC) emissions from amine units typically present at natural gas plants and processing
operations. Amine units that target carbon dioxide (CO2) for removal (amine units in CO2
service) were the primary focus of this study, although data from amine units that target other
acid gases such as hydrogen sulfide were considered.

The Project Team considered the following TCEQ approved methods for inclusion in this study.
• American Petroleum Institute’s (API) AMINECalc Version 1.0 – Amine Unit Emissions
Model (API Publication 4679)
• Aspen HYSYS process simulator
• Bryan Research and Engineering’s (BR&E) ProMax process simulator
• Schneider Electric SimSci Pro/II process simulator
Upon reviewing each of these methods, AMINECalc was the only method that is not a process
simulation package and has been used extensively, so it was included in the study. Of the
remaining three methods, Aspen HYSYS was available to the Project Team at little to no cost to
the project. Therefore, it was included in the study. Given the degree that BR&E ProMax is
reported by the TCEQ being used in permit applications relative to Pro/II, the decision was made
to include ProMax first and Pro/II only if time and budget allowed.

The comparison of AMINECalc, ProMax, and HYSYS showed that AMINECalc predicts the
lowest amount of VOC and BTEX emissions from the rich flash and acid gas streams and
HYSYS the highest. ProMax predictions are in between the AMINECalc and HYSYS
predictions. ProMax predictions for total VOC and BTEX in the combined Rich Flash and Acid
Gas streams are 3.3 and 3.7 times higher, respectively, than AMINECalc. HYSYS predictions
for total VOC and BTEX in the combined Rich Flash and Acid Gas streams are 9.7 and 9.0 times
higher, respectively, than AMINECalc.

ProMax and HYSYS offer recycle loop and make-up/purge stream configuration options, which
generate an iterative steady state H2S and CO2 loading in the amine stream for a given sour gas
stream and specified plant operating conditions.

AMINECalc allows the user to input any H2S and CO2 loading, which can lead to significant
errors. It does not have an iterative recycle stream calculation, which provides a check on user
input. AMINECalc is limited to five single component amine solvents and one process
configuration, which will have limited application. Out of the nine sites evaluated, three sites
used a single component solvent (MDEA), five sites used a multi-component solvent blends, and
one site used a proprietary amine solvent.

iii
1 Introduction
Recent research indicates conventional software programs may not accurately estimate VOC
(specifically benzene, toluene, ethylbenzene, and xylene) emissions from amine units (Skinner et
al., 1997, McIntyre et al., 2001, Duncan et al., 2009). From data the TCEQ has evaluated, it
appears that measurement data in conjunction with process simulator results calculated more
VOC emissions from amine units than were previously estimated using traditional software such
as the American Petroleum Institute's (API) AmineCalc (1999).

The purpose of this study was to evaluate methods (including publicly available direct
measurement data, models and process simulators) for estimating volatile organic compounds
(VOC) emissions from amine units typically present at natural gas plants and processing
operations. Amine units that target carbon dioxide (CO2) for removal (amine units in CO2
service) were the primary focus of this study, although data from amine units that target other
acid gases such as hydrogen sulfide were considered. Direct measurement of amine unit VOC
emissions is not required nor is there a requirement that such measurements, if made, be
submitted to any central office or agency. Field measurement of VOC emissions from amine
units was not within the scope of this project’s budget.

The study gathered publicly available process, operational, and measurement data from amine
units using a range of sources.

Using the data gathered, UT Austin estimated amine unit VOC emissions using a variety of
conventional emissions estimation methods and then performed analysis using two different
approaches. The accuracy of these conventional emissions estimation methods were analyzed by
comparing the predicted emissions to those calculated from measured outlet compositions (direct
measurement data not available), and drawing conclusions about how accurately each method or
model corresponded to the calculated emissions.

UT Austin also compared emissions predicted by each different method for the same amine unit
(i.e., same source) and analyzed the predicted emissions for trends (e.g., consistently predicting
the highest emissions rate) and draw conclusions about the observed performance of the
emissions methods.

2 Technical Approach
2.1 Overview
The focus of this study was to understand the relative accuracy of conventional software
programs and methods commonly used to estimate VOC (specifically benzene, toluene,
ethylbenzene, and xylene) emissions from amine units. To develop this understanding, the
approach used was to first select and recommend to the TCEQ Project Manager the amine unit
VOC emissions estimation methods that would be used in this study based on the list of methods
approved by the TCEQ for use in permit applications, the frequency these programs are used,

4
and the similarity in approach used by the methods. Once approved by the TCEQ Project
Manager and subject to the available budget, these methods would then be included in the study.

The next step was to seek any available direct VOC emissions measurement data of amine units,
along with relevant process and operational data, and any corresponding emissions estimates
developed using conventional software programs and methods. Amine units that target CO2 for
removal (amine units in CO2 service) were a priority. As measurement of amine unit VOC
emissions data is not required nor is there a requirement that such measurements, if made, be
submitted to any central office or agency, it was anticipated that few sources of data would be
identified.

The assistance of the TCEQ was enlisted in seeking data that may be useful from their publicly
available emissions inventory and permit data. UT Austin prepared a Data Collection
Memorandum summarizing the available data sources. An assessment of the completeness and
validity of the data sets for each source was then conducted by the UT Project Team. For
example, UT Austin reviewed the data proposed for use as inputs for the process simulators and
software models to ensure that all required inputs were available or could be determined with
reasonable accuracy, ensure reported pressures are representative of natural gas processing plant
line pressures, ensure operating temperatures are consistent with amine solution specifications,
etc. UT Austin reviewed VOC measurement data to verify, to the extent possible, that the test
methods used were consistent with reference test methods and that sample temperatures and
pressures appeared reasonable.

If direct measurement data were not available for an amine unit, UT Austin used the specified
emissions methods to estimate emissions and compare results determined by each method. The
focus of the analysis was to compare modeled amine unit emissions to emissions determined by
direct measurement data. For each data source identified in the Data Collection Memorandum,
the UT Austin Project Team attempted to determine total VOC and speciated hydrocarbon
emissions (to the extent speciated data were available) using the data collection process and
operational, sampling, and site data in conjunction with the methods approved by the TCEQ
Project Manager.

Total VOC and speciated hydrocarbon emissions were classified by location, site description, the
properties of the amine unit (including the type of acid gas removed, as well as the removal
process itself, and the emissions determination method. UT Austin compared the VOC
emissions estimates generated by each of the specified methods as a set to those calculated from
vent gas analyses because direct measurement data were not available. For amine units without
vent gas analyses, UT Austin compared the VOC emissions estimates generated by each of the
specified methods.

The UT Austin Project Team then analyzed, including statistical analysis as appropriate, how
accurately each of the specified methods corresponded to the available direct measurements. For
amine units without direct emissions measurements, the Project Team performed an analysis of
how well the emissions predicted by each of the specified methods correlated to one another.
Conclusions would then be formulated based on how accurately the amine unit emissions
methods estimated emissions.

5
The Project Team also compared emissions predicted by each different method for the same
amine unit (i.e., same source) and analyzed the predicted emissions for trends (e.g., consistently
predicting the highest emissions rate), drawing conclusions about the observed performance of
the emissions methods.

2.2 Amine Units Emissions Methods Selection

The Project Team considered the following TCEQ approved methods for inclusion in this study.

• American Petroleum Institute’s (API) AMINECalc Version 1.0 – Amine Unit Emissions
Model (API Publication 4679)
• Aspen HYSYS process simulator
• Bryan Research and Engineering’s (BR&E) ProMax process simulator
• Schneider Electric SimSci Pro/II process simulator

Although AMINECalc is not a process simulation package, it is used extensively by industry and
was included in the study. Of the remaining three methods, Aspen HYSYS would be available to
the Project Team through UT Austin’s existing site license agreements with the product vendor
at little to no cost to the project. Therefore, it was included in the study. Of the remaining two
packages, there was sufficient budget to include only one of the two process simulators. Given
the degree that BR&E ProMax is reported by the TCEQ as being used in permit applications
relative to Pro/II, the decision was made to include ProMax first and Pro/II only if time and
budget allowed.

2.3 Data Collected

Data required to conduct the analysis proposed in this study included, at a minimum, mid-stream
gas processing plant process and operational data sufficient to perform VOC emissions estimates
using any of the software emissions models and process simulators listed in Section 2.2 of this
report, and VOC emissions measurement data from amine regenerator (still) vents and associated
flash tanks. UT Austin worked with the TCEQ Project Manager to identify potential sources of
the required data. Potential data sources included TCEQ emissions inventories and/or air permit
applications, midstream gas plant representatives, industry or trade groups, and other states
environmental agencies.

The amine unit data sets that include most of the data described above as needed to conduct the
analysis proposed were identified from emission inventory and permit data by the TCEQ for
possible use in this project. These data sets are summarized in Table 1. An assessment of each
data set is included in Section 2.4.

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 Table 1. Amine Unit Data Sets Identified for Possible Use
County Unit Name/Reference
Priority Units
Brazoria Case Study 00
Bee AMINEPROC1B
Hemphill AMINEGH
Johnson V1
Johnson V4
Montague S6-AS 1100(O-4)
Montague S6-AS 400(O-1)
Wheeler S7-V2 (O)

Secondary Priority Units

Johnson V2
Live Oak AMINE31

2.4 Description and Summary of Assessment of Available Data Sets

A review of the data sets provided by the TCEQ identified two cases that could be used for the
comparison analysis using all three process simulators for VOC and BTEX emissions estimates.
The primary limitation was due to the five solvents and one process configuration supplied with
the AMINECalc software.

AMINECalc cannot simulate mixed amine blends and only the following amines can be selected:
DEA (diethanolamine), MEA (monoethanolamine), MDEA (Methyldiethanolamine), TEA
(triethanolamine), and DGA (diglycolamine). Thus other solvents, such as Piperazine (PZ),
cannot be simulated in AMINECalc. AMINECalc is also limited to the standard amine unit
process configuration, which contains an absorber, rich amine flash, and regenerator

7
 (Figure 1). A summary of the process simulator limitations is shown in

Figure 1. AMINECalc Process Configuration

Table 2.

Based on these criteria, two amine units were identified for the process simulator comparison
analysis: AMINEGH and S7-V2 (O) amine units. Based on the available data, the analyses in
this report focused primarily on the S7-V2 (O) Amine Unit.

8
 Figure 1. AMINECalc Process Configuration

Table 2. Process Simulator Limitations on Data Sets

Site/Plant Amine Solvent Process Flow Process Simulator Limitations
Configuration
Case Study 00 JeffAmine 505 Standard Solvent unavailable in AMINECalc,
ProMax, HYSYS
AMINEPROC1B MDEA/DEA Rich Flash Cannot simulate configuration in
Absorber AMINECalc
AMINEGH MDEA Standard None

V1 MDEA/DEA Standard Cannot simulate MDEA/DEA blend

in AMINECalc
V4 MDEA/DEA Standard Cannot simulate MDEA/DEA blend
in AMINECalc
S6-AS 1100(O-4) MDEA/PZ Standard Cannot simulate MDEA/PZ blend in
AMINECalc
S6-AS 400(O-1) MDEA/PZ Standard Cannot simulate MDEA/PZ blend in
AMINECalc
S7-V2 (O) MDEA Standard None

AMINE31 MDEA/PZ Standard Cannot simulate MDEA/PZ blend in

AMINECalc

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3 Amine Units Emissions Methods Estimates
3.1 Technical Approach
The amine unit gas composition data sets that were provided typically contained only a few
laboratory analyses of gas samples from the following:

1. Inlet sour gas to the amine unit absorber

2. Outlet sweet gas leaving the amine unit absorber (or inlet gas to the glycol dehydrator)
3. Rich amine flash outlet gas (flared or vented)
4. Regenerator/still acid gas (flared or vented)

In some cases, gas analyses results were not consistent with the gas compositions expected for
the sweet gas, rich amine flash gas, and/or acid gas leaving the regenerator.

Some of the amine unit data sets contained process simulations of the plant using either BRE
ProMax or AmineCalc Version 1.0. In the simulations provided by the amine unit operator, the
inlet gas composition from the laboratory analysis was used. However, there were some
differences among the amine operator simulations regarding how the inlet lab gas analysis was
used in the process simulator due to limits with the process simulator itself as well as usage of
the lab data.

3.2 AMINECalc v1.0 Limitations

AmineCalc simulations were provided by several amine unit vendors to estimate VOC and
BTEX emissions. Only a minimal amount of information is needed to complete a simulation in
AmineCalc. Inputs to the AMINECalc inlet sour gas components are limited to the following 26
species:

H2S Hexanes
CO2 Heptanes
MDEA Octanes
H2O Nonanes
N2 C10+
O2 MeSH
C1 EtSH
C2 Benzene
C3 Toluene
i-C4 Ethylbenzene
n-C4 Xylenes
i-C5 n-C6
n-C5 224-Trimethylpentane

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Input parameters for AMINECalc include:
1. Model Selection: Mass Balance, Gas Model, NGL Model
2. Amine type: DEA (diethanolamine), MEA (monoethanolamine), MDEA
(Methyldiethanolamine), TEA (triethanolamine), or DGA (diglycolamine)
3. Weight % of amine
4. Amine circulation rate, T, P
5. Lean loading of H2S and CO2
6. Rich amine flash pressure
7. Inlet gas flow, composition, T, P
8. Absorber stages – 22 stage maximum

While AMINECalc is relatively simple to use, the simulator is limited to single amine solvents
and cannot be used for blended amine systems such MDEA/PZ. AMINECalc allows the user to
input unchecked CO2 and H2S lean loading values, which can have a substantial effect on the
process simulator results. AMINECalc also does not incorporate an iterative recycle loop
calculation like ProMax and HYSYS.

3.3 ProMax and HYSYS Process Simulators

Both ProMax and HYSYS are considered to be more rigorous process simulators relative to
AMINECalc. The two process simulators can simulate a wide range of process configurations,
amine solvent concentrations and blends, but require more input details and user knowledge to
use these simulators correctly and generate more accurate results. The two simulators also allow
the user to incorporate an iterative recycle stream, which serves as a check to user input of H2S
and CO2 loadings. The two process simulators can be operated in an “efficiency” model mode or
by using the rigorous mass and heat transfer model for the absorber and regenerator.

3.4 Gas Sample Analysis Speciation Format

In order to simplify comparison of simulation results between AMINECalc, ProMax, and
HYSYS, the extended laboratory analyses of gas samples were condensed to match the gas
component speciation of AMINECalc. With the exception of benzene, toluene, ethylbenzene,
xylenes, n-C6, heptanes, octanes, nonanes, and 224-Trimethylpentane, higher molecular weight
species were grouped together as n-C10+.

In ProMax, the hexanes component was represented as i-C6 (Table 3). In HYSYS, the hexanes
component was represented by 2-methylpentane. In both ProMax and HYSYS, all xylenes were
represented as m-xylene. All gas compositions inputs to each of the three process simulators
contained the following species:

Table 3. ProMax and HYSYS Component Substititions

Amine Calc ProMax HYSYS
Component
Hexanes i-C6 2-methylpentane
Xylenes m-xylene m-xylene

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3.5 Saturated Sour Gas Composition Input
Most laboratory analysis of the gas samples are typically reported on a dry basis. However, sour
gas is typically saturated with water when it enters the absorber column. In ProMax, a water
saturator is used to add water to the sour gas stream. AMINECalc and HYSYS simulations were
completed using the saturated sour gas stream composition determined from ProMax.

3.6 Amine Unit Operating Conditions and Configuration

Typical operating conditions for an MDEA amine unit with a standard absorber, rich amine
flash, and regenerator are shown in Figure 2. The MDEA solvent concentration is between 40 -
50 wt% and total acid gas lean loading is between 0.001 – 0.005 mol/mol amine. Acid gas rich
loading is typically between 0.35 - 0.5 mol/mol amine. In order to meet pipeline specifications,
sweetened gas must have H2S and CO2 concentrations less than 4 ppm and 2 mol%, respectively.
Overhead gas leaving the regenerator will be greater than 220 °F.

Figure 2. Typical Plant Operating Conditions for MDEA Amine Unit

Amine unit plant operating conditions such as temperature, pressure, flow rate, and amine
solvent composition were extracted from AMINECalc and ProMax simulations provided by the
amine unit operator. It was evident that some process simulations were inconsistent with results
expected from typical amine units. For example, some AMINECalc simulations assumed a zero

12
lean loading. In another AMINECalc case, the lean loading for both H2S and CO2 were assumed
to be the same and were on the order of 0.01 mol/mol amine, which is fairly high.

3.7 ProMax and HYSYS Process Configuration Specifications

In order to simplify the process simulator comparisons, the process configuration specifications
shown in Table 4 were made in both the ProMax and HYSYS process simulations.

Table 4. ProMax and HYSYS Process Configurations Specifications

Parameter Value Unit
Absorber column pressure drop 3 psi
Absorber column internals Sieve tray -
Absorber sieve tray spacing 2 ft
Lean pump efficiency 65 %
Trim cooler pressure drop 5 psi
Lean/Rich exchanger pressure drop (each side) 5 psi
Regenerator rich amine feed temperature 210 F
Regenerator column pressure (top stage) 26.7 psia
Regenerator column pressure drop 4 psi
Regenerator column internals Sieve tray -
Regenerator sieve tray spacing 2 ft
Regenerator condenser temperature 120 °F

3.8 Approach Used in Process Simulation of Amine Units

1. Adjust lean loading and number of stages to match sweet gas
2. Convert inlet sour gas lab analysis format for use in Amine Calc – combined components for
hexanes (except n-C6), heptanes, octanes, nonanes, C10+,
3. Convert inlet sour gas lab analysis format for use in Promax
4. Extract operating conditions, flowrates, and compositions from process simulators
(AMINECalc or Promax) and input into standard table for Promax and AMINECalc
5. Run simulation in AMINECalc
6. Run simulation in ProMax
7. Run simulation in Aspen HYSYS
8. Compare simulated output streams to lab analysis.

4 Analysis and Discussion of Amine Units Emissions Methods

Estimates
4.1 Case Study 1A - S7-V2 (O) Amine Unit
The process flow diagram for the S7-V2 (O) Amine Unit is shown in Figure 3. It was assumed
that the MDEA amine unit had a standard absorber, rich amine flash, and regenerator process
configuration. The results of two AMINECalc process simulations were provided along with
laboratory gas analyses of the sour gas, sweet gas, and acid gas.

13
 Figure 3: the S7-V2 (O) Amine Unit process configuration
4.1.1 Data Set Analysis
A review of the data sheets and process simulations showed a number of inconsistencies between
the laboratory results, process simulations, and reported analyses. Two AMINECalc process
simulations were provided, which had inlet sour gas concentrations of 1200 and 1300 ppmv of
H2S ( S7-V2 (O) Amine Unit AMINECalc Plant Conditions). Each run showed operation at
different H2S and CO2 lean loadings, liquid flow rates, and lean solvent pressure and
temperatures.

Table 5. S7-V2 (O) Amine Unit AMINECalc Plant Conditions

Run H2S H2S Lean CO2 Lean Lean Flow Lean Lean
(ppmv) Loading Loading (gpm) Pressure Temperature
(psia) (°F)
1 1200 0.001 0.01 20 600 90
2 1300 0.01 0.01 200 800 100

In Run 1, the sour gas composition (inlet gas to amine unit) did not match any of the data sheets
or laboratory analyses provided, was limited to component speciation up to hexanes (C6+) and
did not include concentrations for BTEX.

The Run 2 sour gas composition (1300 ppm H2S) was consistent with the laboratory analysis
sample date of 3/10/2011 (Spot sample @ 599 psig / 59 °F). However, the laboratory results for
the sweet gas analysis (inlet gas to dehydrator, sample date 3/10/2011, spot sample @ 605 psig

14
& 84 °F) seemed to show approximately the same H2S and CO2 concentrations as the inlet sour
gas. This implies that either the amine unit was offline, does not exist, or perhaps a sampling
error or sample location error. A laboratory analysis for the acid gas (Amine Unit Gas to Flare)
of the amine unit on the same date was also provided (amine unit gas to flare, sample date
3/10/2011, spot sample @ 0 psig & 58 °F). The acid gas analysis appears somewhat consistent
for CO2 concentration (~80 mol%), but the methane concentration (14.5 mol%) was higher than
expected and H2S (3 mol%) was lower than expected.

The various gas analyses provided showed several inconsistencies. The H2S and CO2
concentrations in the Dehydrator Gas Analysis (sweeten gas leaving the amine absorber unit)
were essentially the same as the separator gas analysis, which is upstream of the amine unit. The
Flare Gas Analysis matched the laboratory analysis for 1300 ppmv H2S analysis, however, the
Inlet Gas Analysis in the same site analysis file showed 1200 ppmv. The Flash Gas Analysis
composition did not seem consistent with that expected from a rich amine flash, which typically
has a C1 concentration closer to 95%. The laboratory analysis showed 73%.

Based on a review of the provided data sets, the process simulation comparison for the S7-V2
(O) Amine Unit case was performed using plant-operating conditions shown in Run 2 and the
sour gas composition from the 1300 ppmv H2S laboratory analysis. The individual H2S and CO2
lean loadings specified in Run 2 were not consistent with that expected in an operating natural
gas plant. For MDEA, total acid gas lean loading is typically between 0.001 – 0.005 mol/mol
amine. Instead, it was assumed that the total acid gas lean loading was equivalent to the total
acid gas lean loading determined from the AMINECalc Run 2 report, 0.02 mol/mol amine, and
individual H2S and CO2 loadings were determined by ProMax (H2S = 0.0187 and CO2 = 0.0013).
A new AMINECalc simulation was developed using the individual H2S and CO2 loadings
calculated by ProMax. Results of the simulations were compared to the laboratory acid gas
analysis sampled on 3/10/2011.

4.1.2 Laboratory Gas Analysis

The extended laboratory analysis for the sour gas, sweet gas, and acid were reformatted and
condensed into the AMINECalc speciation format to perform the process simulator analysis
(Table 6. Extended gas analysis for the S7-V2 (O) Amine Unit (Dry Basis)). C6 and higher
components were combined together by carbon number count with the exception of BTEX, n-
C6, and 2,2,4-Trimethylpentane (Table 7. Gas composition condensed into AMINECalc
speciation format (Dry Basis)). The data set was from the samples taken on 3/10/2011.

15
Table 6. Extended gas analysis for the S7-V2 (O) Amine Unit (Dry Basis)
Component Sour Gas Sweet Gas Acid Gas
Mol% Mol% Mol%
Water 0 0 0
Nitrogen 0.152 0.175 1.213
Oxygen 0 0 0
Carbon Dioxide 2.321 2.457 79.91
Hydrogen Sulfide 0.13 0.138 3
Methane 93.903 93.698 14.481
Ethane 2.083 2.137 0.958
Propane 0.514 0.516 0.187
Isobutane 0.169 0.177 0.018
n-Butane 0.205 0.21 0.025
2,2, Dimethylpropane 0.008 0.014 0
Isopentane 0.103 0.103 0.016
n-Pentane 0.092 0.09 0.014
2,2 Dimethylbutane 0.007 0.006 0.001
Cyclopentane 0.004 0.004 0.002
2,3 Dimethylbutane 0.005 0.004 0
2 Methylpentane 0.029 0.024 0.003
3 Methylpentane 0.016 0.014 0.002
n-Hexane 0.044 0.038 0.004
Methylcyclopentane 0.013 0.011 0.003
Benzene 0.017 0.014 0.062
Cyclohexane 0.026 0.023 0.006
2-Methylhexane 0.009 0.009 0.001
3-Methylhexane 0.009 0.008 0.001
2,2,4-Trimethylpentane 0 0 0
Other C7s 0.014 0.011 0.002
n-Heptane 0.019 0.018 0.002
Methylcyclohexane 0.021 0.021 0.003
Toluene 0.03 0.03 0.073
Other C8s 0.017 0.018 0.001
n-Octane 0.007 0.008 0.001
Ethylbenzene 0.001 0 0.001
m & p -Xylenes 0.005 0.006 0.007
o-xylene 0.002 0.001 0.002
Other C9s 0.005 0.006 0
n-Nonane 0.003 0.003 0
Other C10s 0.002 0.003 0.001
n-Decane 0.001 0.002 0
Undecanes 0.014 0.003 0
Total 100 100 100

16
 Table 7. Gas composition condensed into AMINECalc speciation format (Dry Basis)
Component Sour Gas Sweet Gas Acid Gas
Mol% Mol% Mol%
H2S 0.13 0.138 3
CO2 2.321 2.457 79.91
MDEA 0 0 0
H2O 0 0 0
N2 0.152 0.175 1.213
O2 0 0 0
C1 93.903 93.698 14.481
C2 2.083 2.137 0.958
C3 0.514 0.516 0.187
i-C4 0.169 0.177 0.018
n-C4 0.205 0.21 0.025
i-C5 0.115 0.121 0.018
n-C5 0.092 0.09 0.014
Hexanes 0.096 0.082 0.015
Heptanes 0.072 0.067 0.009
Octanes 0.024 0.026 0.002
Nonanes 0.008 0.009 0
C10+ 0.017 0.008 0.001
MeSH 0 0 0
EtSH 0 0 0
Benzene 0.017 0.014 0.062
Toluene 0.03 0.03 0.073
Ethylbenzene 0.001 0 0.001
Xylenes 0.007 0.007 0.009
n-C6 0.044 0.038 0.004
224Trimethylpentane 0 0 0
Total 100 100 100

4.1.3 AMINECalc Simulation

The Run 2 AMINECalc process simulation conditions provided by the amine unit operator are
show in Table 8 below. However, as noted above, the lean loadings specified for H2S and CO2
do not seem plausible for a typical MDEA gas-treating unit. The liquid circulation rate was also
considerably higher than expected, but may be reasonable because of the high H2S and CO2 lean
loadings that were specified.

17
 Table 8: Run 2 AMINECalc Input from Operator Simulation Results File

One of several issues with AMINECalc is that it allows the user to input any range of H2S and
CO2 lean loadings, even conditions that cannot exist in an operating plant. Another is that the
software only allows inputs to the sour gas of four significant figures in mole % for each gas
component. For BTEX and certain VOC components that are below the 1 ppmv range in sour
gas, these components cannot be inputted into AMINECalc, which affects fidelity of the
simulation results.

Figure 4. AMINECalc Process Simulation Flowsheet

18
4.1.4 ProMax Simulation Parameters
The ProMax simulation was performed using the Amine Sweetening – PR (Peng-Robinson)
vapor-liquid property package. A simulation was performed with a 0.02 mol/mol amine lean
loading, 200 gpm amine circulation rate, and incorporated a recycle loop configuration to
provide more fidelity to the simulation (Figure 5). The ideal stage with TSWEET Kinetics and
TSWEET Stripper model types were used for the absorber and regenerator columns,
respectively. The rigorous mass and heat transfer models were not used in the ProMax
simulations of the absorber and regenerator to help simplify the analysis.

The number of absorber stages was varied to match the 0.06 total acid gas loading obtained in
AMINECalc. However, to match the 0.06 rich loading, the total number of ideal stages was
reduced from 7 to 3 ideal stages (real/ideal ratio of 3), which may or may not match the actual
configuration of the amine plant. The regenerator was specified with 10 stages and the reboiler
duty (5.5 MMBtu/hr) was adjusted to match the lean loading. Sieve trays at 2 feet spacing and 3-
inch weir heights were specified in the absorber and regenerator columns.

Figure 5. ProMax Process Simulation Flowsheet

4.1.5 HYSYS Simulation Parameters
The HYSYS simulation was performed using the Acid Gas – Chemical Solvents vapor-liquid
property package. The HYSYS process simulation did not incorporate a recycle loop because the
H2S and CO2 lean-loading results from the regenerator did not seem to agree well with the
AMINECalc and ProMax results. Incorporating a recycle loop would have complicated the
absorber and rich amine flash results. The absorber and regenerator columns utilized the
“Efficiency” calculation type, which is similar to the ProMax Ideal Stage model. The HYSYS

19
“Advanced Model” calculation type which incorporate rigorous mass and heat transfer
correlations was not used. The “Advanced Model” is equivalent to the ProMax Mass + Heat
Transfer model.

The simulation was performed with a 0.02 mol/mol amine lean loading and 200 gpm amine
circulation rate. Like the ProMax simulation, the number of absorber stages was varied to match
the 0.06 mol/mol amine total acid gas rich loading obtained in AMINECalc. A total of 8 stages
was needed to achieve the 0.06 mol/mol amine rich loading. The regenerator was specified with
10 stages and the reboiler duty (4.9 MMBtu/hr) was adjusted to match the 0.02 mol/mol amine
lean loading. Sieve trays at 2 feet spacing and 3-inch weir heights were specified in the absorber
and regenerator columns.

Figure 6. HYSYS Process Simulation Flowsheet

4.1.6 Absorber Analysis

The absorber simulations in AMINECalc, ProMax, and HYSYS were completed with an amine
circulation rate of 103,197 lb/hr (200 gpm) and a total acid gas loading of 0.02 mol/mol amine
(Table 9). The individual H2S and CO2 lean loadings for AMINECalc and HYSYS were the
same, but the ProMax values were slightly different because the simulation was performed with
a recycle loop. The AMINECalc and HYSYS simulations did not have a recycle loop to help
simplify simulations, which would allow specifying lean and rich loadings in the absorber, flash,
and regenerator.

20
 Table 9. Case 1A Absorber Lean Amine Liquid Flow and Composition

AMINECalc ProMax HYSYS Units

H2S 167.9 165.7 167.9 lb/hr
CO2 11.4 14.9 11.4 lb/hr
MDEA 30,905 30,959 30,905 lb/hr
H2O 72,112 72,057 72,112 lb/hr
Total 103,197 103,197 103,197 lb/hr

H2S Loading 0.0190 0.0187 0.0190 mol/mol amine

CO2 Loading 0.0010 0.0013 0.0010 mol/mol amine
Total Acid Gas Loading 0.0200 0.0200 0.0200 mol/mol amine

The absorber configuration in ProMax and HYSYS was adjusted to match the total acid gas
loading (0.06 mol/mol amine) in the rich amine stream of a 22 stage AMINECalc absorber
(Table 10). The H2S and CO2 loadings were similar between the three process simulators, but
the total mass flow rates differed between 30-50 lb/hr. The results show that the absorber rich
stream predicted by AMINECalc has the lowest VOC and BTEX concentration, followed by
ProMax, and HYSYS, which have the highest concentrations.

Table 11 shows that while CO2 concentration of all three simulations met the 2% CO2 pipeline
specification, none of the gas compositions would have met the 4 ppmv H2S pipeline
specification. The results also show that more than 99% of the VOC and BTEX components of
the sour gas leave the absorber in the sweet gas. Less than 1% of the total VOC and BTEX is
absorbed and subsequently removed in the rich amine flash and regenerator acid gas. The results
show that VOC and BTEX rates in the sweet gas were highest in AMINECalc, followed by
ProMax, with HYSYS being the lowest.

Table 10. Case 1A Absorber Rich Amine Liquid Flow and VOC/BTEX

AMINECalc ProMax HYSYS Units

H2S Loading 0.0227 0.0224 0.0227 mol/mol amine
CO2 Loading 0.0374 0.0382 0.0373 mol/mol amine
Total Acid Gas Loading 0.0601 0.0606 0.0600 mol/mol amine
Total Mass Flow 103,707 103,737 103,752 lb/hr

VOC Components 5.249 21.203 34.429 lb/hr

BTEX Components 4.199 18.749 26.353 lb/hr

21
 Table 11. Case 1A Sweet Gas Composition, Flow, and VOC/BTEX

AMINECalc ProMax HYSYS Units

H2S 5.37 24.75 17.24 ppm
CO2 1.06 1.05 1.07 mol%
Total Mass Flow 12,606 12,594 12,590 lb/hr

VOC Components 659.09 643.93 630.77 lb/hr

BTEX Components 32.43 17.87 10.28 lb/hr

4.1.7 Rich Amine Flash Analysis

The analysis of the rich amine flash gas shows that ProMax and HYSYS predict approximately
the same total mass flow of 60 lb/hr and AMINECalc is about 10 lb/hr lower. The VOC and
BTEX emissions predicted by the three simulators are on the same order of magnitude, with
AMINECalc predicting the lowest VOC emission rates followed by ProMax and then HYSYS.
The HYSYS prediction of the VOC emissions was more than double that of AMINECalc. The
BTEX emissions were on the same order of magnitude with ProMax predicting the lowest BTEX
emissions followed by AMINECalc and then HYSYS. The rich flash temperatures calculated by
ProMax and HYSYS were within 0.2 °F of each other and AMINECalc was about 1.8 °F lower
than ProMax.

Table 12. Case 1A Rich Flash Gas Composition, Flow and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S 0.0149 0.0265 0.0305 mol%
CO2 0.0177 0.0564 0.0498 mol%
Total Mass Flow 49.55 59.50 62.75 lb/hr

VOC Components 1.557 2.392 3.683 lb/hr

BTEX Components 0.646 0.448 0.490 lb/hr
Temperature 102.0 103.8 103.6 F
Pressure 100 100 100 psia

4.1.8 Regenerator Analysis

The rich amine solvent loading to the regenerator was approximately 0.06 mol/mol amine for all
three process simulators (Table 13). The regenerator configuration and reboiler duty in ProMax
and HYSYS were adjusted to match a total acid gas lean loading of 0.02 mol/mol amine (Table
14). While the total acid gas lean loading was 0.02 mol/mol amine, the individual H2S and CO2
loading of HYSYS was quite different than AMINECalc and ProMax, with the HYSYS CO2
loading approximately 7 and 5.4 times higher than AMINECalc and ProMax, respectively.

The lean amine solvent temperatures calculated in ProMax and HYSYS were within 1°F at 254.9
and 253.8 °F, respectively. Although the total mass flow of the regenerator lean solvent for
ProMax is approximately 20 lb/hr lower than AMINECalc and HYSYS, the recycle/make-up
loop adds additional solvent to maintain 103,197 lb/hr of feed to the absorber column.

22
 Table 13. Case 1A Regenerator Feed Rich Amine Liquid Composition, Flow, and
VOC/BTEX

AMINECalc ProMax HYSYS Units

H2S Loading 0.0227 0.0223 0.0227 mol/mol amine
CO2 Loading 0.0374 0.0382 0.0373 mol/mol amine
Total Acid Gas Loading 0.0601 0.0606 0.0600 mol/mol amine
Total Mass Flow 103,657 103,677 103,690 lb/hr

VOC Components 3.690 18.811 30.745 lb/hr

BTEX Components 3.553 18.301 25.862 lb/hr

Table 14. Case 1A Regenerator Lean Amine Liquid Composition, Flow and Conditions

AMINECalc ProMax HYSYS Units

H2S Loading 0.0190 0.0187 0.0130 mol/mol amine
CO2 Loading 0.0010 0.0013 0.0070 mol/mol amine
Total Acid Gas Loading 0.0200 0.0200 0.0200 mol/mol amine
Total Mass Flow 103,197 103,176 103,195 lb/hr

Temperature - 254.9 253.8 °F

Pressure - 30.7 30.7 psia

An analysis of the regenerator acid gas results showed that the VOC and BTEX emissions were
lowest for AMINECalc. The ProMax VOC and BTEX emissions were approximately five times
higher than the values predicted by AMINECalc. The HYSYS VOC and BTEX emissions were
approximately 8.3 and 7.3 times higher than the values predicted by AMINECalc. There was
also some difference in the H2S and CO2 concentrations between the process simulators. The
AMINECalc acid gas composition does not include any water. It assumes that the water is
retained by the solvent. Whereas, ProMax and HYSYS have a water content of 6.4 mol%.

Table 15. Case 1A Regenerator Acid Gas Composition, Flow, and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S 8.68 7.67 13.13 mol%
CO2 85.51 77.68 71.22 mol%
Total Mass Flow 461.31 501.02 489.66 lb/hr

VOC Components 3.690 18.811 30.745 lb/hr

BTEX Components 3.553 18.301 25.862 lb/hr

23
Table 16 shows the detailed mass flow and concentration of the various components of the acid
gas stream predicted by the three process simulators. The results show that AMINECalc
predicts no water in the acid gas stream, whereas both ProMax and HYSYS predict about 6.4
mol% water. A cursory analysis also shows that for each of the BTEX components,
AMINECalc predicts the lowest emission rate, HYSYS is the highest, and ProMax is in between
the two. In particular, the toluene and xylene emission rates predicted by ProMax and HYSYS
are an order of magnitude higher than that predict by AMINECalc.

Table 16. Case 1A Detailed Regenerator Acid Gas Composition

Component AMINECalc ProMax HYSYS

lb/hr mol% lb/hr mol% lb/hr mol%
H2S 32.63 8.68 32.29 7.67 85.72 13.13
CO2 415.21 85.51 422.26 77.68 345.70 71.22
MDEA 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 14.3225 6.4367 14.3000 6.4614
N2 0.0070 0.0023 0.0055 0.0016 0.0081 0.0023
C1 9.2800 5.2438 12.3101 6.2127 12.2300 6.1010
C2 0.4900 0.1477 1.0182 0.2742 0.9557 0.2546
C3 0.1250 0.0257 0.2280 0.0419 0.2635 0.0479
i-C4 0.0000 0.0000 0.0490 0.0068 0.1731 0.0239
n-C4 0.0000 0.0000 0.1178 0.0164 0.1290 0.0178
i-C5 0.0000 0.0000 0.0317 0.0036 1.2360 0.1392
n-C5 0.0000 0.0000 0.0370 0.0041 0.0528 0.0059
Hexanes 0.0060 0.0006 0.0265 0.0025 2.9650 0.2795
Heptanes 0.0000 0.0000 0.0069 0.0006 0.0297 0.0024
Octanes 0.0000 0.0000 0.0019 0.0001 0.0069 0.0005
Nonanes 0.0000 0.0000 0.0001 0.0000 0.0017 0.0001
C10+ 0.0000 0.0000 0.0001 0.0000 0.0025 0.0001
Benzene 2.5530 0.2962 4.9011 0.5080 6.4370 0.6670
Toluene 0.6780 0.0667 9.8093 0.8620 13.5800 1.1942
Ethylbenzene 0.1870 0.0160 0.3229 0.0246 0.3864 0.0292
Xylenes 0.1350 0.0115 3.2673 0.2492 5.4590 0.4215
n-C6 0.0060 0.0006 0.0115 0.0011 0.0220 0.0021
Total 461.31 - 501.02 - 489.66 -

Table 17 shows the acid gas compositions on a dry basis and includes the laboratory analysis for
comparison. The H2S and CO2 concentrations predicted by the AMINECalc and ProMax are
similar to each other at approximately 8% and 83%, respectively. However, the HYSYS values
are higher for H2S (14%) and lower for CO2 (76%). The laboratory gas sample analysis shows
3% for H2S, which is not close to any of the simulations. The CO2 concentration for the gas
sample analysis is in between HYSYS and ProMax. The methane concentration for all three
process simulators is between 5.2 – 6.5 mol%. The lab gas analysis shows a methane
concentration of 14.5 mol%, which is unusual. There may be several reasons for the atypical lab

24
results: operational issues with the amine unit, such as the recirculation rate being too high and
“stripping” more hydrocarbons from the sour gas stream than typical amine units; sampling
location error; sample chain of custody error; or problems with the laboratory gas sample
analysis of the acid gas.

Table 17. Case 1A Detailed Regenerator Acid Gas Composition (Dry Basis)

Component Lab Analysis AMINECalc ProMax HYSYS

mol% mol% mol% mol%
H2S 3.0000 8.6788 8.1992 14.0394
CO2 79.9100 85.5100 83.0267 76.1367
MDEA 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 0.0000 0.0000
N2 1.2130 0.0023 0.0017 0.0025
C1 14.4810 5.2438 6.6401 6.5225
C2 0.9580 0.1477 0.2930 0.2722
C3 0.1870 0.0257 0.0447 0.0512
i-C4 0.0180 0.0000 0.0073 0.0255
n-C4 0.0250 0.0000 0.0175 0.0190
i-C5 0.0180 0.0000 0.0038 0.1488
n-C5 0.0140 0.0000 0.0044 0.0063
Hexanes 0.0150 0.0006 0.0027 0.2988
Heptanes 0.0090 0.0000 0.0006 0.0026
Octanes 0.0020 0.0000 0.0001 0.0005
Nonanes 0.0000 0.0000 0.0000 0.0001
C10+ 0.0010 0.0000 0.0000 0.0002
Benzene 0.0620 0.2962 0.5430 0.7131
Toluene 0.0730 0.0667 0.9213 1.2767
Ethylbenzene 0.0010 0.0160 0.0263 0.0313
Xylenes 0.0090 0.0115 0.2663 0.4506
n-C6 0.0040 0.0006 0.0012 0.0022

4.2 Case Study 1B - Hypothetical S7-V2 (O) Amine Unit Simulation

The individual H2S and CO2 lean loadings specified in the two vendor AMINECalc simulations
did not seem to be representative of what would be expected in an operating plant. In an amine
unit, the solvent circulates as a closed-loop system, with a minor makeup stream for losses from
the absorber column and degradation. The equilibrium ratio of H2S and CO2 in the lean amine
solvent stream will be a strong function of the initial concentration of both components in the
sour gas stream.

AMINECalc does not account for this equilibrium H2S and CO2 ratio in the lean amine solvent,
which can lead to erroneous results if the software user is not skilled. ProMax and HYSYS, on
the other hand, perform a rigorous closed loop analysis with a recycle stream that calculates the

25
individual H2S and CO2 concentrations in the lean amine solvent based on the sour gas stream
composition. The recycle stream calculation is iterative and results in H2S and CO2 lean
loadings that are more representative of a real amine plant.

Two simulations were performed in ProMax using the same lean liquid flows and total acid gas
lean loading conditions shown in the AMINECalc simulation: 200 gpm/0.02 mol/mol amine and
20 gpm/0.011 lean loading, respectively. The total acid gas lean loading is the sum of the H2S
and CO2 lean loadings with units of mol/mol amine. The ProMax “Solver” function was used to
adjust steam flow in the regenerator to attain a final total acid gas lean loading of 0.011 and 0.02
mol/mol amine in the simulations. The 1300 ppm sour gas composition from the gas sample
analysis was used. The ProMax absorber column was configured for 7 ideal stages with a
Real/Ideal stage ratio of 3 and system factor of 0.8.

While the sweet gas CO2 concentration did meet pipeline specification (< 2 mol%), the H2S
concentration did not meet the < 4 ppm pipe line specification. The results showed sweet gas
H2S concentration of 19.7 and 32.9 ppm for Runs 1 and 2, respectively. At a lean amine
circulation rate of 200 gpm, the steam required in the regenerator was much higher (5,996 lb/hr)
than operation at 20 gpm (763 lb/hr). To save on energy costs, the plant would most likely have
been operated at 20 gpm.

Table 18. ProMax Results Using Vendor AMINECalc Simulation Conditions

Steam/ Sweet Gas Absorber
H2S Steam Amine
Run Amine
Concentration Flow Flow H2S CO2 LN Ldg RH LDG
Ratio
lb/hr Gpm lb/gal ppm mol% mol/mol mol/mol
1 1300 5,996 200 0.50 19.7 0.4 0.0200 0.0787
2 1200 763 20 0.64 32.9 0.5 0.0110 0.2170

A hypothetical case was developed to determine the lean loading required to meet H2S and CO2
pipeline specification at a 20 gpm amine circulation rate and minimize steam required in the
regenerator. The results showed Case 5 run conditions to be reasonable, which met the rules of
thumb of 0.005 lean loading and steam/amine ratio of 1 lb/gal, and resulted in sweet gas H2S and
CO2 concentrations that met pipeline specification.

26
 Table 19. Hypothetical Optimized S7-V2 (O) Amine Unit Cases

Run Steam Flow Amine Flow Steam/Amine Sweet Gas Absorber

Ratio H2S CO2 LN Ldg RH LDG
lb/hr gpm lb/gal ppm mol%
1 9,605 200 0.80 2.4 0.5 0.0050 0.0630
2 7,407 200 0.62 40.3 0.5 0.0080 0.0653
3 8,224 200 0.69 19.7 0.4 0.0100 0.0787
4 5,145 100 0.86 2.2 1.2 0.0050 0.0770
5 1,200 20 1.00 2.7 1.9 0.0050 0.1790
6 1,139 20 0.95 3.4 1.9 0.0055 0.1800
7 1,087 20 0.91 4.0 1.9 0.0060 0.1810
8 957 20 0.80 7.0 1.9 0.0080 0.1850
9 880 20 0.73 10.3 1.8 0.0100 0.1890

Simulations in AMINECalc, ProMax, and HYSYS were performed around the absorber, rich
amine flash, and regenerator and the results compared. It was assumed that total acid gas loading
(H2S + CO2) was the most important parameter in defining the performance of each unit
operation. Due to the limited number of adjustable parameters in AMINECalc, the simulation
results of an AMINECalc 20 stage absorber was used as the base case. Adjustments were made
within the ProMax and HYSYS absorber and regenerator configuration to match lean and rich
total acid gas loadings calculated by AMINECalc for the inlet and outlet liquid streams of the
absorber, rich flash tank, and regenerator.

4.2.1 Absorber Analysis

A process flow diagram of the inlet and outlet streams around the absorber is shown in Figure 7.
The absorber simulations in AMINECalc, ProMax, and HYSYS were completed with an amine
circulation rate of 10,232.46 lb/hr (20 gpm) and H2S and CO2 lean loadings of 0.002 and 0.003
mol/mol amine, respectively, for a total acid gas loading of 0.005 mol/mol amine (Table 20).

27
 Figure 7. Case 1B Absorber Process Flow Diagram

Table 20. Case 1B Absorber Lean Amine Liquid Flow and Composition

Lean Amine Flow Units

H2S 1.76 lb/hr
CO2 3.4 lb/hr
MDEA 3068.2 lb/hr
H2O 7159.1 lb/hr
Total Lean Mass Flow 10232.46 lb/hr

H2S Loading 0.0020 mol/mol amine

CO2 Loading 0.0030 mol/mol amine
Total Acid Gas Loading 0.0050 mol/mol amine

The absorber configuration was adjusted in ProMax and HYSYS to match the total acid gas rich
amine loading calculated by AMINECalc (0.319 mol/mol amine). In all three cases, the H2S and
CO2 loadings were determined to be 0.039 and 0.28 mol/mol amine, respectively (Table 21).
The difference in total mass flow of the rich amine liquid stream was within 0.03%. Analysis of
the VOC and BTEX content in the rich amine shows that AMINECalc absorbed the least
amount, followed by ProMax and HYSYS. This is reflected in the sweet gas results, which
shows that AMINECalc has the highest concentration of VOC and BTEX leaving the absorber in
the outlet gas and HYSYS with the least amount of VOC and BTEX in the sweet gas (Table 22).

28
 Table 21. Case 1B Absorber Rich Amine Liquid Flow and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S Loading 0.0394 0.0394 0.0393 mol/mol amine
CO2 Loading 0.2799 0.2802 0.2799 mol/mol amine
Total Acid Gas Loading 0.3192 0.3196 0.3192 mol/mol amine
Total Mass Flow 10,580 10,577 10,577 lb/hr

VOC Components 0.488 1.617 4.730 lb/hr

BTEX Components 0.389 1.426 3.524 lb/hr

Table 22. Case 1B Sweet Gas Composition, Flow, and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S 2.478 2.223 4.493 ppm
CO2 1.373 1.371 1.372 mol%
Total Mass Flow 12,788 12,791 12,791 lb/hr

VOC Components 664.83 663.70 660.60 lb/hr

BTEX Components 36.29 35.25 33.15 lb/hr

4.2.2 Rich Amine Flash Analysis

The absorber rich stream was flashed at 100 psia in the flash tank (Figure 8). The results of the
rich flash show that AMINECalc has the lowest VOC emissions (0.149 lb/hr) and HYSYS has
more than double the VOC emissions at 0.327 lb/hr (Table 23). The ProMax VOC emissions are
slightly higher than AMINECalc at 0.2 lb/hr. The BTEX emissions of AMINECalc and HYSYS
are both approximately the same (0.064 lb/hr) with ProMax predicting 0.44 lb/hr. The flash
stream temperatures of HYSYS are 4-5 °F lower than ProMax and AMINECalc.

29
 Figure 8. Case 1B Rich Amine Flash Process Flow Diagram (100 psia)

Table 23. Case 1B Rich Flash Gas Composition, Flow and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S 0.1627 0.1799 0.1442 mol%
CO2 1.0942 1.8223 1.5227 mol%
Total Mass Flow 4.94 5.59 6.64 lb/hr

VOC Components 0.149 0.200 0.327 lb/hr

BTEX Components 0.064 0.044 0.063 lb/hr
Temperature 107.9 107.0 103.1 °F
Pressure 100 100 100 psia

Table 24 presents a detailed analysis of the rich amine flash gas composition predicted by the
three process simulators. The results show that total flash gas emissions are lowest with
AMINECalc and highest with HYSYS, with ProMax in between. The primary component of the
rich flash gas emission is methane, accounting for 93-94% of the total mass flow.

30
 Table 24. Case 1B Detailed Rich Amine Flash Gas Composition

Component AMINECalc ProMax HYSYS

lb/hr mol% lb/hr mol% lb/hr mol%
H2S 0.0160 0.1627 0.0197 0.1799 0.0186 0.1442
CO2 0.1390 1.0942 0.2573 1.8223 0.2539 1.5227
MDEA 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0580 1.1151 0.0642 1.1098 0.0674 0.9873
N2 0.0060 0.0742 0.0064 0.0717 0.0062 0.0583
C1 4.3730 94.4540 4.8060 93.3659 5.6692 93.2859
C2 0.1970 2.2698 0.2334 2.4193 0.2968 2.6053
C3 0.0610 0.4792 0.0633 0.4470 0.0891 0.5336
i-C4 0.0010 0.0060 0.0182 0.0975 0.0451 0.2049
n-C4 0.0020 0.0119 0.0299 0.1603 0.0427 0.1939
i-C5 0.0020 0.0096 0.0119 0.0513 0.0178 0.0652
n-C5 0.0010 0.0048 0.0115 0.0495 0.0203 0.0742
Hexanes 0.0080 0.0322 0.0101 0.0365 0.0157 0.0481
Heptanes 0.0020 0.0069 0.0045 0.0140 0.0150 0.0396
Octanes 0.0010 0.0030 0.0014 0.0037 0.0044 0.0101
Nonanes 0.0000 0.0000 0.0002 0.0004 0.0013 0.0027
C10+ 0.0010 0.0024 0.0002 0.0005 0.0023 0.0043
Benzene 0.0210 0.0931 0.0131 0.0522 0.0198 0.0669
Toluene 0.0330 0.1241 0.0245 0.0828 0.0405 0.1159
Ethylbenzene 0.0020 0.0065 0.0008 0.0024 0.0017 0.0041
Xylenes 0.0080 0.0261 0.0057 0.0167 0.0014 0.0034
n-C6 0.0060 0.0241 0.0044 0.0160 0.0096 0.0294
Total 4.9380 - 5.5866 - 6.6387 -

4.2.3 Regenerator Analysis

The process flow diagram for the regenerator is shown in Figure 9. Table 25 shows that the H2S
and CO2 loading in the regenerator rich amine stream is approximately the same. The total mass
flow rate for ProMax and HYSYS are both 10,571 lb/hr and AMINECalc is 4 lb/hr higher. The
content of VOC and BTEX in the regenerator rich amine stream in order from lowest to highest
is AMINECalc, ProMax, and HYSYS.

The ProMax and HYSYS regenerator configuration and reboiler duty were adjusted to match a
total acid gas loading of 0.005 mol/mol amine in the lean amine stream leaving the regenerator.
Since a recycle loop was not implemented, the individual H2S and CO2 lean loading results
diverged somewhat between the three process simulators, although the total acid gas loading was
maintained at 0.005 mol/mol amine (Table 26). In AMINECalc, CO2/H2S loading ratio was 1.5.
In ProMax the ratio was 2.8 and in HYSYS the ratio was 49, which was significantly higher and
a questionable result. The regenerator temperature and pressure are not provided in the

31
AMINECalc simulation. The ProMax and HYSYS regenerator lean amine temperatures were
within 1 °F at 255.3 and 254.4 °F, respectively.

Figure 9. Case1B Regenerator Process Flow Diagram

Table 25. Case 1B Regenerator Feed Rich Amine Liquid Composition, Flow, and
VOC/BTEX

AMINECalc ProMax HYSYS Units

H2S Loading 0.0393 0.0393 0.0393 mol/mol amine
CO2 Loading 0.2797 0.2800 0.2797 mol/mol amine
Total Acid Gas Loading 0.3191 0.3193 0.3190 mol/mol amine
Total Mass Flow 10,576 10,571 10,571 lb/hr

VOC Components 0.339 1.417 4.403 lb/hr

BTEX Components 0.326 1.382 3.460 lb/hr

32
 Table 26. Case 1B Regenerator Lean Amine Liquid Composition, Flow and Conditions

AMINECalc ProMax HYSYS Units

H2S Loading 0.0020 0.0013 0.0001 mol/mol amine
CO2 Loading 0.0030 0.0037 0.0049 mol/mol amine
Total Acid Gas Loading 0.0050 0.0050 0.0050 mol/mol amine
Total Mass Flow 10,232 10,212 10,209 lb/hr

Temperature - 255.3 254.4 °F

Pressure - 30.7 30.7 psia

In all three process simulators, the results show that the all of the remaining VOC, BTEX, C1,
and C2 in the amine solvent stream are stripped from the liquid and into the acid gas stream
Table 27). The results show that AMINECalc has the lowest VOC and BTEX emissions
followed by ProMax and HYSYS. The ProMax VOC and BTEX emissions are both
approximately 4.2 times higher than that calculated by AMINECalc. The HYSYS VOC and
BTEX emissions are approximately 13 and 10.6 times higher than AMINECalc, respectively.

Table 27. Case 1B Regenerator Acid Gas Composition, Flow, and VOC/BTEX Content

AMINECalc ProMax HYSYS Units

H2S 11.80 11.19 11.50 mol%
CO2 87.46 81.38 80.71 mol%
Total Mass Flow 347.50 359.25 361.50 lb/hr

VOC Components 0.339 1.417 4.403 lb/hr

BTEX Components 0.326 1.382 3.460 lb/hr

Table 28 shows the detailed mass flow and concentration of the various components of the acid
gas stream predicted by the three process simulators. The results show the same trend
demonstrated in Case 1A that AMINECalc predicts no water in the acid gas stream and 6.4
mol% water in the acid gas streams of ProMax and HYSYS. The table also shows that for each
of the BTEX components, AMINECalc predicts the lowest emission rate, HYSYS the highest,
and ProMax in between the two. The toluene and xylene emission rates predicted by ProMax are
an order of magnitude higher than that predicted by AMINECalc. Whereas, the HYSYS
prediction is two orders of magnitude higher than AMINECalc.

33
 Table 28. Case 1B Detailed Regenerator Acid Gas Composition

Component AMINECalc ProMax HYSYS

lb/hr mol% lb/hr mol% lb/hr mol%
H2S 32.75 11.80 33.35 11.19 34.38 11.50
CO2 313.48 87.46 313.18 81.38 311.40 80.71
MDEA 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 10.1439 6.4396 10.1924 6.4533
N2 0.0010 0.0004 0.0006 0.0002 0.0019 0.0008
C1 0.8810 0.6744 1.0841 0.7728 1.0542 0.7495
C2 0.0440 0.0180 0.0775 0.0295 0.0785 0.0298
C3 0.0110 0.0031 0.0169 0.0044 0.0209 0.0054
i-C4 0.0000 0.0000 0.0034 0.0007 0.0133 0.0026
n-C4 0.0000 0.0000 0.0082 0.0016 0.0100 0.0020
i-C5 0.0000 0.0000 0.0019 0.0003 0.2694 0.0426
n-C5 0.0000 0.0000 0.0023 0.0004 0.0037 0.0006
Hexanes 0.0010 0.0001 0.0015 0.0002 0.6217 0.0823
Heptanes 0.0000 0.0000 0.0004 0.0000 0.0017 0.0002
Octanes 0.0000 0.0000 0.0001 0.0000 0.0004 0.0000
Nonanes 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
C10+ 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
Benzene 0.2250 0.0354 0.3961 0.0580 0.6422 0.0938
Toluene 0.0710 0.0095 0.7232 0.0898 1.3535 0.1676
Ethylbenzene 0.0160 0.0018 0.0220 0.0024 0.0378 0.0041
Xylenes 0.0140 0.0016 0.2403 0.0259 1.4269 0.1533
n-C6 0.0010 0.0001 0.0006 0.0001 0.0014 0.0002
Total 347.50 - 359.25 - 361.50 -

Table 29 shows that the acid gas compositions predicted by the three process simulators on a dry
gas basis have similar H2S and CO2 concentrations at ~12% and ~87%, respectively. The
concentration of methane is also below 1%. The laboratory gas analysis of the acid gas,
however, shows a methane content of 14.5%, which is unusual. It is not clear if the lab analysis
is for the regenerator vent, or a combination of the regenerator and the flash gas. There may be
several other reasons for the atypical lab results: operational issues with the amine unit, such as
the recirculation rate being too high and “stripping” more hydrocarbons from the sour gas stream
than typical amine units; sampling location error; sample chain of custody error; or problems
with the laboratory gas sample analysis of the acid gas.

34
 Table 29. Case 1B Detailed Regenerator Acid Gas Composition (Dry Basis)

Component Lab Analysis AMINECalc ProMax HYSYS

mol% mol% mol% mol%
H2S 3.0000 11.7992 11.9601 12.2981
CO2 79.9100 87.4563 86.9858 86.2752
MDEA 0.0000 0.0000 0.0000 0.0000
H2O 0.0000 0.0000 0.0000 0.0000
N2 1.2130 0.0004 0.0002 0.0008
C1 14.4810 0.6744 0.8260 0.8012
C2 0.9580 0.0180 0.0315 0.0318
C3 0.1870 0.0031 0.0047 0.0058
i-C4 0.0180 0.0000 0.0007 0.0028
n-C4 0.0250 0.0000 0.0017 0.0021
i-C5 0.0180 0.0000 0.0003 0.0455
n-C5 0.0140 0.0000 0.0004 0.0006
Hexanes 0.0150 0.0001 0.0002 0.0880
Heptanes 0.0090 0.0000 0.0000 0.0002
Octanes 0.0020 0.0000 0.0000 0.0000
Nonanes 0.0000 0.0000 0.0000 0.0000
C10+ 0.0010 0.0000 0.0000 0.0000
Benzene 0.0620 0.0354 0.0620 0.1002
Toluene 0.0730 0.0095 0.0959 0.1791
Ethylbenzene 0.0010 0.0018 0.0025 0.0043
Xylenes 0.0090 0.0016 0.0277 0.1639
n-C6 0.0040 0.0001 0.0001 0.0002

4.2.4 VOC Rich Flash and Acid Gas Analysis

The results of the analysis of the total VOC in the amine unit system shows that AMINECalc
predicts 0.02% and 0.05% of the total VOC is released in the Rich Flash and Acid Gas (Table
30). ProMax predicts a comparable Rich Flash value of 0.03%, but 0.21% in the Acid Gas. The
HYSYS VOC prediction for the Rich Flash is twice that of AMINECalc at 0.05% and more than
10 times higher at 0.66% for the Acid Gas stream.

Table 31 compares the split of VOCs between the Rich Flash and Acid Gas. In AMINECalc,
approximately 30% of the total VOCs are in the Rich Flash and the balance in the Acid Gas. For
ProMax, 12% is in Rich Flash and 88% is in the Acid Gas stream. HYSYS predicts 7% of the
total VOC will be in the Rich Flash and the balance in the Acid Gas stream. The last column
shows that the total VOC emissions from the combined Rich Flash and Acid Gas streams of
ProMax is 3.3 times higher than AMINECalc. The total VOC emissions predicted by HYSYS is
9.7 times higher than that of AMINECalc.

35
 Table 30. VOC Split Between Sweet Gas, Rich Flash, and Acid Gas

Sweet Gas Rich Flash Acid Gas Total Units

AmineCalc 664.83 0.149 0.339 665.32 lb/hr
99.93% 0.02% 0.05%
ProMax 663.70 0.200 1.417 665.32 lb/hr
99.76% 0.03% 0.21%
HYSYS 660.59 0.327 4.403 665.32 lb/hr
99.29% 0.05% 0.66%

Table 31. VOC Split Between Rich Flash and Acid Gas

Rich Flash Acid Gas Total VOC Ratio

lb/hr % lb/hr % to AMINECalc
AMINECalc 0.149 30.5% 0.339 69.5% -
ProMax 0.20 12.3% 1.417 87.7% 3.3
HYSYS 0.327 6.9% 4.403 93.1% 9.7

4.2.5 BTEX Rich Flash and Acid Gas Analysis

The results of the analysis of the total BTEX in the amine unit system shows that AMINECalc
predicts 0.17% and 0.89% of the total VOC is released in the Rich Flash and Acid Gas (Table
32). ProMax predicts a slightly lower Rich Flash value of 0.12%, but more than three times at
3.77% in the Acid Gas. The HYSYS VOC prediction for the Rich Flash is the same as
AMINECalc at 0.17%, but is more than 10 times higher at 9.43% for the Acid Gas.

Table 33 compares the split of BTEX between the Rich Flash and Acid Gas. In AMINECalc,
approximately 16.4% of the total BTEX is in the Rich Flash and the balance is in the Acid Gas.
For ProMax, 3.1% is in Rich Flash and 96.9% is in the Acid Gas stream. HYSYS predicts 1.8%
of the total VOC will be in the Rich Flash and the balance in the Acid Gas stream. The last
column shows that the total VOC emissions from the combined Rich Flash and Acid Gas streams
of ProMax is 3.7 times higher than AMINECalc. The total VOC emissions predicted by HYSYS
is 9.0 times higher than that of AMINECalc.

Table 32. BTEX Split Between Sweet Gas, Rich Flash, and Acid Gas

Sweet Gas Rich Flash Acid Gas Total Units

AmineCalc 36.29 0.064 0.326 36.68 lb/hr
98.94% 0.17% 0.89%
ProMax 35.25 0.044 1.382 36.68 lb/hr
96.11% 0.12% 3.77%
HYSYS 33.15 0.063 3.460 36.68 lb/hr
90.39% 0.17% 9.43%

36
 Table 33. BTEX Split Between Rich Flash and Acid Gas

Rich Flash Acid Gas Total BTEX Ratio

lb/hr % lb/hr % to AMINECalc
AMINECalc 0.064 16.4% 0.326 83.6% -
ProMax 0.04 3.1% 1.382 96.9% 3.7
HYSYS 0.063 1.8% 3.460 98.2% 9.0

5 Conclusions
ProMax and HYSYS offer a recycle loop and make-up/purge stream, which generate an iterative
steady state H2S and CO2 loading in the amine stream for a given sour gas stream and specified
plant operating conditions.

AMINECalc allows the user to input any H2S and CO2 loading, which can lead to significant
errors. It does not have an iterative recycle stream calculation, which provides a check on user
input.

AMINECalc is limited to five single component solvents and one process configuration and will
have limited application. Out of the nine sites evaluated, three sites used a single component
solvent (MDEA), five sites used a multi-component solvent, and one site used a proprietary
amine solvent.

A comparison of AMINECalc, ProMax, and HYSYS showed that AMINECalc predicts the
lowest amount of VOC and BTEX emissions from the rich flash and acid gas streams and
HYSYS has the highest. ProMax predictions are in between AMINECalc and HYSYS. ProMax
predictions for total VOC and BTEX in the combined Rich Flash and Acid Gas streams are 3.3
and 3.7 times higher, respectively, than AMINECalc. HYSYS predictions for total VOC and
BTEX in the combined Rich Flash and Acid Gas streams are 9.7 and 9.0 times higher,
respectively, than AMINECalc.

The Aspen HYSYS regenerator H2S and CO2 predictions seem to be inconsistent with
AMINECalc and ProMax predictions. The laboratory gas sample analyses for this case did not
fall within expected ranges and should be reviewed for inconsistencies.

6 Recommendations
1) Develop standard data reporting requirements for amine units that provide more information
about details of plant operating conditions
a) Amine unit process configuration
b) Amine concentration
c) Amine circulation rates
d) Absorber lean and rich H2S and CO2 acid gas loadings
e) Absorber, flash, and regenerator temperatures and pressures

37
2) Better organization and labeling of laboratory gas sample analyses
3) Evaluate other sour gas stream compositions
4) Evaluate results generated by rigorous ProMax and HYSYS mass and heat transfer models

38
 References
“AMINECalc Version 1.0 User’s Manual,” Health and Environmental Safety Department, API
Publication Number 4679.

Duncan C, Diaz A, Bagajewicz M, “BTEX Removal from Natural Gas Streams.” The University
of Oklahoma, 2009.

IPCC, 2007: Climate Change 2007: Synthesis Report. Contribution of Working Groups I, II and
III to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Core
Writing Team, Pachauri, R.K and Reisinger, A. (eds.)]. IPCC, Geneva, Switzerland, 104 pp.
Accessed August 2019 at:
https://www.ipcc.ch/site/assets/uploads/2018/02/ar4_syr_full_report.pdf

McIntyre GD, Hernandez-Valencia VN, Lunsford KM. “Recent GPA Data Improves BTEX
Predictions for Amine Sweetening Facilities.” GPA Annual Convention Proceedings, 2001.
Skinner FD, Reif DL, Wilson AC, Evans JM, “Absorption of BTEX and Other Organics and
Distribution Between Natural Gas Sweetening Unit Streams.” SPE 37881 Society of Petroleum
Engineers, Presented at 1997 SPE/EPA Exploration and Production Environmental Conference,
Dallas, Texas, March 3-5, 1997.

39
 Appendix
This analysis compares the AMINECalc predictions for two amine treaters, S6-AS 400 (O-1) and
S6-AS 1100 (O-4), to the lab analysis of the streams exiting each treater on their way to the next
plant unit. As stated in the main body of the report (see Table 2), these amine treaters could not
be included in the simulator analyses because AMINECalc is unable to model the MDEA/PZ
amine blend used at this plant. The analysis in this appendix was performed to illustrate how
some limitations in the simulator models can lead to erroneous results when alternate inputs,
which are not representative of the actual process operating conditions, are used in the model.
These results should be not be used to extract any meaningful performance guidance but rather
as a caution about using the process simulator AMINECalc.

Assumptions
The inlet gas stream lab analysis provided was used as the input for the AMINECalc run for each
amine treater. The process operating conditions were obtained from output of a Promax
simulation. The following process conditions were obtained from this output:

Total gas stream to both units: 110 MMscf/day (this flow was split between the two amine
treaters, S6-AS 400 (O-1) – 30 MMscf/day and S6-AS 1100 (O-4) - 80 MMscf/day.

Since the actual MDEA/PZ amine blend could not be simulated and PZ is not an an amine option
in AMINECalc, MDEA was used and inputted on a mole basis substituting 2 moles of MDEA
per mole of PZ used in the blend since PZ absorbs 2 CO2 molecules per PZ mole while MDEA
is 1:1.

Summary of Process Conditions Used as Inputs in the AMINECalc Runs

Model: Gas Model

Amine: MDEA

Lean Amine Pressure: 849.700 [ psia ]

Lean Amine Temperature: 130.000 [ F ]

Lean Amine Flowrate: 360.000 [ gal/min ] for S6-AS 400 (O-1) treater
Lean Amine Flowrate: 990.000 [ gal/min ] for S6-AS 1100 (O-4) treater

Lean Amine Weight: 50.570 [ % ]

H2S Loading: 0.000 [ mol/mol ]
CO2 Loading: 0.014 [ mol/mol ]

Emission Control Efficiency 95.000

Operating Hours/Day: 24 [ hours/day ]
Operating Days/Year: 365 [ days/year ]

Gas Feed Pressure: 874.700 [ psia ]

40
Gas Feed Temperature: 120.000 [ F ]

Gas Feed Flowrate: 29.400 [ MMSCFD ] for S6-AS 400 (O-1) treater
Gas Feed Flowrate: 80.700 [ MMSCFD ] for S6-AS 1100 (O-4) treater

Number of Trays in Column: 20

Flash Tank Pressure: 114.696 [ psia ]

Inlet Gas Stream Composition (mole %)

H2S 0.00000 [ % ]
CO2 10.24400 [ % ]
MDEA 0.00000 [ % ]
H2O 0.00000 [ % ]
N2 2.12200 [ % ]
O2 0.00000 [ % ]
C1 70.21800 [ % ]
C2 9.12900 [ % ]
C3 5.57800 [ % ]
i-C4 0.43000 [ % ]
n-C4 1.34600 [ % ]
i-C5 0.28200 [ % ]
n-C5 0.32200 [ % ]
Hexanes 0.19700 [ % ]
Heptanes 0.09900 [ % ]
Octanes 0.02200 [ % ]
Nonanes 0.00200 [ % ]
C10+ 0.00000 [ % ]
MeSH 0.00000 [ % ]
EtSH 0.00000 [ % ]
Benzene 0.00600 [ % ]
Toluene 0.00300 [ % ]
Ethylbenzene 0.00000 [ % ]
Xylenes 0.00000 [ % ]
n-C6 0.00000 [ % ]
224Trimeth 0.00000 [ % ]

Analysis of Results

Table A-1 tabulates the results of the AMINECalc runs for the vent gas streams of the amine
treaters and the plant’s lab analysis of these two streams.

41
 Table A-1. Comparison of AMINECalc Results and Lab Analysis for Output Flows from
S6-AS 400 (O-1) and S6-AS 1100 (O-4) Amine Treaters

S6-AS 400 (O-1) S6-AS 1100 (O-4)

Lab Lab
Component AMINECalc Analysis Analysis AMINECalc Analysis Analysis
Provided Provided
lb/h Weight % Weight % lb/h Weight % Weight %
H2S 0.000 0.00 0.00 0.000 0.000 0.000
CO2 22.871 84.30 98.413 75.977 86.619 98.108
MDEA 0.000 0.00 - 0.001 0.001 -
H2O 0.171 0.63 - 0.504 0.575 -
N2 0.082 0.30 0.900 0.225 0.257 1.083
O2 0.00 0.00 - 0.00 0.00 -
C1 2.797 10.31 0.239 7.687 8.764 0.106
C2 0.655 2.41 0.388 1.799 2.051 0.500
C3 0.489 1.80 0.021 1.339 1.527 0.028
i-C4 0.006 0.02 NIL 0.017 0.019 0.002
n-C4 0.019 0.07 0.007 0.052 0.059 0.011
i-C5 0.007 0.03 NIL 0.019 0.022 0.002
n-C5 0.008 0.03 NIL 0.022 0.025 0.002
Hexanes 0.009 0.03 0.003 0.026 0.030 0.010
Heptanes 0.005 0.02 0.001 0.013 0.015 0.007
Octanes 0.001 0.00 NIL 0.002 0.002 0.006
Nonanes 0.000 0.00 NIL 0.000 0.000 0.012
C10+ 0.000 0.00 0.001 0.000 0.00 0.040
MeSH 0.000 0.00 - 0.000 0.00 -
EtSH 0.000 0.00 - 0.000 0.00 -
Benzene 0.007 0.03 0.020 0.020 0.023 0.052
Toluene 0.004 0.01 0.006 0.011 0.013 0.018
Ethylbenzene 0.00 0.00 NIL 0.000 0.00 NIL
Xylenes 0.00 0.00 NIL 0.000 0.00 0.011
n-C6 0.00 0.00 0.001 0.000 0.00 0.002
224Trimethylp
0.00 0.00 - 0.000 0.00 -
entane
Total: 27.131 100.00 100.000 87.714 100.000 100.000

It should be pointed out that the vent gas streams for these two units do not vent directly to the
atmosphere and are routed to a thermal oxidizer (S6-AS 400 (O-1)) or a regenerator. If they
were, emission estimates for these two units would be based on the AMINECalc predictions in
Table A-1.

42
Less CO2
AMINECalc predicts the quantity of CO2 in the stream to be significantly less than found in the
lab analysis (approximately 85% vs 98%). Since the primary purpose of these units is removal of
CO2, this error could lead to overdesign of the system. Typically, piperazine is added as
promoter to enhance CO2 absorption and is most likely the cause of this discrepancy.

More C1 (Methane)
AMINECalc predicts 43 (10.31/0.239) to 83 times more methane than found in the lab analysis.
While methane is not considered a VOC for regulatory purposes, it is considered a greenhouse
gas, with a warming potential more than 25 times greater than CO2 over a 100-year period (IPCC
2007). Such levels of methane emissions may raise concerns if these estimates were predicted to
be emitted.

Discussion of Results
In examining the output from AMINECalc, it is clear that the under estimation of CO2 in the
stream is the result of using the incorrect amine solution because AMINECalc cannot model the
amine blend that is actually used at the plant. This is a significant limitation of this model
considering that this and other blends are used quite frequently. In this analysis, we had the
advantage of knowing the actual stream composition. Without the actual stream compositions, as
might be the case before equipment is installed, the magnitude of the erroneous predictions and
components in the stream that are incorrectly estimated or possibly omitted are unknown.
Therefore, this software model should be used with great caution in these applications.

43