Optimization of ethane extraction plants

from natural gas containing carbon dioxide*

L. Fernandez, J.A. Bandoni, A.M. Eliceche and E.A. Brignole
PLAPIQUI, UNS-CONICET, CC 717 8000 Bahia Blanca, Argentina

The extraction of ethane and NGL from natural gas is generally based on some of the following
alternatives: turboexpansion (TE); Joule-Thompson expansion (JT); external refrigeration; and
absorption. In many processing schemes a combination of these effects is used to improve the energy
efficiency or to obtain greater recoveries. The selection of the basic process technology is based on an
energy analysis. The determination of the final structure and optimum process conditions are found by
successive quadratic programming. The optimization process is based on a rigorous simulation of the
plant. An initial feasible point for the optimization procedure is derived from the feed phase-envelope
properties. The effect of carbon dioxide on process design is taken into account by introducing as a
constraint, in the optimization process, the conditions of carbon dioxide precipitation in the
demethanizer unit. The sensitivity of the optimum design to different configurations, residual gas
pressures, Cp+ fraction and carbon dioxide concentration are presented.

Keywords: carbon dioxide solidification; natural zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFED

gas plants; LPG recovery

Nomenclature
Feed gas flowrate (kmol h-‘) Activity coefficient of CO2
n0 v2
4 Residual gas flowrate (kmol h-‘) @2 Fugacity coefficient for CO2 in a liquid
nP
Liquefied final product flowrate (kmol h-‘) mixture
(Am,, Minimum cooling load (kJ h-‘) 6 Fugacity coefficient for pure CO2
Q External refrigeration (kJ h-‘) PCr Cold-tank pressure (bar)
Expansion work (kJ h-‘)
( ZJ’,xXP zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBATCT Cold-tank temperature (K)
T Temperature (K) P DC Demethanizer column pressure (bar)
Fugacity of CO2 as a subcooled liquid & External refrigeration (%)
; Fugacity of CO2 in the solid phase
x2 Solubility of CO2 in the liquid phase (mole
fraction)

Introduction becomes a significant portion of the total and operating

cost of the plant.
The extraction of ethane and NGL from natural gas is
Wang’ made a systematic search of optimum processing
generally based on some of the following alternatives:
conditions for a turboexpansion plant, for different
turboexpansion (TE); Joule-Thompson expansion (JT);
natural gas feed compositions with very low CO, content.
external refrigeration; and absorption. In many processing
He found that a combination of turboexpansion and
schemes a combination of these effects is used to improve
mechanical refrigeration led to minimum energy require-
the energy efficiency or to obtain greater recoveries.
ments. In recent work2, a methodology was developed for
The TE process, through the use of cryogenic tem-
the selection of gas processing technology before the
peratures, recovers the ethane and NGL fraction from
optimization of process conditions. In this study the effect
natural gas, with less power consumption than refrigerated
of the Cz+ fraction upon the process configuration was
absorption. The cryogenic temperatures used in TE or
investigated. Again, the effect of CO, on the process
refrigerated processes require proper consideration of the
configuration and optimum process conditions was not
CO2 content of the natural gas to avoid the precipitation of
considered. Wilkinson and Hudson3 have pointed out the
solid COZ.
economic interest of turboexpander plant designs for
When the CO2 in the natural gas is removed by feed
ethane recovery, without CO2 front removal. They have
pretreatment (front removal). this separation stage
presented alternative processing schemes that can avoid
*Paper presented at GAS Separation International, Austin. TX, USA. CO2 precipitation by running the demethanizer unit at
22-24 April 1991 warmer conditions than standard turboexpansion units,

0950-42 14/91/040229-06
0 1991 Butterworth-Heinemann Ltd Gas Separation & Purification 1991 Vol 5 December 229
Optimization of ethane extraction plants: L. Fernandez et al.

while maintaining a high ethane recovery. However,

detailed information on process conditions in connection
with the CO, concentration in the feed is lacking.
The determination of the optimum operating con-
ditions of an ethane and NGL extraction plant requires
first the definition of the refrigeration and process
scheme. In the present work, an initial feasible point for
the optimization procedure is found through a thermo-
dynamic analysis.
The effect of CO2 concentration on process design was
taken into account by introducing as a constraint, in the
optimization process, the conditions of CO, solidification 92-f--
in the demethanizer unit. The sensitivity of the optimum Feed configuration
I
Feed configurotlon II 1
design to different residual gas pressures, C,, and CO?
concentration are presented. Figure 2 Demethanizer feed configurations

Ethane and NGL recovery process

fed to the top plate and the vapour to the third. The liquid
A large number of design parameters characterize each fraction from the expander is again fed to the top plate.
particular ethane and NGL recovery problem. Some of The designer is faced with many questions before going
the typical design parameters are pressure and temperature into a detailed process design. Does turboexpander
of gas supply and delivery, recovery levels, feed flowrate refrigeration satisfy all the cooling needs of the process? Is
and composition, physical state of the products, ambient mechanical refrigeration (external) required? What is
temperature, water and CO1 concentration in the feed. the performance of IT process under similar conditions?
A typical process flow diagram is shown in zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCB
Figure 1.
How to avoid COz precipitation in cryogenic processes? Is
The natural gas is compressed and air-cooled before TE a feasible alternative?The lasttwentyyears have seen a
entering the area of heat exchange and separation. The large change in process technologies for NGL recovery,
feed gas is cooled by heat exchange with the residual gas with a big decrease in technologies based on refrigerated
and with the side and/or bottom reboiler of the demethan- absorption and adsorption and a significant increase in
izer column, sometimes combined with external TE, JT processes, mechanical refrigerated plants or
refrigeration. combined processes.
After the cold recovery process the feed is sent to a The different process schemes that have been proposed
vapour-liquid separator (cold tank), before entering the have usually been justified in terms of improving the
demethanizer column. The low temperatures required to process energy consumption, to avoid CO? precipitation
achieve high ethane recoveries are obtained by expansion or to achieve higher recoveries’-6.
of the vapour phase from the cold tank to the demethanizer A methodology to search for the proper technology and
pressure. operating conditions was proposed by Bandoni et al.‘.
The recovery level is also dependent upon the tem- This procedure is based on an energy analysis over the
perature and pressure of the cold tank. These variables, cold section of the plant and is extended in the present
together with the demethanizer operating pressure, are work to CO?-containing mixtures.
the key optimization variables. For this analysis the process is divided into hvo sectors
Two column feed schemes are considered (Figure 2). In (Figure 3): sector I, compression, recompression and
feed configuration I. the liquid fraction obtained after the ambient heat exchange; sector II, separation, expansion.
expansion is fed to the top of the column. The liquid phase refrigeration and heat exchange at sub-ambient tem-
from the cold tank is fed to the third plate, after a JT peratures. Two streams leave sector II: the residual gas at
expansion to the demethanizer pressure. In feed con- T,, P, and the liquid fraction extracted at T,,, Pp. On the
figuration II, the liquid fraction after the JT expansion is basis of the feed composition and specified recoveries it is
possible to compute energy and material balances for
Sector I Sector II sector II:
I
n, = n, + np (1)

Figure 1 General process flow diagram: 1, air coolers; 2, inlet

compressor; 3, cold tank; 4, turbo expander; 5, JT valves;
6, demethanizer; 7, booster compressor; 8, compressor Figure 3 Ethane extraction-plant energy analysis

230 Gas Separation 8 Purification 1991 Vol 5 December

 Optimization of ethane extraction plants: L. Fernandez et al.

(AH),, = n,Hs+ npHp- @&I (2) zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDC

8 inlet gas stream splitting;
9 different demethanizer feed configuration.
= (AH),, - ( WJexp
Qrer (3)
The determination of the optimum process scheme and
The ‘minimum’ refrigeration load for sector II zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
[(AH),,] operating conditions are formulated as a nonlinear
considering complete cold recovery (no heat integration programming (NLP) problem, where the objective function
limitations) and adiabatic conditions is given by is to maximize the net annual benefits (scales-costs) for
Equation (2). The energy analysis is based on comparing an ethane and LPG recovery plant given the feed
the minimum refrigeration load in sector II with a realistic composition, inlet pressure, residual gas delivery pressure,
upper limit of the refrigeration attainable by expansion temperature of the inlet gas (after air-cooling) and
work. Wang’ proposed a maximum value of six for the maximum methane/ethane ratio in the liquefied product.
expansion ratio. However, this ratio may be too high for The range of process specifications covered in the present
CO*-containing natural gas feeds. The values of minimum work is given in Table 1. The solid CO* solubility is taken
refrigeration load and (IV&, are shown in Figure 4 as a into account by introducing as a constraint in the
function of the C,, fraction in the feed. For lean mixtures optimization problem, the value of CO2 solubility at the
(AH),, is nearly zero and a IT-based process is feasible. temperature and composition of each plate of the
However, when the Cz+ fraction in the feed increases, TE demethanizer column. The nonlinear programming
processes alone or in combination with external refrigera- problem is solved with a successive quadratic pro-
tion are required. In this region, IT-based processes gramming code (OPT)‘. Under these conditions the main
always require external refrigeration. In this preliminary process optimization variables are: cold-tank pressure,
process analysis, the amount of CO, in the feed is cold-tank temperature and demethanizer-column
considered within the C,, fraction. pressure.
The basic process scheme is chosen on the basis of
Figure4, as a function of the Cz+ fraction. However, the Demethanization in the presence of COP
problem of CO, precipitation, and the identification of
process configuration and optimum operating conditions The separation of methane-CO, mixtures by direct
requires a detailed optimization study. fractionation is not possible because of the problem of
In this regard a general process superstructure (Figure l), CO, solid formation. This problem becomes evident by
taking into account the typical components found in looking at the phase diagram for the methane-CO, binary
natural gas processing plants, was adopted. This super- mixtureK9 (FgI ure5), which shows that, working at
structure includes as possible operations and units: pressures below the methane critical pressure, it is not
possible to go over the whole concentration range without
inlet and residual gas compressor; passing through the solid-vapour region. However, in the
expansion of gas and liquid through JT valves; presence of mixtures of methane with ethane, propane
TE gas expansion and residual-gas booster and butane, the solubility of CO, increases considerably’.
compressor: Therefore a rigorous prediction of CO? solubility is
knock-out drums. cold tank and demethanizer reflux required at each stage of the demethanizer unit. A
tank; predictive method, based on experimental CO? (solid)
heat integration of feed gas with demethanizer
bottoms;
external refrigeration of inlet gas; T a ble 1 Design bases and inlet gas compositions used in this work
cold recovery (heat exchangers and side reboilers);
Flow 16000.00 kg mol hh’
Plant inlet gas pressure 40.00 bar
Inlet gas temperature
P zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
310.00 K
60.: 20 3
“‘I Product specifications
60: zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
IO Cl /C2 in bottom, 0.02
---_6
5000 Demethanizer Nine theoretical trays, including
the reboiler
Residual gas outlet pressure 35.00, 40.00, 50.00 bar
External refrigeration Refrigeration cycle efficiency, 0.8
Heat exchangers Temperature approach, 10 K
Compressors Mechanical efficiency 75.00%
Raw material price 6.75 c kg-’
Bottom-product sale price 20.00 c kg-’
Residual gas sale price 6.00 c kg-’

Inlet gas compositions

Components Mixture A Mixture B

(mol%) (mol%)

Nitrogen 0.27 0.25

Carbon dioxide 1.25 4.00
Methane 91.72 75.63
Ethane 4.23 13.42
Propane 1.32 4.44
Butane 0.71 1.62
Pentanes 0.24 0.41
Hexanes 0.26 0.23
Figure 4 Process refrigeration load and TE refrigeration as a Cz+ (%) 6.00 23.00
function of Cp+ in the feed

Gas Separation B Purification 1991 Vol 5 December 231

Optimization of ethane extraction plants: L. Fernandez et al.

liquid-phase composition on CO? solubility. The solubility

is considerably lower in methane than in mixtures of
methane with higher alkanes. zyxwvutsrqponmlkjihgfedcbaZYX

Proc e ss opt im iza t ion

The’ determination of a feasible initial point for the
optimization procedure is obtained with the help of the
feed phase-envelope properties. The pressure versus
temperature line for a given liquid fraction in the cold
tank presents maximum temperature and pressure values
Temperature (K) (Figure 7). The initial liquid fraction adopted is twice the
value of the C,, fraction in the feed. The pressure at the
Figure 5 Phase diagram for the binary methane-CO, mixture maximum temperature point (P*) is a limiting pressure
for the cold tank, because beyond this value the system
saturation pressures and computation of fugacity co- enters retrograde condensation conditions. To avoid the
efficients zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
by using the Soave-Redlich-Kwong”.“equation retrograde region, the maximum cold-tank operating
of state, was developed for the computation of the pressure is chosen as the minimum of P* and the critical
solubility of CO? in multicomponent hydrocarbon pressure. In previous work, a maximum value for the
mixtures. The ratio between the CO] liquid and solid operating pressure of the demethanizer column was
fugacities has been correlated on the basis of the predicted obtained by the condition of cold recovery from the
(liquid) and experimental (solid) fugacities by using an demethanizer bottom and side reboilers. For
expression based on classical thermodynamics: CO!-containing mixtures, this bound on the maximum
operating pressure has to be removed at the expense of a
greater requirement for external refrigeration.
lnt) = -4.693(?- 1) The objective function for the ethane extraction-plant
optimization is the net annual benefit (B) computed as:
+ 0.332
216.6 -_l-ln2F$j
T B=S-O-I

The CO? solid solubilities are obtained by taking into where S are sales per year. 0 are operating costs per year
and I are annual investment costs. The prices of products
account that zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
and natural gas are shown in Table 1 and the capital
f, investment is based on G.D. Ulrich’s cost correlations’“.
(5) The simulation of the entire plant is achieved by using
fi=xzyz
a rigorous simulator (PROSYD). The thermodynamic
where the activity coefficient of CO, is obtained as properties were predicted by using the SRK equation of
state. The simulation of the plant begins at the cold tank.
with the assumed value of temperature and pressure of
this unit. The refrigeration required to meet these
operating conditions is evaluated. If the total refrigeration
The computation of CO, solubility is made at the provided by cold recovery is insufficient to achieve the
hydrocarbon composition, pressure and temperature of cold-tank temperature at the selected pressure, the
each stage of the demethanizer unit. The standard amount of external refrigeration required is computed.
deviation between predicted and experimental” solubility The CO? concentration profile and operating con-
data for the binary mixtures CO,-methane. COz-ethane ditions of the demethanizer column are obtained by a
and CO,-propane was 3.7%. Figure 6 shows the effect of rigorous distillation-column simulation that uses the
Naphtali-Sandholm’4 method with a control loop on the
0.15 bottom flowrate to keep the methanefethane ratio at a zyxwvu

1
RI
s
z 0.10

.-:,
5
‘k
$ 0.05
P

160 165 200 250

Temperature (K) Temperature (K)

Figure 6 Solid-CO*-liquid equilibria in methane and methane- Figure 7 Natural-gas phase envelope: selection of initial values
butane mixtures for the optimization

232 Gas Separation 8 Purification 1991 Vol 5 December

 Optimization of ethane extraction plants: L. Fernandez et al.

specified value (0.02). A maximum liquid fraction of 0.5 1

is allowed in the cold tank.

Results and discussion

Two basic technologies were applied: TE+ER or JT+ER
with two demethanizer feed configurations. Two different
natural gas mixtures zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA
(Table I) were studied: mixture A is a
lean mixture with a C,, fraction of 6% (free from CO,);
mixture B is a rich gas mixture with a C,, fraction of 23%.
The effect of CO* composition on optimum conditions
was studied for mixture A in the range O-5%; the CO2
concentration of mixture B was 4%.
A typical composition profile of CO, in the liquid 225 250
phase of a demethanizer column is shown in Figure 8 as a Temperature (K)
function of the plate temperature. In the same figure the
solid formation barrier, computed at each plate condition, 0.4
is shown. In Figure 9a the CO, concentration profile for
the same feed as before is shown, but with a small
reduction in the demethanizer bottom flowrate. In this go.3
case there is a region in the column where the CO1
Z
composition crosses the solid formation barrier. This is
S
not a feasible operating point because the column will \
‘5 0.2 \
freeze in this region. A reduction in the demethanizer .k ‘\
‘\
operating pressure also leads to solidification conditions b
(Figure 96). Under these conditions, it is necessary to shift g 0.1
the CO? composition profile to the left or downwards to
make the column operable. An increase in column
operating pressure has the effect of moving the profile to
the left. If the demethanizer bottom flowrate is increased 200 225 250 275 300
the composition of CO? in the column decreases and there Temperature (K)
is a shift downwards of the concentration profile.
The effect of CO, concentration in the feed on Figure 9 Effects on CO z profile of (a) bottom flowrate;
(b) pressure decrease
optimum conditions was studied for mixture A. The main
result of an increase in CO, concentration is an increase in
demethanizer column operating pressure and con-
sequently a significant
(Figure IO). The constraint
reduction in ethane recovery
on CO? solubility raises the
column operating pressure and reduces the TE cooling
35290
effect from 81% to 74% of the total cooling load. The
recovery of cold from the demethanizer bottoms requires
a maximum operating pressure of 20 bar. However, this
value is exceeded when the concentration of CO2 in the
feed exceeds 1%. In this case the cold recovery from the
bottom reboiler is lost.
The effect of C,, fraction can be seen by comparing the

151 I
0 0 01 0.02 0.03 0.04 o.075°
Feed molar fraction of CO,

Figure 10 Effect of CO, feed concentration on demethanizer

pressure and recovery for mixture A

results obtained v$h the same COZ concentration in the

feed (4%) for mixtures A and B. For the richer mixture, the
demethanizer column pressure is 18.6 bar against a value
of 28.7 bar for mixture A. This is a clear indication that
rich feed mixtures are able to handle greater CO* feed
concentrations more efficiently than lean mixtures.
The effect of feed configurations I and II were studied
for both mixtures. The change from feed configuration,
from I to II, can be justified in view of the favourable effect
225 250 of the concentration of higher alkanes on CO* solubility
Temperature (K)
in the liquid phase. By feeding the liquid fraction from the
Figure 8 CO, profile in the demethanizer column cold tank to the top plate, an increase in higher alkanes

Gas Separation 8 Purification 1991 Vol 5 December 233

Optimization of ethane extraction plants: L. Fernandez et al.

Table 2 Synthesis and optimization results

Technology RCr R, R, Objective function Cz recovery

Mixture/structure (bar) (bar) (96) (USS h-‘) (W

JT+ ER 60.0 208.0 22.0 26.43 2371.72 81.20

AA
TE + ER 57.8 208.0 21.9 22.30 2583.20 83.13
A/I
TE+ ER 59.9 208.0 23.9 26.90 2487.71 83.15
A/II
JT+ ER 43.5 208.0 19.0 40.00 1503 1.84 87.81
8/l
TE + ER 43.27 208.0 18.6 42.31 15746.55 84.67
8/I
TE + ER 40.00 208.0 15.60 36.70 15805.30 84.82
B/II

Cz recovery: the ethane in the demethanizer bottom product divided by the ethane in the inlet gas
R,: amount of external refrigeration divided by total refrigeration load (R,/(cold recovery + R,))

concentration in the coldest section of the column can be technology and determination of optimum operating
obtained. However, for mixture A configuration I was conditions.
superior to II. This can be justified in view of the low
concentration of C,, in this case. However, for a rich References
mixture, configuration II is the best and the demethanizer
I Wang, W.B. PhD Thesis Tulsa University (1985)
operating pressure is reduced to a lowervalue (15.6 bar). In
2 Bandoni, J.A., Eliceche, A.M., Mabe, G.D.B. and Brignole,
other words, configuration II gives greater column EA. Compur Chem Engng (1989) 13 587
operability with regard to CO* concentrations or column 3 Wilkinson, J.D. and Hudson, H.M. Oil and Gus J (1982) 80
operating temperatures. (18) 281
A comparison between the two basic technologies 4 Herrin, J.P. Hydrocarbon Processing (1966) 45 (6) 144
5 Tomlison, T.R. and Banks, R. Oiland GasJ (1985) 83 (28) 81
(Tuble2) indicates that TE+ER is the best alternative for 6 Holmes, AS., Ryan, J.M., Price, B.C. and Styring, R.E. Proc
lean mixtures. For mixture B both TE+ER and JT+ER 61sr Ann Convention Gas Processors Assoc Dallas, Texas, USA
have a similar performance with regard to the objective (1982) p 65
function (Equation (7)). 7 Biegler, L.T. and Cuthrell, J.E. Corn Chem Engng (1985) 9
257
The effect of residual pressure was studied for mixture
8 Davis, J.A., Rodewald, N. and Kurata, F.AIChEJ( 1962)8 537
B. For obvious reasons the objective function increases for 9 Nagahma, K., Konishi, H., Hoshino, D. and Hirata, M.
decreasing values of residual pressure. However, the J Chem Eng Data (1974) 7 323
process optimum conditions do not change. 10 Soave, G. Chem Engng Sci (1972) 27 1197
Finally, these results show that to design natural gas, II Soave, G. Chem Engng Sci (1979) 34 225
12 Kurata, F. Gas Processors Assoc Re.s Rep RR-IO (1974)
containing CO,, processing plants under cryogenic 13 Ulrich, G. A Guide to Chemical Engineering Proce.ss De.sign and
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234 Gas Separation & Purification 1991 Vol 5 December