Getting the Most Out of Your Sulfur Recovery Unit

Performance Test
Richard J. Wissbaum
Technology Director
URS – Energy & Construction

Michael Anderson
Grand Pooh-bah
Brimstone STS Limited

Presented at the 2012 Brimstone Sulfur Recovery Symposium

Vail, Colorado, September 11 – 14, 2012

ABSTRACT

Measuring the performance of a sulfur recovery unit is a difficult task. It requires special
sampling techniques, special sample handling techniques, and special analytical techniques.
(This is why there are only a few companies in the world who perform this work.) It should,
therefore, come as no surprise that special techniques are also required to analyze the raw data to
obtain a clear snapshot of the performance of the facility.

Because performance measurement is so difficult (that is, expensive), most companies obtain test
data only on an as-needed basis. Therefore, it is important to extract the maximum amount of
information from every performance test report. The purpose of this paper is to provide the
facility engineer a few insights and simple tools to aid in that effort.

In addition, we will examine a few examples – taken from actual performance test reports –
illustrating the benefits of an independent analysis of the test results.

DISCLAIMER
It is NOT the purpose of this paper to question the results reported by any of the various
companies who conduct performance tests on sulfur recovery facilities. The reports provided by
these companies are consistently high in quality and beneficial to the user. However, as
engineers it is our job to collect and analyze data and to form our own conclusions based on that
data. The methods presented in this paper are intended to allow the facility engineer to perform
his or her own analysis and to reach independent conclusions. Often, those conclusions will
agree with the official report; occasionally, they may not agree. In either case, the
understanding of the actual performance of the facility will be improved.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 2 
 
INTRODUCTION

Performance test reports often contain 50 – 100 pages, and even longer reports are commonly
encountered. These reports are packed with raw data, analyzed data, general discussion and
specific conclusions. It takes a considerable amount of effort to understand, and make use of, all
of the information provided is these reports. Unfortunately, pressures of time and workload can
result in only a cursory review of these reports. The process engineer assigned to the SRU
(among his or her many other tasks) may have time to (a) read the Executive Summary and (b)
scan the report and take note of items highlighted in bold text. (You know who you are!)

However, these reports contain significantly more information than can be summarized and
understood quickly. A thorough review of the report, including some simple analysis of the raw
data and understanding the reasoning behind the report’s conclusions and recommendations, can
lead to an improved understanding of the unit performance. It can also greatly increase the
benefits obtained from the performance test work.

Performance tests vary widely in their complexity. Some very simple tests – or “front-to-back”
tests – consist of nothing more than acid gas and incinerator stack gas (or, alternately, SRU tail
gas) analysis. These tests are performed simply to estimate sulfur recovery efficiency on an
overall unit basis. Similar limited tests might be performed to determine extent of destruction of
impurities (BTEX, ammonia, etc.) or formation of COS and CS2. Full performance tests can
include sampling of every intermediate in the facility to allow evaluation of the performance of
every reactor, reheater, condenser in the SRU (and, if present, the TGU).

This paper will focus on the analysis of overall unit (as opposed to stage-by-stage) performance:
either the SRU, or the SRU plus TGU. Since most performance test data provides incinerator
stack gas composition, the incinerator is almost always included when analyzing the overall
performance; however, this should not be taken to mean that the incinerator is the most important
part of the unit. (In fact, the presence of the incinerator both complicates and simplifies the
analysis, as we will see.)
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 3 
 
PART 1 – ANALYTICAL METHODS

Calculation of Sulfur Recovery Efficiency by the Carbon Balance Method

The Carbon Balance method – also called the C/S ratio method – compares the relative amounts
of carbon and sulfur in the process stream as sulfur is removed (recovered) from the process.
Surprisingly little information is required to calculate a good estimate of sulfur recovery
efficiency. The equation is:

Efficiency = 1.0 – (Sd/Sa) · (Ca/Cd + Qf/Qa · Cf/Cd) + Qf/Qa · Sf/Sa

Where:1
Q is the flow rate of the stream (in any consistent molar units);
S is the sum of the sulfur atoms in the stream;
C is the sum of the carbon atoms in the stream;
The subscript ‘a’ refers to the combined acid gas stream;
The subscript ‘f’ refers to the combined fuel gas stream;
The subscript ‘d’ refers to the downstream effluent.

Example: Sulfur recovery unit ABC has two feeds: amine acid gas and SWS acid gas. Stream
flow rates, compositions and conditions are given in the following table. Estimate the sulfur
recovery using the carbon balance method.

  Amine Acid Gas SWS Acid Gas Fuel Gas  Stack Gas

Hydrogen    1.005
Argon    1.018
Oxygen    2.559
Nitrogen  1.227  85.081
Methane  0.014 0.014 95.911  0.027
Carbon Monoxide    0.641
Carbon Dioxide  17.840 6.292 0.688  8.924
Ethylene  0.031 0.036  
Ethane  0.013 0.006 2.048 
Hydrogen Sulfide  81.827 44.880  
Carbonyl Sulfide  0.004 0.022  
Propane  0.143 0.134 0.097 
Sulfur Dioxide    0.745
Butanes  0.041 0.129 0.022 
Pentanes  0.065 0.613 0.007 
Hexanes  0.022 0.492  
Ammonia  47.382  
TOTAL  100.000 100.000 100.000  100.000
   
Temperature, F  90 183  
Pressure, psig  25.02 25.22  
Flow, SCFH  221,100 34,925 16,400 
                                                            
1
   This nomenclature is consistent with Paskall and Sames [1]. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 4 
 

Step 1:
Since flow rates are measured on a total basis (i.e. wet), we must first convert the acid gas
compositions to wet basis, assuming the partial pressure of water in each stream is equal to the
vapor pressure of water at the stream temperature. At the same time, we normalize the
compositions. The fuel gas stream at this facility is dry.

Step 2:
Because the carbon balance method allows only one acid gas stream, we must blend the two acid
gas feed streams into a combined acid gas stream, based on their relative flow rates and
individual compositions.

The table below shows the results of steps 1 and 2.

  Amine Acid Gas SWS Acid Gas Total Acid Gas 

Hydrogen   
Argon   
Oxygen   
Nitrogen   
Methane  0.014 0.010 0.013 
Carbon Monoxide   
Carbon Dioxide  17.345 4.296 15.565 
Ethylene  0.030 0.025 0.029 
Ethane  0.013 0.004 0.011 
Hydrogen Sulfide  79.555 30.646 72.883 
Carbonyl Sulfide  0.004 0.015 0.005 
Propane  0.139 0.092 0.133 
Sulfur Dioxide   
Butanes  0.040 0.088 0.046 
Pentanes  0.063 0.419 0.112 
Hexanes  0.021 0.336 0.064 
Ammonia  32.354 4.414 
Water  2.776 31.716 6.724 
TOTAL  100.000 100.000 100.000 
   
Flow Rate, SCFH  221,100 34,925 256,025 

Step 3:
Now compute the carbon and sulfur atom sums for acid gas, fuel gas, and stack gas. These sums
are shown in the table on the next page.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 5 
 

  Total Acid Gas Fuel Gas Stack Gas 

Hydrogen  1.005 
Argon  1.018 
Oxygen  2.559 
Nitrogen  1.227 85.081 
Methane  0.013 95.911 0.027 
Carbon Monoxide  0.641 
Carbon Dioxide  15.565 0.688 8.924 
Ethylene  0.029  
Ethane  0.011 2.048  
Hydrogen Sulfide  72.883  
Carbonyl Sulfide  0.005  
Propane  0.133 0.097  
Sulfur Dioxide  0.745 
Butanes  0.046 0.022  
Pentanes  0.112 0.007  
Hexanes  0.064  
Ammonia  4.414  
Water  6.724  
   
Carbon Sum  0.1719 1.0111 0.0959 
Sulfur Sum  0.7289 0.0000 0.0075 

Step 4:
Now compute the recovery efficiency using the formula.2

Efficiency = 1.0 – (/) · (/ + 16400/256025 · /) +

16400/256025 · 0.0000/0.7289

Efficiency = 0.9748, or 97.48% sulfur recovery

Comments on the Method

Note that this method does not require measurement of either stack gas flow, or sulfur product
flow.

Note also that although we converted the acid gas and fuel gas streams to a wet basis (although
the wet basis fuel composition in this example contained no water), we did not convert the stack
gas composition to a wet basis. This apparent inconsistency is allowable, as demonstrated in the
derivation of the formula in the next section.

The derivation will also illustrate the inaccuracies in this method, namely: (1) this method
ignores the CO2 content of the combustion air (normally about 390 ppm, or 0.0004 mole
fraction), and (2) this method assumes that none of the sulfur contained in the fuel is recovered
                                                            
2
   Note that we use volumetric flow (in SCFH) instead of molar flow. Since this is a low pressure system, the gas is 
nearly ideal, and volumetric flow is related to molar flow by a constant (379.79 SCF/lb∙mol in English units.) 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 6 
 
(which would be true if the only fuel use is in the incinerator). These assumptions mean that the
calculated recovery will be inaccurate (although usually in just the fourth decimal place.)

Derivation of the Method

Assumptions:

1. One acid gas stream

2. One fuel gas stream
3. Ignore carbon in the combustion air
4. Assume no recovery of sulfur in fuel is possible

Define the following streams:

a is the acid gas stream, molar flow rate Qa

f is the fuel gas stream, molar flow rate Qf
d is the downstream effluent (e.g. stack gas) with unknown molar flow rate

Define the following terms:

The carbon sum (denoted C) is the sum, over all components in a stream, of the mole fraction
of the component times the number of carbon atoms in that component.

The sulfur sum (denoted S) is the sum, over all components in a stream, of the mole fraction of
the component times the number of sulfur atoms in that component.

We can now make the following statements:

Atoms of Carbon entering the process:3 Qa · Ca + Qf · Cf

Atoms of Sulfur entering the process:3 Qa · Sa + Qf · Sf
Atoms of Carbon in the effluent:4 Qa · Ca + Qf · Cf = Qd · Cd
Moles of dry gas in the effluent (Qd): (Qa · Ca + Qf · Cf ) / Cd
Atoms of Sulfur in the effluent: Sd · (Qa · Ca + Qf · Cf ) / Cd

Efficiency = 1 - (Atoms S in effluent – Atoms S in fuel) / (Atoms S in Acid Gas)

= 1 - (Atoms S in effluent) + (Atoms S in fuel)

(Atoms S in Acid Gas) (Atoms S in Acid Gas)

= 1 - Sd · (Qa · Ca + Qf · Cf ) + Qf · Sf

Cd · Qa · Sa Qa · Sa

                                                            
3
   Since flow rates are measured on a total (i.e. wet basis), the atom sums must be calculated on a wet basis. 
4
   Since there is no carbon or sulfur in water, the right hand side of the equation can be on a dry (i.e. water free) 
basis. This allows us to use the water free sample analysis. The calculated flow rate, Qd, is on a water free basis. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 7 
 
= 1 - Sd · (Ca + Qf · Cf ) + Qf · Sf
Sa (Cd Qa · Cd) Qa · Sa

Calculation of Sulfur Recovery by the Analytical Flow Ratio Method

There is another method of calculating sulfur recovery which does not require the simplifying
assumptions of the previous method, and which yields additional useful information as well. This
method, which was developed by Harold Paskall, is called the Analytical Flow Ratio method, or
AFR.

The AFR method is based on atom balances around a generic sulfur recovery facility. A
schematic of the generic facility is shown in Figure 1.

Figure 1
Generic Sulfur Recovery Facility

ACID GAS (1) DRY EFF (8) WET EFF (8+5)

PARTIAL OR
FUEL GAS (2) WATER (5)
COMPLETE SULFUR
AIR (3) PLANT

SULFUR (6)

We can write five atom balances around this generic facility – one each for carbon, hydrogen,
oxygen, nitrogen and sulfur. We then have the following system of equations:

Q1·C1 + Q2·C2 + Q3·C3 = Q5·C5 + Q6·C6 + Q8·C8

Q1·H1 + Q2·H2 + Q3·H3 = Q5·H5 + Q6·H6 + Q8·H8
Q1·O1 + Q2·O2 + Q3·O3 = Q5·O5 + Q6·O6 + Q8·O8
Q1·N1 + Q2·N2 + Q3·N3 = Q5·N5 + Q6·N6 + Q8·N8
Q1·S1 + Q2·S2 + Q3·S3 = Q5·S5 + Q6·S6 + Q8·S8

The compositions (and therefore the atom sums) of air (stream 3), water (stream 5) and sulfur
(stream 6) are all known. The compositions (and therefore the atom sums) of acid gas (stream 1),
fuel gas (stream 2) and dry effluent (stream 8) are analyzed (although we must correct the
compositions of acid gas and fuel gas to account for water, as before). Finally, Q1 and Q2 are
known. The remaining unknowns are: Q3 (often unknown because many facilities have a natural
draft incinerator), Q5, Q6 and Q8. We have a system of five equations with only four unknowns.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 8 
 
Since we have more equations than unknowns, we can solve this system in either of two ways.
First, we can ignore the known flow rate of fuel gas and calculate the fuel gas flow required to
satisfy all five equations. This is called a Type I AFR.

Alternately, we can ignore the nitrogen balance equation, solve for the unknown variables, and
check the error in the nitrogen balance using the solution. This is called a Type II AFR.

Example:

Prepare a Type I and a Type II AFR balance using the data from the previous example.

Steps 1 and 2 are the same as before: convert the acid gas and fuel gas stream compositions to
wet basis and blend the acid gas feeds into a single stream.

Step 3:
Compute all five atom sums – carbon, hydrogen, oxygen, nitrogen and sulfur. The results are
shown in the table below. (The composition of air has been converted to a wet basis using
ambient temperature and humidity.)

  Total Acid Gas Fuel Gas Air  Stack Gas

Hydrogen    1.005
Argon  0.929  1.018
Oxygen  20.819  2.559
Nitrogen  1.227 77.612  85.081
Methane  0.013 95.911   0.027
Carbon Monoxide  0.033  0.641
Carbon Dioxide  15.565 0.688   8.924
Ethylene  0.029  
Ethane  0.011 2.048  
Hydrogen Sulfide  72.883  
Carbonyl Sulfide  0.005  
Propane  0.133 0.097  
Sulfur Dioxide    0.745
Butanes  0.046 0.022  
Pentanes  0.112 0.007  
Hexanes  0.064  
Ammonia  4.414  
Water  6.724 0.607 
   
Carbon Sum  0.1719 1.0111 0.0003  0.0959
Hydrogen Sum  1.7646 3.9701 0.0121  0.0212
Oxygen Sum  0.3786 0.0138 0.4231  0.2510
Sulfur Sum  0.7289 0.0000 0.0000  0.0075
Nitrogen Sum  0.0441 0.0245 1.5522  1.7016
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 9 
 
Step 4:
Formulate the five atom balances for a Type I AFR, grouping the unknown terms on the left side
of the equation and the known terms on the right side of the equation, and eliminating terms with
coefficients equal to zero:

Carbon: -1.0111·Q2 – 0.0003·Q3 + 0.0959·Q8 = 256025·0.1719

Hydrogen: -3.9701·Q2 – 0.0121·Q3 + 2.0000·Q5 + 0.0212·Q8 = 256025·1.7646
Oxygen: -0.0138·Q2 – 0.4231·Q3 + 1.0000·Q5 + 0.2510·Q8 = 256025·0.3786
Sulfur: -0.0000·Q2 + 1.0000·Q6 + 0.0075·Q8 = 256025·0.7289
Nitrogen: -0.0245·Q2 – 1.5522·Q3 + 1.7016·Q8 = 256025·0.0441

After considerable manipulation (not for the faint hearted!) we arrive at the following result:5

Q2 = 101,655
Q3 = 1,675,188
Q5 = 421,589
Q6 = 175,169 (which is the ideal gas equivalent of the molar flow rate, 461.58 lb·mol/hr.)
Q8 = 1,536,255

Comparing the calculated fuel gas volumetric rate (Q2) to the reported fuel gas rate of 16,400, we
can see that there is a significant source of error in the data. Unfortunately, AFR does not tell us
where the error lies – it only points out the existence and approximate magnitude of the error.
We must use a different approach to try to determine where the error lies. 

Step 5:
Formulate the four atom balances for a Type II AFR, again grouping the unknown terms on the
left side of the equation and known terms on the right side, and eliminating terms with
coefficients equal to zero:

Carbon: – 0.0003·Q3 + 0.0959·Q8 = 256025·0.1719 + 16400·1.0111

Hydrogen: – 0.0121·Q3 + 2.0000·Q5 + 0.0212·Q8 = 256025·1.7646 + 16400·3.9701
Oxygen: – 0.4231·Q3 + 1.0000·Q5 + 0.2510·Q8 = 256025·0.3786 + 16400·0.0138
Sulfur: + 1.0000·Q6 + 0.0075·Q8 = 256025·0.7289 + 16400·0.0000

Solving the system of equations as before, we arrive at the following result:

Q3 = 752,384
Q5 = 256,297
Q6 = 181,888 (which is the ideal gas equivalent of the molar flow rate, 479.28 lb·mol/hr.)
Q8 = 634,365

                                                            
5
   It turns out that the matrix is less prone to accumulated roundoff errors if we divide all equations by Q1. In 
actuality, we are solving for Q2/Q1, Q3/Q1, etc. Thus the name Analytical Flow Ratio. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 10 
 
Substituting these values into the nitrogen balance equation gives the following results:

N in: 3107.18 lb·mol/hr

N out: 2844.40 lb·mol/hr
Error: 8.5 percent

This is a more reasonable result. The calculated air flow of 752,000 SCFH compares well with
the measured air flow (SRU + Incinerator) of 784,600 SCFH.

Knowing molar flows of all streams, we can now calculate sulfur recovery efficiency very easily:

Type I AFR: Sulfur in = 0.7289·256025/379.5 = 491.74

Sulfur out = 461.58
Recovery = 461.58 / 491.74 = 93.87 percent

Type II AFR: Sulfur in = 0.7289·256025/379.5 = 491.74

Sulfur out = 479.28
Recovery = 479.28 / 491.74 = 97.47 percent

Note that the Type II AFR recovery matches the carbon balance recovery very closely. This is
because the carbon balance method used the measured fuel gas flow rate.

Comments on the Method

The AFR method provides not only a more accurate calculation of sulfur recovery, but also an
indication of the consistency of the data. As seen above, use of the carbon balance method will
provide an estimate of recovery efficiency, but will not expose any problems that may exist in
the data.

The AFR method is easily extended to account for different feed streams such as external
hydrogen to the TGU, or fuel gas streams of different composition. The composition and flow
rates of these additional streams must be known; this will simply be an additional contribution to
the right hand side of the equations.

So far, we have focused only on overall performance. But thorough performance testing – which
includes compositions of the process stream throughout the unit – provides enough data to
perform stage-by-stage AFR balances, calculating required air flow at each point in the process.
Since each stage of the Claus unit can be compared to the previous stage, the calculated air flows
should be consistent. This lends considerable credence to the data set as a whole.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 11 
 
PART 2 – SOFTWARE TOOLS

As noted above, solution of five simultaneous equations by manual methods is not a task to be
undertaken lightly. Therefore, Brimstone and URS have collaborated to make an Excel
spreadsheet available which will automate most of the process. The spreadsheet is available in
two versions – one for English units and one for metric units.6

DISCLAIMER: The spreadsheets described below have been developed and verified with the
level of care customary within the industry. However, neither the Author, nor URS Corporation,
nor Brimstone STS Ltd. assume any liability whatsoever for any errors contained within the
spreadsheet, nor for any misuse of the spreadsheet.

The spreadsheet contains Visual Basic code which solves the simultaneous equations. Therefore,
Excel will do one of the following when you open the spreadsheet: (a) it might silently disable
all Visual Basic code, rendering the spreadsheet non-functional, or (b) it might prompt you with
an unobtrusive warning, like this:

If you plan to use the spreadsheet routinely, you should copy it into a separate folder, and
designate all files within that folder as trusted. This will cause Excel to open the spreadsheet with
full macro functionality every time.

The spreadsheet contains six worksheets, as follows:

Air Composition Which allows you to enter air conditions of ambient temperature, pressure
and relative humidity.
Stream Analyses Which allows you to enter analytical data, normalize the data, and add
water to saturate acid gas streams.
Recoveries Which summarizes sulfur recovery by the carbon balance method and by
both AFR methods. This sheet also provides the command button to solve
the AFR matrices.

                                                            
6
   Scholars of engineering have been known to disagree violently about what constitutes a “metric” set of units. I 
refuse to enter into this debate. If the units provided are not suitable, you may easily change to different units. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 12 
 
AFR Matrix Which collects the matrix coefficients for both the Type I and Type II
AFR methods and stores the solutions. DO NOT insert or delete any cells,
columns or rows in this sheet. The Visual Basic macros read and write to
specific row/column locations on this sheet.
Type I Balance Which presents the results of the Type I AFR balance, along with
calculated recovery efficiency and fuel gas flow error.
Type II Balance Which presents the results of the Type II AFR balance, along with
calculated recovery efficiency and nitrogen balance error.

The spreadsheets are not protected in any way: you may insert or delete rows, columns and cells
(however, you are strongly advised not to do so: the Visual Basic code reads and writes cell
contents by absolute location; shifting cell locations can cause the spreadsheet to stop
functioning properly); you may modify formulas; you may even view and modify the Visual
Basic code. However, this is quite a complicated spreadsheet and I do not recommend making
changes unless you fully understand the workings of the spreadsheet.

Values in cells are color coded: cells colored in dark blue text contain input values – feel free to
change these values as desired. Cells colored in brown text contain default values which should
be good for most situations – change these values if appropriate. Cells colored in black text
contain the results of calculations – change these cells only if absolutely necessary.

The Air Composition Worksheet

This sheet provides the analysis of all combustion air streams. You should enter values for
atmospheric pressure, ambient temperature and relative humidity. The spreadsheet will
automatically estimate the vapor pressure of water based on ambient air temperature, correct that
vapor pressure for relative humidity, and calculate the wet basis composition. The air
composition is only used for AFR calculations, so you need not modify this worksheet at all if
you are not performing an AFR analysis.

Water vapor pressure is calculated by the IAPWS-97 engineering and scientific formulation. The
formulation provided by IAPWS requires temperature in Kelvin and provides vapor pressure in
MPa. The routines built into the worksheets have built-in units conversion. The English version
assumes the input temperature is in degrees F and converts the output value to psia. The metric
version assumes the input temperature is in degrees C and converts the output value to kPa.

The Stream Analyses Worksheet

This worksheet is used to enter the analytical data from the test program. Space is provided to
enter the sample date and time to avoid confusion. Space is provided to enter two different fuel
compositions (some facilities use different fuel in the SRU/TGU than in the incinerator) and to
enter both tail gas (i.e. effluent from the SRU, or even a process stream somewhere within the
SRU) and stack gas compositions.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 13 
 
This worksheet also saturates the acid gas streams based on stream temperature, pressure, and
calculated water vapor pressure (calculated as described above). The worksheet also normalizes
all compositions.

The Recoveries Worksheet

This worksheet is used to enter stream flow rates. Volumetric flow rates are converted to molar
flow rates – the calculated molar flow rates are used as the Qn coefficients in all calculations.

This worksheet also computes all atom sums used in both the carbon balance method and in the
AFR methods.

Sulfur recovery by the carbon balance method is calculated based on the tail gas composition (if
provided) and on the stack gas composition (if provided).

Sulfur recovery by both AFR methods is also shown on this worksheet for comparison with the
recoveries calculated by carbon balance. The values shown are not updated automatically (the
matrix solution is only performed when you click the “Solve” button). The spreadsheet
automatically prepares AFR balances for both the tail gas composition or the stack gas
composition, unless one or the other is missing. Note that a Type I AFR balance is not provided
based on tail gas composition.7

The AFR Matrix Worksheet

This worksheet is provided to allow you to examine the AFR matrix and the solutions.

The coefficients for the Type I matrix (using stack gas) are in cells C7 through G11; the RHS for
the Type I matrix is in cells H7 through H11. The solution vector is in cells C16 through G16.

The coefficients for the Type II matrix (using stack gas) are in cells D7 through G10; the RHS
for the Type II matrix is in cells I7 through I10. The solution vector is in cells D22 through G22.

The coefficients for the modified Type II matrix (using tail gas) are in cells D30 through G33;
the RHS for this matrix is in cells I30 through I33. The solution vector is in cells D38 through
G38.

Checks of the solution of the system of equations are provided in columns J and K: these values
should all be zero. If there is a non-zero value, chances are you have changed the input and not
yet clicked the “Solve” button on the Recoveries worksheet.8

                                                            
7
   This is because the Type I AFR calculates the fuel gas flow rate; but since any fuel burned in the SRU or TGU is 
included as “SRU Fuel Gas”, it is blended into the combined acid gas feed stream and sulfur contained in this fuel 
is counted in the recovery calculation. 
8
   If, for example, a tail gas composition is not provided, the spreadsheet will not attempt to solve the Type II 
matrix using tail gas as stream 8. In that case, the solution check values for that matrix will almost certainly be 
non‐zero. These are “leftover” values and may safely be ignored. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 14 
 
The Type I Balance Worksheet

This worksheet presents a stream-by-stream mole balance based on the Type I AFR solution.
Since this solution forces all atom balances, this tabulation will provide an overall mass balance.
However, the fuel gas flow will vary from the measured fuel gas flow by the indicated error.

The Type II Balance Worksheet

 
This worksheet presents stream-by-stream mole balances based on the Type II AFR solution.
Note that this tabulation may not provide an overall mass balance. The calculated error in the
mass balance is shown on this sheet.

One balance is provided based on stack gas analysis; the other balance is provided based on tail
gas analysis. If you do not provide one of the analyses, the results shown for that case will be
meaningless. The balances also report the nitrogen balance error (in the case of stack gas
analysis) and hydrogen balance error (in the case of tail gas analysis.)9

                                                            
9
   I have found that discarding the hydrogen balance equation tends to provide overall better results in the case of 
Type II AFRs based on tail gas analyses. Small analytical errors resulting from the difficulty of quantifying the 
various sulfur species in SRU tail gas tend to magnify in the solution algorithm, leading to wildly inaccurate sulfur 
product stream flow rates. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 15 
 
PART 3 – REAL-WORLD EXAMPLES

NOTE: The following examples have been taken from actual performance test reports prepared
by sulfur testing companies. The analytical data are unchanged, and any quotes from the test
report are verbatim. However, the stream rates have been scaled – sometimes up, and sometimes
down – to avoid any possibility of identifying the facility under discussion.

Example 1: Refinery SRU Performance Test

The following analytical data were reported (zero values omitted for clarity):

  Acid Gas SRU Tail Gas Incin Fuel Gas  Stack Gas

Hydrogen  2.095 37.792 
Argon  0.944   0.976
Oxygen    7.882
Nitrogen  0.047 78.904 6.828  81.623
Methane  0.194 26.621 
Carbon Monoxide  1.634 1.838  0.083
Carbon Dioxide  29.811 16.232 0.289  9.262
Ethane  0.260 20.770 
Hydrogen Sulfide  68.057 0.144  
Carbonyl Sulfide  0.004 0.003  
Propane  0.765 3.507 
Sulfur Dioxide  0.036   0.173
Carbon Disulfide  0.007  
Butane  0.303 1.343 
Pentane  0.045 1.012 
Hexane  0.074  
Benzene  0.055  
Ammonia  0.386  
   
Temperature, F  147  
Pressure, Psia  24.7  
Flow, SCFH  241,200  

Reported recovery based on the tail gas analysis was 99.16% and recovery based on the stack gas
analysis was 98.84%. Ambient air temperature was 52 °F.

The report also noted the following:

1. Based on process simulator results, the measured SRU combustion air rate of 544,000
SCFH was estimated to be about 30% high;
2. Based on process simulator results, the measured SRU furnace temperature was estimated
to be about 250 °F low;
3. Based on process simulation to match the measured incinerator temperature, the
measured fuel gas flow to the incinerator was estimated to be about 50% high, and the
measured air flow to the incinerator was estimated to be about 15% high.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 16 
 

By entering analytical data and ambient conditions into the spreadsheet, the following results are
calculated (see Example1.xls for additional detail):

Recovery based on tail gas analysis: 99.43% (99.16% was reported)

Recovery based on stack gas analysis: 98.58% (98.84% was reported)

The Type II AFR balances have mass balance errors on the order of 0.1 percent. This tends to
confirm the validity of the raw data.

The Type I AFR balance shows a fuel gas flow error of -9 percent; that is, the calculated fuel gas
flow is 9% higher than measured. The report indicated the calculated fuel flow was 30% lower
than measured.

The Type II AFR balance based on SRU tail gas calculates an SRU combustion air flow of
414,000 SCFH – about 25% less than measured. This is consistent with the report.

Comparing the Type II AFR balances based on stack gas and on tail gas allows us to infer an
incinerator air flow rate of about 790,000 SCFH. Measured total air flow was about 760,000
SCFH. This seems to confirm the measured flow rate.

Blais et. al. [3] noted that reaction furnace heat loss effects can be significant, especially in
smaller units or in units operating at extreme turndown. It seems likely that the report assumed
optimistically low heat losses from the incinerator, leading to lower calculated fuel and air flow
rates to achieve the measured temperature. (Heat loss effects in the incinerator can be huge and
must be thoroughly understood.) This would lead to an erroneous conclusion that measured
flows were too high. See the table below.

Comparison of Measured and Calculated Incinerator Air and Fuel Flows

  Measured By AFR Reported
Fuel Gas Flow, SCFH  38,500 42,000 25,500
Incinerator Air Flow, SCFH  760,000 790,000 660,000
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 17 
 
Example 2: Gas Plant SRU/TGU Performance Test

The following analytical data were reported (zero values omitted for clarity):

  Combined Acid  SRU Tail Gas TGU Recycle  Incin Fuel Gas  Stack Gas

Gas  Gas 
Hydrogen    2.971   0.389
Argon    1.027   1.050
Oxygen      2.116
Nitrogen    85.865 0.136 1.144  87.850
Methane  1.033  97.816  0.057
Carbon Monoxide    1.199   0.102
Carbon Dioxide  13.325  7.982 43.277 1.013  8.407
Ethane    0.026 
Hydrogen Sulfide  85.576  0.438 56.586  
Carbonyl Sulfide  0.066  0.119  
Propane    0.011 
Sulfur Dioxide    0.355   0.027
Carbon Disulfide    0.044  
     
Temperature, F  103  120  
Pressure, Psia  27.8  26.8  
Flow, SCFH  378,800   

Reported recovery of the SRU was 97.0% and recovery of the SRU+TGU was 99.93%. Ambient
air temperature was 33 °F.

Note that neither fuel gas flow nor recycle gas flow was available. (Where possible, testing
protocols should include recording both fresh acid gas flow and combined acid gas flow in such
cases, to allow a reasonable estimate of recycle gas flow.) Lacking both the fuel gas and the
recycle gas flow rates makes analysis of the data difficult. There are three possible strategies to
employ:

1. Use a calculated fuel gas flow, either from the report or from a separate incinerator
simulation, and use a Type I AFR to calculate the TGU recycle flow which satisfies all
atom balances. There are two disadvantages to this strategy: (1) as seen in Example 1,
fuel gas flows calculated by simulation can be very error prone if incinerator heat loss
effects are significant; and (2) the spreadsheet model is not configured to allow
calculation of the TGU recycle flow by AFR. (However, this modification is possible for
a person skilled in Excel.)
2. Assume a TGU recycle flow rate and perform a Type I AFR to calculate the fuel gas
flow. Adjust the assumed recycle flow rate until a satisfactory nitrogen balance is
achieved using the Type II AFR. The disadvantage to this strategy is that the recycle
stream is such a small fraction of the overall mass balance that the results of the Type II
AFR balance are very insensitive to the recycle flow rate. If the data is not very
consistent, a wildly unlikely flow rate might be required to achieve overall atom
balances.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 18 
 
3. Use the reported recoveries for the SRU and for the STU+TGU to estimate the recycle
gas flow rate. This strategy has the disadvantage that it will not be possible to arrive at an
independent check on the SRU+TGU combined recovery. (It will be possible to check the
SRU recovery using the tail gas analysis.) However, this is almost always the best
strategy to follow.

Using strategy 3, we estimate TGU recycle flow using the following procedure:

A. Calculate the fractions of combined H2S feed contributed by acid gas and recycle gas as
follows:

Acid gas fraction = 1.0 / (0.9993 / 0.970) = 97.07%

Recycle gas fraction = 100 – 97.07 = 3.03%

B. Using the spreadsheet, determine number of moles of H2S in combined acid gas feed:

Combined feed molar flow (wet basis) = 378800 / 379.79 = 997.39 lb·mol/hr
Combined feed H2S concentration (wet basis) = 0.82374
Moles H2S in feed = 997.39 · 0.82374 = 821.59 lb·mol/hr

C. Now calculate molar flow of TGU recycle gas:

TGU Recycle H2S concentration (wet basis) = 0.53005

TGU Recycle molar flow rate = 821.59 · 0.0303 / 0.53005 = 47.0 lb·mol/hr

Now use the calculated flow of 47 lb·mol/hr (or 17,850 SCFH) to calculate the fuel gas flow
using the Type I AFR. The calculated flow is 76,200 SCFH, or 200.6 lb·mol/hr. The Type II
AFR nitrogen balance error and the mass balance error are tabulated below for this case (and for
±20% cases, to demonstrate the insensitivity to recycle flow rate) in the table below.

Type II AFR Results at Varying TGU Recycle Flow Rates

Flow Rate, SCFH  Fuel Flow, SCFH N2 Balance Error Mass Balance Error
14,300  71,400 0.00 0.02
17,850  76,200 ‐0.01 0.02
21,400  81,100 0.00 0.02

The report calculated a fuel gas firing rate of 11,400 SCFH – 15% of the rate calculated by the
Type I AFR. This large discrepancy could indicate some inconsistencies in the data. The fuel gas
rate should be checked against the data sheet or against a simulation. (Using the reported fuel gas
rate results in a -20% nitrogen balance error and a 10% mass balance error.)

Based on the SRU tail gas analysis, the spreadsheet calculates SRU recovery at 98.2% (versus
97.0% reported). The overall SRU+TGU recovery is 99.88% (versus 99.93% reported.)
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 19 
 
Example 3: When Data Goes Wild

If the performance test data is inaccurate or inconsistent, we might obtain some very surprising
results. Consider the following example:

The performance test of a sub-dewpoint sulfur recovery unit reported the following analytical
data (zero values omitted for clarity):

  Amine Acid Gas SWS Acid Gas Fuel Gas  Stack Gas

Hydrogen  51.84 
Argon    1.05
Oxygen    2.63
Nitrogen  3.77 2.55  87.65
Methane  0.02 0.02 30.51 
Carbon Monoxide  0.01 0.02   4.51
Carbon Dioxide  1.80 0.32 0.32  3.98
Ethylene  10.98 
Ethane  0.03 0.02 0.21 
Hydrogen Sulfide  98.03 60.09 0.01 
Propane  0.08 0.05 2.12 
Sulfur Dioxide    0.17
Butanes  0.03 0.05 0.87 
Pentanes  0.01 0.07 0.14 
Hexanes  0.06 0.44 
Ammonia  35.53  
TOTAL  100.01 100.00 99.99  99.99
   
Temperature, F  119 192  
Pressure, Psia  20.8 27.7  
Flow, SCFH  19,673 3,700 2,457 

The carbon balance method gives a calculated sulfur recovery efficiency of 99.8% (these
samples were taken during the adsorb-adsorb portion of the cycle.) This agreed closely with the
expected recovery.

However, the Type I AFR calculated a fuel gas flow of 24,885 SCFH – ten times the recorded
flow rate. If that fuel gas flow rate was correct, the sulfur recovery was closer to 98.2%. Further,
the Type II AFR – using the recorded fuel gas flow rate – had a nitrogen balance error of nearly
60%; more nitrogen was entering the unit than was leaving the unit. The mass balance error was
over 30%.

Clearly, either the reported analyses were not consistent with each other, or one or more flow
rates were incorrect. Although the AFR methods will normally detect – and, to an extent,
quantify – such data errors, they will not provide any assistance in determining where the error
lies. In this example, assuming the reported fuel gas flow rate is indeed off by a factor of ten
leads to a very good Type II AFR nitrogen balance. Unfortunately, it also leads to an
unreasonably high predicted incinerator temperature.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 20 
 
PART 4 – BEYOND THE AFR

The Analytical Flow Ratio methods are powerful, but application over the years has revealed a
few areas where additional analysis is required. Some of the deficiencies noted include:

 As seen in Example 2, the Type I AFR method can produce a fuel gas flow rate which is
wildly in error compared to the measured value. This is because the fuel gas stream
usually represents a very small fraction of the overall mass balance; adjusting this flow to
close the unit mass balance (which is, effectively, what the Type I AFR does) can result
in large differences between calculated and measured fuel gas flow rates.
 The Type II AFR forces the error into the nitrogen balance, which has the opposite effect:
nitrogen accounts for more than 50% of the mass flow in air-only SRUs. Therefore, the
Type II balance will diminish the apparent magnitude of data errors by “hiding” the error
in the nitrogen balance.
 As hinted by the footnote on page 15, the Type II AFR balance may be used to force the
error into any of the five atom balances. Nitrogen is by far the most commonly used for
the reason described in the previous bullet. Oxygen, hydrogen, carbon, or even sulfur,
may be used instead. However, there does not seem to be any perfect solution which is
applicable in all cases.

As a result, performance testing companies generally rely on additional analytical tools when
they prepare performance test reports. Some companies document their approach very
thoroughly; others provide less information. (However, all are willing to discuss their methods
with their clients.)

In 1996, Anderson [2] described a method which may be used to calculate the combustion air
flow rate given only the acid gas feed composition and flow and the dry tail gas (or stack gas)
composition. This method provides a quick check of measured combustion air flow rates, both in
the SRU and in the TGU and Incinerator. It is readily implemented in an Excel spreadsheet and
may be adapted to the extent of analytical speciation of hydrocarbons. (This method could – and
should – be used in Example 1 to confirm the air flow rate as predicted by the Type II AFR.)
However, when using an SRU tail gas composition for this analysis, the composition must be
adjusted to include elemental sulfur (both vapor and entrained liquid) as described in the next
section.

The extra degree of freedom provided by the Type II AFR can be used in more creative ways
than described in the third bullet above. As discussed earlier, using the Type II AFR and forcing
all the error into the nitrogen can result in unacceptably large errors in the nitrogen balance. It
turns out that if compounds other than nitrogen are allowed to float, overall material balance
errors can be reduced. One testing company – Brimstone – creates a virtual stream, consisting of
one or more real or imaginary compounds. This introduces an additional unknown: the flow rate
of the virtual stream, which allows the use of all five atom balances in the solution.

In addition to reducing the overall material balance error, this approach can help diagnose
problems with the data set. By using different compounds in the virtual stream, sensitivity
studies generally yields clues about the source or errors within the data set, including whether
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 21 
 
those errors arise from analytical or process data issues. Based on experience, the compound that
normally yields the smallest material balance error is CO2. Brimstone claims that when the flow
rate of this virtual stream is less than 0.2 percent of the mass balance, the overall balance will be
very satisfactory. (There are occasions when using compounds other than CO2 in the virtual
stream will result in a mass balance with a smaller error.)

As noted earlier, when intermediate stream compositions are known (as is typical during a full
performance test), the AFR analysis may be repeated with successive downstream “effluent”
streams as the outlet stream. Comparing the magnitude of the various virtual streams can help
identify a specific unit operation within the unit where a significant material balance error
occurs. (The software tool provided will not perform such a sophisticated analysis; however, the
fundamental techniques are the same.)
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 22 
 
PART 5 – MAKING SENSE OF IT ALL

There are a few additional important items to note:

1. Correcting for Elemental Sulfur in SRU Tail Gas

Example 1 illustrated a significant difference – over a percent – between the sulfur

recoveries calculated by SRU tail gas composition and by incinerator stack gas
composition. None of the sulfur testing companies analyze for elemental sulfur in process
gas streams, so SRU tail gas is always reported on an “elemental sulfur free” basis.

In order to obtain a valid estimate of sulfur recovery based on SRU tail gas, you must
adjust the composition to include elemental sulfur which is present (a) due to the vapor
pressure of sulfur, and (b) due to entrainment of liquid sulfur.

Lacking any other data, you can estimate the vapor pressure of sulfur using the following
equation from Shuai and Meisen [4]:

ln(p) = 89.273 – 13463/T – 8.9643·ln(T)

where p is pressure in Pascals and T is temperature in Kelvin.10

Liquid entrainment is usually on the order of 0.1 mole percent (wet basis), which is about
3 lbs/100 lb·moles of gas.

The spreadsheet tool does not include these calculations; you may easily modify the
“Stream Analyses” worksheet to incorporate them.

2. Issues with Incinerator Balances

Incinerators can drive you crazy.

As noted earlier, natural draft incinerators have no air flow measurement, and forced
draft incinerators often have very poor air flow measurement. This makes it difficult to
reconcile calculated combustion air flow with measured air flow.

To make this harder, fuel gas flow metering at the incinerator is an issue at many
facilities. Compared to other fuel users, this flow is minor and often receives little or no
attention. Since this flow is a minor contributor to the overall mass balance, large errors
in fuel flow rate will have only slight effects on the overall mass balance.

To complete the problem, heat losses from incinerators are significant. A careful analysis
of the mechanical design of the incinerator, as well as knowledge of where (and how!)
temperature measurements are taken, is required to make even a rough estimate of

                                                            
10
  The same equation (in English units) is shown in the GPSA Engineering Data Book. 
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 23 
 
incinerator heat loss. This makes it difficult to properly incorporate heat balance
information into the incinerator balance.

Finally, attempts to measure stack gas flow (obtained, for example, as part of RATA
tests) have been known to produce results that cannot possibly be reconciled with
material balances obtained from performance testing. The reasons behind this are beyond
the scope of this paper; it is mentioned simply as a precaution not to take the results of
stack gas flow measurements too seriously. (Suffice to say that the rigorously formalized
methods specified for this type of compliance testing are not always rigorously applied).

3. Accounting for Sulfur in Fuel Gas

If the fuel gas contains significant sulfur, it must be properly accounted for in the
calculation of sulfur recovery efficiency. The methods described (and the accompanying
spreadsheet) ignore sulfur burned in the incinerator in the recovery calculations.

If your facility burns sulfur-bearing fuel in the SRU (e.g. in-line heaters) or in the TGU
(e.g. reducing gas generator), then it is likely that the sulfur contained in that fuel will be
recovered and should be included in the recovery calculation. (However, the amount of
fuel is likely too small to affect the calculation.)

In order to use the spreadsheet, you should include SRU and TGU fuel gas in the
“SRU/TGU Fuel Gas columns in the “Stream Analyses” and “Recoveries” worksheets.
These fuel streams will be combined with the acid gas, causing that sulfur to be included
in the sulfur recovery calculation.

4. Specific Balances around Individual Equipment

As noted in the Introduction, the issue of estimating material balances around individual
equipment items is beyond the scope of this paper. However, using the techniques
described, it is possible (with sufficient compositional data) to perform successive
balances starting with the waste heat boiler effluent and moving downstream, equipment
item by equipment item.

If this approach is attempted, we recommend using Brimstone’s “virtual stream” method,

adding a stream with unknown flow rate but known composition. This allows you to
specify fuel flow (which should be well known for fuels fired in the SRU and/or TGU)
and solve all five atom balances.

By tabulating the calculated flow rates of the virtual stream as you move farther and
farther downstream in the unit, you should be able to identify significant data errors.
These should be resolved appropriately before continuing downstream through the unit.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 24 
 
CONCLUSION

Understanding the methods behind the calculation of sulfur recovery, and using the very
powerful Analytical Flow Ratio methods (and variations on those methods), gives the engineer
another tool to analyze sulfur recovery unit performance.

Although it is tempting to fire up the process simulator and attempt to duplicate the test
conditions, a few simple checks – such as the AFR balances – can quickly tell you if there is any
hope of matching test flows and analyses. In Example 1 above, a simulation has a very good
chance of matching the test data. After all, simulators force all five atom balances (along with a
number of other constraints.) In Example 3, however, it seems likely that matching the test data
with a simulator is a hopeless task.

It is also tempting to accept the observations and recommendations in the official test report at
face value. After all, these reports are prepared by skilled professionals. However, as shown in
Example 1, the conclusions reached by the professionals might not always withstand close
scrutiny. We certainly owe it to our employers to exercise our sound engineering judgment when
acting on the recommendations of others.
Getting the Most Out of Your Sulfur Recovery Unit Performance Test  Page 25 
 
REFERENCES

1. Paskall and Sames, Sulphur Recovery, Western Research, 1992.

2. Anderson, “A Method for Calculation of Claus Unit Sulfur Recovery Efficiency”, 1996
Brimstone Sulfur Symposium, September 26, 1996.

3. Blais, Marshall and Wissbaum, “How Hot is Your Reaction Furnace – Really?” 62nd
Laurance Reid Gas Conditioning Conference, Norman, Oklahoma, February 26 – 29,
2012.

4. Shuai and Meisen, “New correlations predict physical properties of elemental sulfur,” Oil
and Gas Journal, October 16, 1995.