Dev~lopment and Application of the

Controlled-Freeze-Zone Process
R.C. Haut, * SPE, R.D. Denton, and E.R. Thomas, SPE, Exxon Production Research Co.

Summary. The controlled-freeze-zone (CFZ) process is a cryogenic distillation technique for separating CO 2 and heavier compounds
from methane (C). This paper describes how the process controls the freezing and melting of CO 2 in a specially designed section of
an otherwise conventional distillation tower. In addition to describing the process, this paper compares the CFZ process to other gas-
treating processes, discusses pilot-plant operational results, and gives examples of potential CFZ applications. The CFZ process is a
simple, cost-effective method to process gas streams containing CO 2 using proven facilities, equipment, and control philosophies and
has been demonstrated through the operation of a large-scale pilot plant.

Introduction
Natural gas processing has developed over the last 2 decades from
lean-oil technology to cryogenics to separate C) from heavier com-
ponents present in the gas streams. Cryogenic processing has been
proved to reduce capital and operating costs of recovering natural
gas liquids (NGL's). Cryogenic fractionation, however, encounters
potential problems when more than about 5 % C02 is present in
the gas stream. When a gas containing large quantities of CO 2 en-
counters the process conditions of a cryogenic demethanizer, the
CO 2 may freeze, thereby plugging the trays or packing and
preventing tower operation.
To avoid such problems, C02-rich gas processing involved an
extra treating step. A physical or chemical solvent was used to
absorb the CO 2, or a freeze-suppression additive was used to
prevent the CO 2 from solidifying. In both cases, the extra treaticg
step involved the recovery of the solvent or additive after the
C)/C0 2 separation.
The CFZ process was developed to take advantage of cryogenic
processing for C) /C02 separation without additives.) The process
uses a cryogenic distillation tower with a special internal section·
designed to handle the solidification and melting of CO 2, The sepa-
ration occurs in a single column with no solvent or additive recovery
required.
Fig. 1 illustrates the major steps involved for the CFZ process
compared with solvent or additive processes. After dehydration,
the CFZ process separates acid-gas components by cryogenic dis-
tillation through the controlled freezing and melting of the CO 2
in a single column. The solvent and additive processes require a
second column to regenerate the solvent or to recover the additive.
The solvent or additive is then recirculated. The CFZ process elim-
inates the regeneration/recovery column and fluid recirculation. Ad-
ditionally, the acid components leave the CFZ column as a liquid,
enabling economical transportation by pumps.
This paper describes how the process controls the freezing and
melting of CO 2 in a specially designed section of an otherwise con-
ventional distillation tower. In addition, the paper compares the CFZ
process to other gas-treating technologies, discusses operational re-
sults of a large-scale pilot plant, and gives examples of potential
CFZ applications.
CFZ Process
The CFZ process uses distillation, solidification, and melting to
separate C) and CO 2 physically in a single column. The process
achieves direct separation without use of solids-processing
equipment. Solid CO 2 forms in a vapor space and falls into a spe-
cially designed melting tray. Fig. 2 illustrates the CFZ column.
The top and bottom sections of the column are similar to a conven-
tional cryogenic demethanizer. The top section removes CO 2 and
heavier components from the overhead product. The bottom section
strips C) from the liquid CO 2 product. The solidification and
melting of C02 occurs in the specially designed CFZ middle
section. That section does not contain packing or trays like a con-
"Now with Esso Norge.
Copyright 1989 Society of Petroleum Engineers
ventional column; instead, it contains spray nozzles and a melting
tray. Liquid containing 3 to 8 mol % CO 2 is spray contacted with
vapor containing about 15 mol % CO 2 that is rising from the
melting tray. The liquid that is sprayed is collected in a chimney
tray located at the bottom of the top section. Solid CO 2 forms and
falls onto the warm liquid layer below. Vapor from the lower section
heats the liquid on the melting tray, maintaining the temperature
above the freezing point of C02' All solids are confined to the
CFZ section and do not enter or leave the section, thereby elimi-
nating any need for solids-processing equipment. The liquid from
the melting tray is fed into the conventional bottom section.
Fig. 3, based on the work reported in Ref. 2, illustrates the ne-
cessity for the CFZ section in cryogenic distillation. The
pressure/temperature diagram shows the pure-C I and pure-C02
saturation curves. For various C I /C02 mixtures, a locus can be
drawn connecting the mixture critical points. Operations above the
critical pressure of C) (Feed B in Fig. 3) approach the critical
locus, where the liquid and vapor phases become indistinguishable
and thereby prevent further distillation. The limitation of the critical
locus is reached before a C) product of < 2 to 4 mol % C02 is ob-
tained. Operating a distillation column at pressures below the critical
pressure of C) (Feed A of Fig. 3) would result in the formation
of solid CO 2 before the desired C I purity is attained. A CFZ
section allows the distillation path to proceed straight through the
solid-C0 2 region and produces a high-purity C) product.
The operation of a CFZ tower can be described with the temper-
ature/composition diagram for the C)/C0 2 system in Fig. 4.
Regions for a given pressure phase are mapped to show the presence
of vapor, liquid, vapor and liquid, and vapor and solid. The limits
of the vaporlliquid regions at the vertical axes are defined by the
saturation temperatures of both pure C I and pure CO 2, Operation
of a CFZ column would occur in the vapor/solid and vapor/liquid
regions. Vapor in the lower section of the column becomes leaner
in C02 and colder while rising through the liquid of each stage.
The vapor eventually reaches a phase region where, upon further
cooling, a liquid mixture of C) and C02 cannot exist. Rather, a
solid, pure-C0 2 phase will form in equilibrium with a C I /C02
vapor. Further cooling will continue to form pure, solid CO 2 from
the vapor. Solidification from the vapor phase continues as long
as the C02 vapor concentration is greater than about 5 mol %. At
that point, further cooling of the vapor results in the formation of
a liquid mixture of C) and C02' Conventional vaporlliquid distil-
lation can then be used to reduce further the amount of C02 in the
vapor. In the CFZ section, solid C02 is formed by simultaneously
cooling a vapor of about 15 mol % C02 and evaporating a liquid
being sprayed that has about 3 to 8 mol % CO 2 ,
Points on the temperature/composition diagram can be related
to the schematic ofthe tower. Warm vapor from the bottom section
(Point Av) is used to melt the solids on the CFZ melting tray. The
liquid at the free surface of the CFZ melting tray is slightly warmer
than the solid CO 2 condition (Point BL). The cold, C I -rich liquid
(Point DL) is sprayed into the CFZ section. Vapor exiting the spray
section is cold, depleted in CO 2 , and enriched in C I (Point Cv).
The CFZ section may represent more than one equivalent
vaporlliquid-equilibrium theoretical stage for heat and mass transfer
because the solids formed are essentially pure C02'

SPE Production Engineering, August 1989 265

 SOLVENT
SOLVENT
, - - _ . - - MAKE·UP
CFZ
Fig. 1-MaJor steps Involved In the CFZ, solvent, or additive processes.
METHANE
VAPOR
~~~:=~__ METHANE
k CARBON DIOXIDE
FEED
CARBON DIOXIDE
LIQUID
Fig. 2-Slmplifled illustration of a CFZ column.
Application of the CFZ Proce••
Ref. 3 discusses various applications of CFZ technology. The CFZ
process may be applicable when removing CO 2 from a gas stream
is desirable. CFZ technology may be integrated into a complete
gas-processing scheme, such as N2 rejection, liquefied natUral gas
(LNG) production, NGL recovery, H2S sweetening, and EOR in-
jection. Ref. 4 shows how the thermal efficiency of gas-processing
facilities may be increased by integrating cryogenic, acid-gas
removal with other cold-temperature processes-for example, N2
rejection or LNG production. CFZ technology integrates well with
these processes because it produces a cold C I fraction with a CO 2
concentration suitable for colder cryogenic processing. Refriger-
ation requirements in the downstream processing will be reduced
because the feed will be below -84°C [-120°F].
Sour-gas streams having a low concentration of NGL's may be
processed with CFZ technology to produce a vapor C I fraction and
a liquid acid-gas fraction. The liquid bottoms product may be
pumped to desired sales or reinjection pressures requiring less power
than the compression of an acid-gas product produced by solvent-
type processes. The refrigeration potential of the CFZ bottoms liquid
alternatively may be realized by expanding and vaporizing at low
266
ADDITIVE
3.447 kPa
TOP TRAYS
S+V CFZ
r----4.---------------_*sv
T
BOTTOM
TOWER
TRAYS
x.Y
Fig. 3-Thermodynamic basis for CFZ technology.
pressure. The low-pressure bottoms product may be vented or, if
needed, fed to a sulfur-recovery plant.
In EOR where C02 is used as an injectant, the associated gases
produced may approach 80% C02 when the injected CO 2 breaks
through the formation. Only one CFZ tower may be required to
remove C I from the associated gas to produce a liquid-C0 2/NGL
miscible injectant that can be pumped to injection pressure. Addi-
tional separation may be integrated into the process if NGL's are
desired for sale. The CFZ process may be designed to handle
changing CO 2 feed compositions.
Processes that can remove C02 from natural gas are dry bed,
chemical solvent, physical solvent, hybrid (physical/chemical)
solvent, membrane, and cryogenic distillation (including the CFZ,
freeze-suppression additive, and bulk fractionation). Refs. 5 through
7 discuss the applicability of various process alternatives.
The CFZ offers a number of advantages over other CO 2 removal
processes.
I. It can economically remove larger amounts of CO 2 than dry
bed, chemical solvent, or hybrid solvent processes.
2. CFZ requires no solvent-regeneration equipment such as that
needed for chemical, physical, or hybrid solvent processes.
SPE Production Engineering, August 1989
 9.853
CRITICAL LOCUS
8.274
. /"
"." ..... -------- ...................

:. 6.895
100% ../
~
METHANE / " FEE~
W 5.518 _~*~--------B----------y
a:
::l 4.137 ~~--~------A--------~
en
en
w
a:
Do

-100 -78 -58 -34 -12

TEMPERATURE, °C
METHANE-C0 2 SYSTEM 80nOMS co 2 PRODUCT

Fig. 4- Temperature/composition diagram for C l/CO 2

system. Fig. 5-Slmpllfled schematic of the CFZ large-scale pilot plant.

3. This process requires no additive-regeneration equipment, as

the additive process does.
4. CFZ can obtain a much higher-purity C 1 product than either
membranes or bulk cryogenic CO 2 removal.
·5. Unlike every other process, the CFZ produces a C02-rich
liquid stream.
6. This process can heat-integrate very well with other cryogenic
processes, such as LNG production or N2 rejection, unlike non-
cryogenic treating processes.
7. The column can be designed to reject H 2 S to parts-per-million
levels, unlike membrane and bulk cryogenic processes.
8. Because the CFZ process is dry, owing to upfront dehydration,
the system is noncorrosive, unlike many solvent processes.
The major tradeoff in using the CFZ is the increased need for
refrigeration, but this additional refrigeration is frequently more
than offset by the overall simplicity and flexibility of the CFZ
process. In general, the CFZ is applicable whenever cryogenic de-
methanization is preferred but hampered by possible solid CO 2 for-
mation.
CFZ Proce•• Development
The development of the CFZ process began with a conceptual eval-
uation in 1983. In May 1986, a large-scale pilot plant was com-
missioned and operated until May 1987. Flexibility was built into
the design of the pilot plant to measure the plant performance at
various operating conditions and to evaluate design parameters. Op-
erations of the pilot plant successfully proved the CFZ concept.
Fig. 5 is a simplified schematic of the pilot plant. The plant con-
sisted of mole sieve dehydration, inlet cooling, C02 feed blending,
and the CFZ tower. Refrigeration was provided by a cascaded eth-
ylene/propane system.
The pilot plant achieved multiweek operation at 4240 kPa [615
psia], producing overhead compositions ranging frdro 700 ppm to
2 mol% C02 and bottoms products with 0.5 to 1.0 mol% C 1 for
inlet gas rates of 5663 to 16990 std m 3 /d [200 to 600 MscflD]
and feed compositions of 15 to 65 mol% C02' The temperatures,
compositions, and flows around the CFZ section were consistent
with thermodynamic predictions. Typically, vapor containing about
20 mol % C02 rose from the bottom tower trays into the CFZ
section. Vapor off the top of the CFZ section typically contained
about 3 mol % CO 2, The vapor from the CFZ section was depleted
further to concentrations ranging from 2 mol % to 700 ppm CO 2,
depending on the reflux rate and location. The overhead product
purity was limited by inadequate insulation at the top of the tower,
which limited reflux capacity owing to excessive heat leak. The
liquid CO 2 from the bottom of the tower consistently contained < 1
mol% C 1 .
During prolonged operation, there was no indication that solid
C02 was accumulating in either the tower trayed sections or the
CFZ. Measured differential pressures across the trays in the middle
section were steady and consistent with the design hydraulics.
Fig. 6 illustrates typical conditions during successful operations.
Feed rates were varied from 7929 to 10 760 std m 3/d [280 to 380
Mscf/D], with the C 1 content varied from 75 t'o 85 mol% and the
SPE Production Engineering, August 1989
METHANE
0.1 - 0.2% CO 2
CFZ
SECTION
7.9 - 10.8 km 3/d
75 - 85% C1
15 - 25% CO 2
-2&OC/-4&°C
4.240 kPa
CARBON DIOXIDE
0.1 - 3% C1
Fig. 6- Typical conditions during successful operations of
the CFZ pilot plant.
CO 2 content from 15 to 25 mol %. Feed temperature varied from
-26 to -46°C [-15 to -51°F], and the pressure was maintained
at 4240 kPa [615 psia]. Methane product containing 0.1 to 0.2 mol %
CO 2 was produced out the top of the column at -86°C [-123°F].
Liquid from the top distillation section was sprayed into the CFZ
section at a temperature of -79°C [ -110°F], and the CFZ melting
tray was maintained between -54 and -65°C [-65 and -85°F).
The bottoms CO 2 product contained 0.1 to 3 mol% C 1 and was
produced at temperatures between 4 and 10°C [39 and 50°F).
The CFZ melting tray both performs the normal functions of a
distillation tray and provides a large, warm reservoir that can melt
the solid CO 2 formed in the CFZ section. A test was conducted
to vary the height of the liquid on the melting tray. The column
was operated with liquid heights ranging from 0.76 to 1.83 m [2.5
to 6.0 ft]. The operation was relatively insensitive to the liquid level
and insensitive to changing liquid levels. A liquid level ofO.76·m
[2.5 ft] was adequate to maintain operation, but a lower level may
be possible.
The CFZ section was designed and built with sprays located at
four different heights to determine the effect of various locations
and rates of spray. The pilot plant was best controlled by having
full flow through the top nozzle located 6.86 m [22.5 ft) above the
267
 present in large enough quantities to necessitate removal. Because-'
TABLE 1-RESIDUE GAS PROCESSING FEED
N2 is rejected at very low temperatures, the CFZ to remove CO 2
AND PRODUCT CONDITIONS
may be integrated with the NRU. In this case,8 the CFZ tower is
Dry NGL Fuel Gas C1 used to separate the C" N2, and helium from the CO 2, producing
Feed Product Product Product an overhead vapor stream containing 2,000 ppm CO 2 at -101°C
-- --- --- [-150°F]. The CO 2 is rejected as a liquid product at 3895 kPa
Flow rate, 10 3 m3 /d 775 12 121 642
Pressure, kPa 4240 4137 4137 4137 and 2°C [565 psia and 36°F]. The NRU column separates the C,
Temperature, °C 24 79 3 -29- and CO 2 from the helium and N 2. Use of available internal
Composition, mol% refrigeration resulted in a high overall thermal efficiency. Addi-
C1 80.73 0 1.50 97.09 tionally, integrating the CFZ with the NRU design allows the normal
C2 5.05 31.35 28.79 0.11 NRU feed specification for CO 2 to be relaxed. The process uses
C3 1.49 42.69 5.47 0 an external C, refrigeration loop to generate reflux for the N2/C,
iC 4 0.13 5.96 0.26 0 separation so that the coldest temperature seen by CO 2-containing
nC 4 0.28 14.34 0.42 0 liquid is about -126°C [-195°F]. At this temperature, 5,000-ppm
iC s 0.03 1.80 0.02 0
nC s 0.03 1.86 0.01 0 CO 2 would not freeze. Relaxing the C02 specification reduces the
N2 0.66 0 0 0.80 energy and capital cost requirements. The integrated CFZ/NRU
CO 2 11.60 2.00 63.53 2.00 design has a 20% power consumption advantage over a comparably
sized physical-absorption-based design. Additionally, the capital
cost for the CFZ/NRU design was estimated to be about 16% less,
melting tray, with a second nozzle located 1.37 m [4.5 ft] below while the annual gross income realized was estimated to be about
the first to maintain proper levels and temperatures in the tower. 6% higher.
The testing also showed that the nozzle spray feed temperature must
be below -81°C at 4240 kPa [-114°F at 615 psia] to prevent high CFZ for Fuel Gas Treating. CFZ technology may be applied to
concentrations of CO 2 from accumulating, and subsequently produce fuel gas from a high-C0 2, low-heat-value gas stream. The
freezing, in the top part of the column. design is similar to a cryogenic expander plant with the addition
The pilot plant was generally operated at a maximum flow rate of an ethylene refrigeration loop to provide reflux to the CFZ de-
of 16990 std m3 /d and 4,240 kPa [600 MscflD and 615 psia]. methanizer. The fuel gas unit requires no heat and less than 0.00216
Subsequent testing to operate the unit at pressures below 4033 kPa kW /std m 3 • d [82 hp/MMscf-D] of feed. 8
[585 psia] at the maximum flow rate were unsuccessful because
of the inadequate refrigeration capacity built into the pilot plant. Residue Gas Processing. The first two examples were for rela-
With the process successfully demonstrated through the operation tively high concentrations of C02 (58 and 63.3 mol%). This ex-
of the large-scale pilot plant, the next step was to develop various ample illustrates the use of CFZ technology for a lower
conceptual designs to quantify the incentives for using the CFZ for concentration of C02, 11.6 mol %. Table I lists the feed and
various applications. product streams for a conceptual design for processing a residue gas.
The objectives of the process illustrated in Fig. 7 are to produce
CFZ Example Applications a clean methane product, to produce a suitable fuel gas, and to re-
Ref. 8 gives two potential applications for CFZ technology: the cover any remaining NGL's. The process is designed around the
first example explores the integration of the CFZ with a downstream concept of a base-load cascade refrigeration system. Four levels
N2 rejection process; the second discusses a process for generating (-26.4, -40.2, -57.8, and -87.1 °C [-15.5, -40.4, -72.0,
fuel gas from a low-Btu gas. These cases have a high concentration and -124.8°FD and two refrigerants (propane and ethane) are used
of CO 2 in the feed stream, 58% for the integrated CFZ/N 2- to meet the necessary cooling requirements for the process to
rejection-unit (NRU) design and 63.3% for the CFZ fuel-gas- produce the C" fuel gas, and NGL product streams, as shown in
treating unit. Following a review of these two designs, a detailed Table I.
discussion of a CFZ conceptual design for a residue gas containing The feed gas enters the process from a dehydration unit at 24°C
a lower concentration of CO 2 is given. and 4240 kPa [75°F and 615 psia]. The inlet gas is cooled and par-
tially condensed by a combination of the CFZ column reboilers,
Integrated CFZ/NRU Design. Low-temperature CO 2 removal propane/ethane refrigeration, and heat exchange with the CFZ tower
technology may be applied effectively when both N2 and C02 are overhead product. The inlet stream enters the first tower at - 54°C

FEED

OUTSIDE
HEAT

Fig. 7-Process flow diagram with CFZ technology used to process a residue gas stream.

268 SPE Production Engineering, August 1989

 4
\~
7
I a
\ 0
~ '--....
13
~ II..
18
~ ....W
19
-100 -78 -58 -34 -12
\ 10
TEMPERATURE,oC
Fig. 8-Predlcted temperature profile for a CFZ column to
process a residue gas stream.
[-65°Fl The NGL product exits the bottom of the first tower.
The overhead from the first tower is cooled further by a combi-
nation of ethane refrigeration and heat exchange with the CFZ tower
overhead product- The temperature of the feed stream entering the
CFZ tower is -65°C [-85°F]. The CFZ section is located in the
column above the feed. In this section, CO 2 lean vapor rises off
a specially designed chimney tray and is contacted with C 1-rich
liquid that is being sprayed into the top of the CFZ section. The
CO 2 in the rising vapor freezes, thereby reducing the vapor-C0 2
content level enough that, when the vapor reaches the upper distil-
lation section, the CO 2 content of the liquid condensed is low
enough to avoid freezing. The CO 2 frozen out in the CFZ section
is remelted when it falls into the CFZ chimney-tray liquid.
Figs. 8 and 9 illustrate the temperature profile of the CFZ column
simulation and the predicted region of CO 2 solidification. The CFZ
section is shown to operate between -80 and -69°C [-112 and
-92°F]. That is, the C1-rich liquid is sprayed into the CFZ section
at a temperature less than - 80°C [-112 OF] and the COz-rich
liquid is drawn off the CFZ chimney tray at a temperature greater
than -69°C [-92°F]. Freezing of the C02 is not avoided but is
controlled in the specially designed section.
The overhead vapor leaves the CFZ reflux accumulator at - 84 °C
[-119°F]. The stream is then used to subcool the ethane refrigerant,
to cool the feed stream, and to condense the propane refrigerant,
heating the stream to 4°C [39°Fl The stream may then be com-
pressed to an appropriate sales pressure.
The fuel gas product stream exits the bottom of the CFZ column,
is produced as a liquid at 2.5°C [36.5°F], and has a net heating
value of 23400 kJ/m 3 [628 Btu/ft3].
The cascade refrigeration system is supplied by two levels of
propane and two levels of ethane refrigeration. Low- and high-
pressure propane is used to cool the feed stream and to condense
the ethane refrigerant. Low-pressure ethane is used to condense
reflux for the CFZ column; high-pressure ethane is used to cool
the feed stream. The propane is condensed by its use to supply heat
to the reboiler of the CFZ tower and by its exchange of heat with
the CFZ tower overhead product. An air cooler condenses the re-
maining propane. Figs. 10 and II illustrate the propane and ethane
refrigeration loops.
The total power required to compress the ethane and propane is
estimated to be 16 112 kW [21,597 hpJ (ethane-5439 kW [7,291
hpJ; propane-1O 673 kW [14,306 hp]) for a feed gas rate of
7.08x106 m 3/d [250 MMscflD]. This power requirement
(0.00227 kW/m 3 'd [86 hp/MMscf-D]) does not include com-
pression of the product streams or power required for pumps.
The conceptual design generates a C 1 product meeting a sales
specification of 2 % CO 2 with essentially no heavier hydrocarbons.
The fuel gas product may be flashed to generate a miscible-gas in-
jectant along with fuel gas.
SPE Production Engineering, August 1989
Q
5
:::;
!
N
(J
I- 10
Z
W
(J
a:
w
0
::!
100
-100 -78 -58 -34 -12 10
TEMPERATURE, °C
Fig. 9-Predlcted formation of solid CO 2 when CFZ technol-
ogy Is used to process a residue gas stream.
An alternative design to process the same residue gas stream is
illustrated in Fig. 12. The objectives of the design are to produce
a methane stream for reinjection, to maximize the recovery of
propane and heavier hydrocarbons, and to produce a suitable mis-
cible injectant- The alternative design recovers about 97 % of the
propane and heavier hydrocarbons and produces a miscible' injectant
containing 62% CO 2 , 36% ethane, 1% Cl> and I % propane. The
C 1 stream for reinjection contains 0.3% ethane and 3% CO 2 , This
design illustrates how the CFZ process can be heat-integrated with
other cryogenic processes, such as liquid petroleum gas (LPG) pro-
duction.
The inlet gas is cooled and partially condensed by a combination
of the CFZ column reboilers (HX-001 and HX-002), propane
refrigeration (HX-003 and HX-004), and heat exchange with the
CFZ tower overhead product (HX-005). The stream enters the first
tower (T-OOI) at -47°C [-53°F]. The methane and light ends are
stripped out in this first tower, with the liquids produced at 93°C
[199°F]. The liquids are then cooled (through A-ooI) to 32°C
[90°F] and fed into the second tower (T-002). The overhead gas
from the first tower is cooled with ethane refrigeration (HX-006)
to -65°C [-85°F] and fed into the CFZ tower (T-003). The CFZ
tower uses ethane refrigeration in the condenser (HX-007) cooling
the overhead to -83°C [-117°F]. The overhead product (C 1) is
heated by cooling the ethane (HX-009 and HX-OIO), the inlet stream
(HX -005), and the propane (HX-0 11). The CFZ tower reboiler (HX-
008) is used to condense the propane. The bottoms product stream
of the CFZ tower is fed into the second tower (T-002), which uses
propane refrigeration (HX-003) to condense the overhead (the mis-
cible injectant). The LPG product is produced from the bottom of
this second tower.
Conclusions
The CFZ technology is being developed to process effectively the
gases containing appreciable quantities of C02' The CFZ has four
major advantages in processing C02-rich gases.
1. It performs the C 1/C0 2 separation in a single column with
no solvent or additive recovery required.
2. It can be integrated efficiently with other cryogenic processes.
3. CFZ produces a CO 2-rich liquid from the bottom of the
column that can be economically pumped to pipeline or reinjection
pressure or used for refrigeration.
4. It can be designed to handle changing CO2 feed compositions,
such as that seen in some EOR projects.
The CFZ process is a simple, cost-effective method to process
gas streams containing CO 2 and has been successfully demon-
strated through the operation of a large-scale pilot plant- The process
uses proven facilities, equipment, and control philosophies. Con-
ceptual designs have been developed for a variety of feed gas com-
269
 AIR COOLER

CFZ TOWER CFZ TOWER

OVERHEAD REBOILER
EXCHANGER

193 kPa
110 kPa 586 kPa

COMPRESSOR
LIQUID

FEED/ETHANE CHILLER

Fig. 10-Propane refrigeration loop required to process a residue gas stream with CFZ tech-
nology.

-44°C

CFZTOWER LOW HIGH PRESSURE

OVERHEAD PRESSURE PROPANE COOLER
SUBCOOLER PROPANE
COOLER

414 kPa 110 kPa 896 kPa

-87°C
-58°C
CFZTOWER
CONDENSER COMPRESSOR
LIQUID

CFZTOWER TOWER 1
FEED CHILLER FEED CHILLER

Fig. 11-Ethane refrigeration loop required to process a residue gas stream with CFZ tech-
nology.

positions containing 11.6 to 63.3 mol% CO 2 . In general, CFZ
technology may be applied when cryogenic demethanization is pre-
ferred and when solid CO 2 formation may be encountered.
R.f.........
1. Valencia, I.A. and Denton, R.D.: "Method and Apparatus for
Separating Carbon Dioxide and Other Acid Gases from Methane by
the Use of Distillation and a Controlled Freeze Zone," U.S. Patent
No. 4,318,723 (March 9, 1982).
2. Donnelly, H.G. and Katz, D.L.: "Phase Equilibria in the Carbon
Dioxide-Methane System," Ind. & Eng. Chern. (March 1954) 46, No.
3, 511.
3. Victory, DJ. and Valencia, J.A.: "The CFZ Process: Direct Methane-
Carbon Dioxide Fractionation," Proc., Gas Processors Assn. Annual
Convention, Denver (March 16-18, 1987).
4. Denton, R.D. and Rule, D.D.: "Integrated Low-Temperature Proc-
essing of Sour Natural Gas," Proc., Gas Processors Assn. Annual Con-
vention, Houston (March 18-20, 1985) 92-96.
5. King, J.C. et al.: "Rigorous Screening Selects Sour-Gas Plant Process,"
Oil & Gas J. (Sept. 1986) 101-10.

270 SPE Production Engineering, August 1989

 MISCIBLE
HX-010 HX-009
INJECTANT

V-002

1
-22"C

V-OO-l -I ,=u-44'--_-3"C_

-------------i( PROPANE
LPG
L-==~ rc
•
METHANE
..
Fig. 12-Alternatlve process flow diagram with CFZ technology used to process a re81due ga8 stream.

6. Maddox. R.N. and Morgan. D.J.: "Select EOR Processes for C02." 81 Metric Conversion Factors
Hydrocarbon Processing (Aug. 1986) 59-63.
7. Price. B.C .• Zey. A.F .• and Ryan. J.M.: "Sour Gas Processing for
fi3 x 2.831 685 E-02 m3
Gas Sales and LNG Production." paper SPE 14057 presented at the OF (OF-32)/1.8 °C
1986 SPE IntI. Meeting on Petroleum Engineering. March 17-20. psi x 6.894757 E+OO kPa
Beijing.
8. Thomas. E.R. and Denton. R.D.: "Conceptual Studies Using the Con-
SPEPE
Original SPE manuscript received for review Feb. 5, 1988. Paper accepted for publication
trolled Freeze Zone (CFZ) Process." Proc.• American lost. of Chemical May 12, 1988. Revised manuscript received Aug. 15, 1988. Paper (SPE 1nOO) fire!
Engineers Summer Natl. Meeting. Minneapolis. MN (Aug. 16-19. presented' at the 1988 SPE Offshore South East Asia Conference held In Singapore, Feb.
1987). 2-5.

SPE Production Engineering. August 1989 271