Natural Gas Sweetening

TASK In this exercise, you will simulate a process that uses MEA to remove
H2S and CO2 from a natural gas stream. Figure 18 shows the flowsheet
along with the desired (or measured) operating conditions. The pressures
labeled bar are absolute bar. As previously mentioned on page 90, the
constraint that the rich amine contain 0.3 moles acid gas per mole MEA
is imposed to minimize corrosion. Table 42 describes the natural gas
stream. Makeup water and MEA is available at 1.5304 bar (7.5 psig) and
21.11°C (70°F).

Figure 18: Flowsheet

Showing Desired - 8.5
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Table 42: Sour Gas Feed

Component Mole %
CO2 1.37
H2S 1.71
Methane 88.37
Ethane 6.43
Propane 1.72
n-Butane 0.40
Flowrate 1.1185 x105 std m3/hr 3.95x106 std ft3/hr
Temperature 32.22°C 90°F
Pressure 17.216 bar abs 235 psig

Part A: Before running the problem, answer the following questions:

Preliminaries
1. What thermo-physical property prediction methods should you
select for this system?
2. Which column solving algorithm(s) should you use?

40 Natural Gas Sweetening

 3. Which column initial estimate generator should you select?
4. For both columns, PRO/II requires you to estimate one of the prod-
uct rates. What are good estimates, and how can you get PRO/II to
automatically estimate the rates for you?
5. This flowsheet contains a recycle. What are good estimates for the
recycle rate, composition, temperature, and pressure? HINTS: It is
usually best to provide estimates for streams you know the most
about. Also, 15 wt% aqueous MEA is equivalent to 4.95 mole per-
cent MEA. You can determine the molar composition using the flash
hot key, on a 15 wt% MEA stream.
6. How can you impose the specification that the rich amine stream
contain 0.3 mole acid gas per mole of MEA?
7. This flowsheet will not converge unless the two-sided heat
exchanger is calculated after the absorber and the stripper. Why is
this true, and what can you do to ensure that calculations are carried
out in the correct order?
8. The flowsheet will not converge unless you provide an initial esti-
mate for the regenerator feed. What is a good estimate?
9. How can you calculate the makeup stream requirements?

Part B: Run Build the amine sweetening flowsheet and calculate the following quan-
the Simulation tities:

■ The sweet gas, acid gas, and lean amine compositions and flowrates.
■ The makeup rate of MEA and water.
■ The absorber column temperature and flowrate profiles.

Estimate the lean amine composition as 15 weight percent MEA and 85

weight percent water.

Note: Tighten all column and loop convergence tolerances by an

order of magnitude.

Many natural gas contracts require the gas to contain no more than 2.3
grams H2S per 100 standard cubic meters (1 grains of H2S per 100 stan-
dard cubic feet). To safely meet this specification, gas sweetening units
are commonly designed to reduce the H2S content of the sale gas to 0.57
grams per 100 standard cubic meters (0.25 grains per 100 standard cubic
feet). Does the sweet gas meet this specification? Hint: Use a CALCULA-
TOR to compute the sweet gas composition in these units of measure.
There are 7000 grains per pound.

Hydrocarbon Distillation Workbook 41

 If You Finish Although you entered an estimate of 15 weight percent MEA for the
Early LEAN_AMINE stream, at convergence the stream contained 14.8% MEA.
Similarly an initial composition guess of 20 weight percent MEA yields
19.68% MEA at convergence, and an initial guess of 10 weight percent
yields 9.92%. Based on these results, the following are apparent:
■ The flowsheet has a solution for a variety of recycle compositions.
This is to be expected since the process can operate over a range of
recycle compositions. The composition of the recycle stream is a
design variable.
■ The converged recycle composition is not identical to its initial
guess. Again, this is no surprise. The separations in the process are
not perfect and the recycle stream will contain components other
than MEA and water. This dilutes the MEA from the initial guess
you supplied.

In this run, solve the flowsheet so that the lean amine stream contains
exactly 15 weight percent MEA (not 14.8). One strategy is to adjust your
initial guess for the lean amine stream composition and re-run the prob-
lem until the converged composition is 15 weight % MEA. Although this
procedure works well for this particular process, it is in general very
time consuming, because it requires your constant attention.

A better strategy for this type of specification is to use a CALCULATOR

and a CONTROLLER to automatically make the composition adjustments
for you. The CONTROLLER specification is obvious: Mass fraction of MEA
in LEAN_AMINE = 0.15. To meet this specification you would like to vary
the LEAN_AMINE stream composition. Unfortunately, the CONTROLLER
has no way to do this. The CALCULATOR utility, however, does have this
ability through its SRVSTR subroutine. Simply instruct the CALCULATOR
to store result R(1) for the MEA component flowrate in stream
LEAN_AMINE and use the CONTROLLER to vary this value. The CONTROL-
LER variable is now CALCULATOR result R(1).

Note: You will have to enter the flowsheet sequence with the CALCU-
LATOR and CONTROLLER preceding the absorber.

The value of R(1) must be initialized on the first call to the CALCULATOR.
On all other calls, the CONTROLLER will adjust R(1) and the CALCULA-
TOR should not change R(1). A convenient way to initialize R(1) is with
a statement like If(R(1) .lt. 0) R(1) = 1500.

42 Natural Gas Sweetening


SOLUTION

Part A: The Amines package is designed

Thermo-physical property prediction method:
Preliminaries for natural gas sweetening using various amines.

Column algorithm selection:The components in this problem behave less

ideally than simple hydrocarbon systems but more ideally than multi-
phase azeotropic problems. Therefore you may be unsure whether to
choose CHEMDIST or Inside/Out (I/O). When in doubt, try Inside/Out
since it is faster and more forgiving of initial guesses than CHEMDIST. If
I/O fails, you can always switch to CHEMDIST.

For less-than-ideal systems, you can sometimes make I/O converge by

lowering the damping parameter. We were able to converge both col-
umns using either algorithm, but chose I/O for its very large speed
advantage.

Note: The regenerator column does not converge unless the damping
factor is below 0.5. We used 0.4 and increased the number of
iterations to 30.

Again the choice is not obvious. The

Initial Estimate Generator selection:
Simple IEG is faster, but the Chemical IEG is more reliable for highly
nonideal systems. We were able to converge both columns using either
IEG. We chose the Simple IEG with the I/O algorithm and the Chemical
IEG with the CHEMDIST column algorithm.

The purpose of this gas sweetening process

Column Product Rate Estimates:
is to separate the H2S and CO2 from the hydrocarbons in the sour gas. In
a perfect world, all of the hydrocarbons are recovered in the
SWEET_GAS product stream, all of the H2S and CO2 are recovered in the
ACID_GAS stream, and all of the MEA and water remains in the recycle.
These best-case scenario results often provide excellent initial estimates
for real-world processes. With this in mind, estimate the SWEET_GAS
flowrate to be that of the SOUR_GAS feed less the H2S and CO2. Esti-
mate the ACID_GAS flowrate to be the flowrate of H2S and CO2 in the
SOUR_GAS.

You can use the flash hot key to determine the molar rates of these com-
ponents in the sour gas. You will have to do some arithmetic by hand to
determine the actual rate estimates. A more efficient approach is to use
the Define feature to automatically calculate the estimates. For example:
define the SWEET_GAS rate estimate to be the SOUR_GAS flowrate of
components methane through n-butane and define the ACID_GAS rate to
be the SOUR_GAS flowrate of components CO2 through H2S.

Hydrocarbon Distillation Workbook 43

 We chose to provide an estimate for the lean amine
Recycle Estimate:
stream because its temperature and pressure are known. You are told to
estimate its composition as 15 weight percent (4.95 mole percent) MEA
and 85 weight percent water. At convergence this stream will contain
small amounts of other components, particularly CO2.

The flowrate of MEA must be such that there is enough amine present to
remove essentially all of the H2S and CO2 from the sour gas. The reac-
tion stoichiometry indicates that you need at least 2 moles of amine for
each mole of acid gas absorbed. The composition constraint on the rich
amine stream, however, requires an excess MEA; the ratio of H2S and
CO2 to MEA in the rich amine must be 0.3. Assuming all of the H2S and
CO2 (153.7 kg-mol/hr [320.6 lb-mol/hr]) in the sour gas is picked up in
the rich amine stream, the lean amine should contain approximately
153.7/0.3 = 512.34 kg-mol/hr (320.6/0.3 = 1068 lb-mol/hr) of amine.
Thus a good estimate for the total lean amine flowrate is 512.34 /0.0495
= 10350 kg-mol/hr (1068/0.0495 = 21589 lb-mol/hr). This flowsheet
converges for a very wide range of recycle rate estimates-from 4500 to
over 45000 kg-mol/hr (10000 to over 100000 lb-mol/hr).

You can avoid all of this hand calculation by building the simple flow-
sheet shown in Figure 19. The stream XS-AMINE contains 15 wt % MEA
and 85% water with a very large flowrate. The splitter specification
states that the LEAN_AMINE flowrate should be calculated so that the
molar rate of MEA in LEAN_AMINE divided by the molar rate of CO2 and
H2S in SOUR_GAS is 3.333. This is the reciprocal of the acid gas pickup
specification (CO2 + H2S)/MEA = 0.3.

Figure 19: Flowsheet

to Estimate Lean- SOUR_GAS

Amine Flowrate
JUNK

XS-AMINE

LEAN_AMINE
AMINE_ESTI

Rich amine composition specification:You must adjust the recycle rate esti-
mate until the composition of the rich amine stream satisfies the con-
straint. This specification fixes the recycle rate. The simplest way to
impose this constraint is via a specification on the absorber column. The
specification will look like this: RICH_AMINE stream flowrate of H2S
through CO2 / RICH_AMINE stream flowrate of MEA = 0.3. The associated
variable is the flowrate of stream LEAN_AMINE.

An alternative is to use a CONTROLLER to impose the same specification

and variable. This strategy is slower and less reliable for this problem.

44 Natural Gas Sweetening

 Calculation Sequence: If the two-sided heat exchanger is calculated after
the
absorber and before the regenerator, then its hot-side feed will be
unknown. When PRO/II encounters a unit operation with an unknown
feed, it assumes that stream has zero flowrate. Thus the hotside product
stream will have a zero flowrate and the feed to the absorber will be
almost zero. It will be slightly greater than zero because of the small
makeup of water and MEA. The absorber will fail to solve, and the flow-
sheet will never recover.

To guarantee a correct calculation sequence, explicitly define one your-

self. We used: absorber, valve, regenerator, two-sided heat exchanger,...

Estimating the regenerator feed:This is quite easy with PRO/II's reference

stream utility. It is identical in composition to the VALVE'S liquid prod-
uct, HXFEED, and has a temperature of 82.22°C (180°F). The pressure is
that of HXFEED less the pressure drop across the heat exchanger.

Makeup Streams: Small amounts of MEA and water will be lost from the
process in the product streams. For true steady state operation, they must
be replenished at their net rate of loss. The best way to determine the
makeup rates is to calculate them exactly at every iteration. The makeup
rate of a component is the sum of its flowrates in product streams minus
the sum of its rate in feed streams. The CALCULATOR procedure shown in
Figure 20 calculates and stores the MEA makeup rate in result R(1) and
the water makeup rate in R(2).

The CALL SRVSTR line stores these calculated results for the component
flowrates of MEA and water in the stream labeled MAKEUP. The SRVSTR
subroutine is a very powerful feature that allows the CALCULATOR to
build streams from calculated quantities.

The stream, MAKEUP, must be initialized in the flowsheet. The tempera-

ture and pressure should be 21.11°C and 1.5304 bar (70°F and 7.5 psig).
The component rates you supply do not matter since the calculator will
reset them at every iteration.

Figure 20: Makeup

Calculations CALCULATOR UID=CALC_MAKEUP
SEQUENCE STREAM=MAKEUP
DEFINE P(1) AS STREAM=SWEET_GAS, RATE(LBM/H), COMP=8
DEFINE P(2) AS STREAM=HC_PURGE_VAP, RATE(LBM/H), COMP=8
DEFINE P(3) AS STREAM=ACID_GAS, RATE(LBM/H), COMP=8
DEFINE P(5) AS STREAM=SWEET_GAS, RATE(LBM/H), COMP=7
DEFINE P(6) AS STREAM=HC_PURGE_VAP, RATE(LBM/H), COMP=7
DEFINE P(7) AS STREAM=ACID_GAS, RATE(LBM/H), COMP=7
PROCEDURE
$ R(1) = MEA MAKEUP
$ R(2) = WATER MAKEUP
R(1) = P(5) + P(6) + P(7)
R(2) = P(1) + P(2) + P(3)

$ STORE THE MAKEUP RATES FOR MEA AND WATER IN THE STREAM "MAKEUP"
$ IN THIS FLOWSHEET, MEA IS COMPONENT 7 AND WATER IS COMPONENT 8
CALL SRVSTR(SCMR,R(1),MAKEUP,7,8)
RETURN

Hydrocarbon Distillation Workbook 45

 Part B: Run We modeled the process using the flowsheet shown in Figure 21. To sim-
the Simulation plify the flowsheet, we replaced the PUMP and trim cooler with a single
FLASH unit operation. If you desire more detailed information about the
operation of the PUMP and trim cooler, you could model them separately.

Figure 21: Flowsheet

Used for PRO/II
Simulation ACID_GAS

1
SWEET_GAS

GRAIN_CALC

1 3

4
CALC_MAKEUP
LEAN_AMINE
2 MAKEUP 5

REGENFEED
6
S1
3
7
FLASH

8
E1
4
9

10
SOUR_GAS
5
HC_PURGE_VAP HXFEED 11

ABSORBER
REGENERATOR 12
RICH_AMINE

V1 REGEN_BTMS

The units FEED_CALC and FEED_CONTROL do not apply to this run.

Table 43 and Figure 22 show selected results for this simulation. The
makeup rates of MEA and water are 0.0143 and 31.3 kg-mol/hr respec-
tively (0.031 and 69.0 lb-mol/hr).

Table 43: Selected Results

Component Sweet Gas Lean Amine Acid Gas
(mole fraction) (mole fraction) (mole fraction)
CO2 8.01e-07 5.09e-03 0.408
H2S 3.76e-06 4.22e-04 0.509
Methane 0.908 0 4.85e-03
Ethane 0.0661 0 3.70e-04
Propane 0.0177 0 6.36e-05
n-Butane 4.11e-03 0 4.10e-05
MEA 2.88e-06 0.0492 3.23e-07
Water 3.68e-03 0.945 0.0778
Flowrate 4845 kg-mol/hr 16615 kg-mol/hr 167.6 kg-mol/hr
10107 lb-mol/hr 34655 lb-mol/hr 349.5 lb-mol/hr

46 Natural Gas Sweetening

 Figure 22:
Regenerator English UOM
Column Profile
-------- NET FLOW RATES ---------- HEATER
TRAY TEMP PRESSURE LIQUID VAPOR FEED PRODUCT DUTIES
DEG F PSIG LB-MOL/HR MM BTU/HR
---- ------ ------ -------- -------- --------- --------- -----------
1C 120.0 7.00 1397.9 349.5V -27.2207
2 227.0 8.00 37800.2 1747.4 34500.3L
3 231.9 8.15 38059.6 3649.4
4 234.2 8.30 38196.3 3908.8
5 235.6 8.45 38281.2 4045.5
6 236.5 8.60 38342.1 4130.4
7 237.3 8.75 38391.0 4191.3
8 238.0 8.90 38434.1 4240.2
9 238.6 9.05 38475.1 4283.3
10 239.1 9.20 38517.3 4324.3
11 239.7 9.35 38564.1 4366.4
12R 240.7 9.50 4413.3 34150.8L 77.3921

Metric UOM

--------- NET FLOW RATES --------- HEATER

TRAY TEMP PRESSURE LIQUID VAPOR FEED PRODUCT DUTIES
DEG C BAR KG-MOL/HR M*KCAL/HR
---- ------ ----- -------- -------- --------- --------- ---------
1C 48.9 1.50 670.3 167.6V -7.2512
2 108.3 1.56 18124.2 837.8 16542.0L
3 111.0 1.58 18248.6 1749.8
4 112.3 1.59 18314.2 1874.2
5 113.1 1.60 18354.9 1939.7
6 113.6 1.61 18384.1 1980.4
7 114.1 1.62 18407.5 2009.6
8 114.4 1.63 18428.2 2033.1
9 114.8 1.64 18447.8 2053.8
10 115.1 1.65 18468.0 2073.4
11 115.4 1.66 18490.5 2093.6
12R 115.9 1.67 2116.1 16374.4L 20.6155

To determine the sweet gas composition in both grains/std ft3 and in

grams/std m3, use the CALCULATOR procedure shown in Figure 23.

Figure 23: Calculator

Procedure for
Computing Sweet Gas
Composition

Hydrocarbon Distillation Workbook 47

 At convergence, it reports that the SWEET_GAS stream contains 0.5717
grams H2S per 100 std m3 (0.2498 grains H2S per 100 std ft3.)

If You Finish Figure 24 shows the CONTROLLER procedure that we used to implement
Early the LEAN_AMINE stream composition specification. The CALCULATOR
procedure is shown in Figure 25.

Figure 24: Controller

to Specify Lean
Amine Composition

Figure 25: Calculator

Procedure to CALCULATOR UID=FEED_CALC
SEQUENCE STREAM=LEAN_AMINE
Manipulate DEFINE P(1) AS STREAM=LEAN_AMINE, RATE(LBM/H), COMP=7
LEAN_AMINE PROCEDURE
$ FOR FIRST ITERATE, USE R(1) = P(1) = CURRENT FLOWRATE OF MEA IN
Composition LEAN_AMINE
$ FOR ALL OTHER ITERATES, A VALUE FOR R(1) IS PASSED FROM THE CONTROLLER
IF(R(1) .LT. 0) R(1) = P(1)
$ STORE R(1) IN THE COMPONENT FLOWRATE OF MEA IN STREAM LEAN_AMINE
$ COMPONENT 7 IS MEA

CALL SRVSTR(SCMR,R(1),LEAN_AMINE,7,7)
RETURN

The statement IF(R(1).LT.0)R(1)=P(1) prevents the CALCULATOR from

changing R(1) except at the first iteration. As you may know, PRO/II ini-
tializes CALCULATOR variables to a very large negative number; there-
fore the first time this CALCULATOR is called, R(1) is set to P(1). In all
other iterations, R(1)>0 so the CALCULATOR skips this operation and uses
the value that is passed to it by the CONTROLLER.

We explicitly defined the sequence to be "calculator, controller, absorber,

valve, regenerator, HX, makeup calculations, flash".

Don't be intimidated by the use of the CALCULATOR in implementing this

specification; its sole purpose is to adjust the stream component flow-
rate: a task the CONTROLLER cannot perform by itself.

48 Natural Gas Sweetening