United States Patent (19) 11) 4,157,904

Campbell et al. 45) Jun. 12, 1979

(54) HYDROCARBON GAS PROCESSING 3,292,380 12/1966 Bucklin .................................... 62/28
3,292,381 12/1966 Bludworth ............................... 62/28
75 Inventors: Roy E. Campbell; John D. Wilkinson, 3,360,944 1/1968 Knapp et al. ............................ 62/23
both of Midland, Tex. 3,433,026 3/1969 Swearingen ............................. 62/23
73 Assignee: The Ortloff Corporation, Midland, 3,626,448 12/1971 Crawford ................................. 62/23
Tex. 3,808,826 5/1974 Harper et al............................. 62/28
21 Appl. No.: 843,321 Primary Examiner-Norman Yudkoff
Attorney, Agent, or Firm-Brumbaugh, Graves,
22 Filed: Oct. 18, 1977 Donohue & Raymond
57 ABSTRACT
Related U.S. Application Data
A process for separating hydrocarbon gases is described
63 Continuation-in-part of Ser. No. 728,963, Oct. 4, 1976, for the recovery of gases such as ethane and heavier
abandoned, which is a continuation-in-part of Ser. No. hydrocarbons from natural gas streams or similar refin
712,771, Aug. 9, 1976, abandoned. ery or process streams. In the process described, the gas
(51) Int. Cl’................................................. F25J 3/02 to be separated is cooled at a high pressure to produce
(52) U.S. C. ........................................... 62/27; 62/23; partial condensation. The liquid from the partial con
62/38 densation is further cooled and then expanded to a
58) Field of Search ................... 62/23, 24, 27, 28, 38, lower pressure. At the lower pressure, the liquid is then
62/39 separated into fractions in a distillation column. The
56) References Cited basic separation process is improved by combining the
condensed high-pressure liquid with a stream having a
U.S. PATENT DOCUMENTS lower bubble point, with cooling of one or both streams
Re. 25, 193 7/1962 Schilling et al. ......................... 62/38 prior to expansion.
2,964,914 12/1960 Schuftan et al. ......................... 62/38
3,277,655 10/1978 Geist et al. ............................... 62/28 32 Claims, 9 Drawing Figures
U.S. Patent Jun. 12, 1979 Sheet 1 of 8 4,157,904

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 U.S. Patent Jun. 12, 1979 Sheet 5 of 8 4,157,904

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U.S. Patent Jun. 12, 1979 Sheet 7 of 8 4,157,904

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U.S. Patent Jun. 12, 1979 Sheet 8 of 8 4,157,904

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methanizer is a fractionating column in which the ex
HYDROCARBON GAS PROCESSING. pansion-cooled stream is fractionated to separate resid
This application is a continuation-in-part of our co ual methane, nitrogen and other volatile gases as over
pending application, Ser. No. 728,963, filed Oct. 4, 1976, head vapor from the desired products of ethane, pro
now abandoned, which, in turn, is a continuation-in-part pane and heavier components as bottom product.
of our co-pending application Ser. No. 712,771, filed If the feed stream is not totally condensed, typically it
Aug. 9, 1976 now abandoned. is not, the vapor remaining from this partial condensa
This invention relates to the processing of gas streams tion is passed through a turbo-expander, or expansion
containing hydrocarbons and other gases of similar valve, to a lower pressure at which additional liquids
volatility to remove desired condensable fractions. In 10 are condensed as a result of the further cooling of the
particular, the invention is concerned with processing stream. The pressure after the expansion is usually the
of gas streams such as natural gas, synthetic gas and same pressure at which the demethanizer is operated.
refinery gas streams to recover most of the propane and Liquids thus obtained are also supplied as a feed to the
a major portion of the ethane content thereof, together demethanizer. Typically, remaining vapor and the de
with substantially all of the heavier hydrocarbon con 15
methanizer overhead vapor are combined as the resid
tent of the gas. ual methane product gas.
Gas streams containing hydrocarbons and other gases In the ideal operation of such a separation process the
of similar volatility which may be processed according vapors leaving the process will contain substantially all
to the present invention include natural gas, synthetic of the methane found in the feed gas to the recovery
gas streams obtained from other hydrocarbon materials 20 plant, and substantially no hydrocarbons equivalent to
such as coal, crude oil, naphtha, oil shale, tar sands, and ethane or heavier components. The bottoms fraction
lignite. The major hydrocarbon components of natural leaving the demethanizer will contain substantially all
gas are methane and ethane, i.e., methane and ethane of the heavier components and essentially no methane.
together comprise at least 50% (molar) of the gas com In practice, however, this ideal situation is not obtained
position. There may also be lesser amounts of the rela 25 for the reason that the conventional demethanizer is
tively heavier hydrocarbons such as propane, butanes, operated largely as a stripping column. The methane
pentanes, and the like as well as H2, N2, CO2, and other product in the process, therefore, typically comprises
gases. A typical analysis of a natural gas stream to be vapors leaving the top fractionation stage of the column
processed in accordance with the invention would be, together with vapors not subjected to any rectification
in approximate mol %, 80% methane, 10% ethane, 5% 30 step. Substantial losses of ethane occur because the
propane, 0.5% iso-butane, 1.5% normal butane, 0.25% vapors discharged from the low temperature separation
iso-pentane, 0.25% normal pentane, 0.5% hexane plus, steps contain ethane and heavier components which
with the balance made up of nitrogen and carbon diox could be recovered if those vapors could be brought to
ide. Sulfur-containing gases are also often found in natu
ral gas. 35 lower temperatures or if they were brought in contact
Recent substantial increases in the market for the with a significant quantity of relatively heavy hydrocar
ethane and propane components of natural gas has pro bons, for example C3 and heavier, capable of absorbing
vided demand for processes yielding higher recovery the ethane.
levels of these products. Available processes for sepa As described in our prior applications Ser. No.
rating these materials include those based upon cooling 698,065 filed June 21, 1976, Ser. No. 712,825 filed Aug.
and refrigeration of gas, oil absorption, refrigerated oil 9, 1976 (both now abandoned), and our co-pending
absorption, and the more recent cryogenic processes application Ser. No. 728,962, filed Oct. 4, 1976, of
utilizing the principle of gas expansion through a me Campbell, Wilkinson and Rambo, improved ethane
chanical device to provide power while simultaneously recovery is achieved by cooling the condensed high
extracting heat from the system. Depending upon the 45 pressure liquid prior to expansion. Such cooling will
pressure of the gas source, the richness (ethane and reduce the temperature of the flash-expanded liquid
heavier hydrocarbons content) of the gas and the de feed supplied to the demethanizer and thus improve
sired end products, each of these prior art processes or ethane recovery. Moreover, as described in the afore
a combination thereof may be employed. mentioned applications, Ser. No. 698,065, Ser. No.
The cryogenic expansion type recovery process is 50 712,825, and Ser. No. 728,962, by pre-cooling the high
now generally preferred for ethane recovery because it pressure liquid feed, the temperature of the expanded
provides maximum simplicity with ease of start up, liquid may be sufficiently reduced that it can be used as
operating flexibility, good efficiency, safety, and good top column feed in the demethanizer, while the ex
reliability. U.S. Pat. Nos. 3,360,944, 3,292,380, and panded vapor is supplied to the demethanizer at a feed
3,292,381 describe relevant processes. 55 point intermediate the top feed and column bottom.
In a typical cryogenic expansion type recovery pro This variation permits recovery of ethane contained in
cess a feed gas stream under pressure is cooled by heat the expanded vapor which would otherwise be lost.
exchange with other streams of the process and/or It will be obvious that to supply external refrigeration
external sources of cooling such as a propane compres at this stage of the process is difficult because of the
sion-refrigeration system. As the gas is cooled, liquids extremely low temperatures encountered. In typical
are condensed and are collected in one or more separa demethanizer operations the expanded liquid and vapor
tors as a high-pressure liquid feed containing most of the feeds are at temperatures in the order of -120 F. to
desired C2-- components. The high-pressure liquid feed - 190 F. Accordingly, cooling of the condensed high
is then expanded to a lower pressure. The vaporization pressure liquid stream feed can best be achieved by heat
occurring during expansion of the liquid results in fur 65 exchange of the condensed high-pressure liquid stream
ther cooling of the remaining portion of the liquid. The feed with streams derived within the process as de
cooled stream comprising a mixture of liquid and vapor scribed in the above-identified applications Ser. No.
is demethanized in a demethanizer column. The de 698,065, Ser. No. 712,825, and Ser. No. 728,962.
 4,157,904
3 4
It will be recognized from the foregoing discussion FIG. 4 is a flow diagram illustrating the application
that the high-pressure liquid feed generally contains of the present invention to a feed pre-cooling process as
volatile gases (such as methane), as well as gases of described in FIG. 3; and
lower volatility and that cooling of the high-pressure FIG. 5 is a fragmentary flow diagram of the applica
liquid feed upon expansion results from vaporization of 5 tion of the present invention to a feed pre-cooling pro
a portion of the volatile gases. In accordance with the cess wherein the liquid feed is pre-cooled by a flash
present invention, the temperature drop obtained upon expanded portion of said liquid feed.
expansion of the high-pressure liquid feed can be in FIGS. 6A and 6B are graphs of carbon dioxide vs.
creased by combining that feed with a process stream temperature from one embodiment of this invention
compared to the prior art.
having a bubble point lower than the bubble point of the 10 FIG. 7 is a process flow plan illustrating the impor
high-pressure liquid feed at the pressure to which the
high-pressure feed is expanded. Prior to expansion, the tance of work expanding at least part of the high-pres
combined stream is cooled to a temperature below the sure vapor.
temperature of the high-pressure liquid feed. FIG. 8 is a carbon dioxide-temperature diagram com
This may be accomplished by cooling the high-pres 15 paring the processes of FIGS. 4 and 7.
sure liquid stream or the gaseous process stream (or In the following explanation of the above figures,
both) prior to combining them; or by cooling the com tables are provided summarizing flow rates calculated
bined streams if that is more convenient. Upon expan for representative process conditions. In the tables ap
sion, the combined stream will achieve a lower refriger- 20 pearing herein, the values for flow rates (in pound moles
ated temperature because of the presence of enhanced per hour) have been rounded to the nearest whole num
ber, for convenience. The total stream flow rates shown
quantities of the more volatile components which re in the tables include all non-hydrocarbon components
duces the bubble point of the combined stream and and hence are generally larger than the sum of the
which vaporizes at the lowest pressure to absorb in stream flow rates for the hydrocarbon components.
creased quantities of heat of vaporization. 25 Temperatures indicated are approximate values,
. It will be recognized that in practical situations, the rounded to the nearest degree.
bubble point temperature of the high-pressure liquid Referring to FIG. 1, for a fuller description of a typi
feed may be several degrees or more above its actual cal conventional ethane recovery process, plant inlet
process temperature due to non-equilibrium conditions gas from which carbon dioxide and sulfur compounds
arising during the condensation and separation of high- 30 have been removed (if the concentration of these com
pressure liquid and vapor feeds. Such a condition also pounds in the plant inlet gas would cause the product
arises when the high-pressure liquid feed is cooled in stream not to meet specifications, or cause icing in the
accordance with the invention disclosed in applications equipment), and which has been dehydrated enters the
Ser. No. 698,085 of June 21, 1976, Ser. No. 712,825 process at 120' F. and 910 psia as stream 23. It is divided
dated Aug. 9, 1976, and Ser. No. 728,962 of Oct. 4, 1976, 35 into two parallel streams and cooled to 45 F. by heat
which are identified above. When the bubble point exchange with cool residue gas at 5' F. in exchanger 10;
temperature significantly exceeds the actual process with product liquids (stream 26) at 82 F. in exchanger
temperature of the high-pressure liquid feed, the tem 11; and with demethanizer liquid at 53' F. in demeth
perature drop on expansion is less than the temperature anizer reboiler 12. From these exchangers, the streams
drop which would be obtained by expanding a high- 40 recombine and enter the gas chiller, exchanger 13,
pressure liquid feed at its bubble point. In accordance where the combined stream is cooled to 10 F. with
with the present invention, such a high-pressure liquid propane refrigerant at 5 F. The cooled stream is again
feed can be combined with a more volatile process divided into two parallel streams and further chilled by
stream as described above, and with moderate further heat exchange with cold residue gas (stream 29) at
cooling, provide improved process operations. This is 45 - 107 F. in exchanger 14, and with demethanizer liq
because addition of the gaseous process stream to the uids at -80 F. in demethanizer side reboiler 15. The
high-pressure liquid feed will result in absorption of streams are recombined, as stream 23a, and enter a high
pressure separator 16 at -45 F. and 900 psia. The
volatile gases until the actual bubble point temperature condensed
of the high-pressure liquid feed can be reduced to the SO demethanizer liquid (stream 24) is separated and fed to the
process temperature of the high-pressure liquid feed. sion engine may 19through expansion valve 30. An expan
Expansion of a liquid of such a reduced bubble point if desired. be used in place of the expansion valve
will result in colder refrigerated temperatures being The cooled gas from the high-pressure separator 16
achieved.
For a fuller understanding of this invention, reference flows through expander 17 where it is work expanded
may be had to the following drawings in which:
55 from 900 psia to 290 psia. The work expansion chills the
FIG. 1 is a flow diagram of a single-stage cryogenic gas to -125 F. Expander 17 is preferably a turbo
expander natural gas processing plant of the prior art expander, having a compressor 21 mounted on the ex
pander shaft. For convenience, expander 17 is some
incorporating a set of conditions for a typical rich natu times hereinafter referred to as the expansion means. In
ral gas stream; certain prior art embodiments, expander 17 is replaced
FIG. 2 is a flow diagram of single-stage cryogenic by a conventional expansion valve.
expander natural gas processing plant of the prior art Liquid condensed during expansion is separated in
incorporating a set of conditions for a typical lean natu low pressure separator 18. The liquid is fed on level
ral gas stream; control through line 25 to the demethanizer column 19
FIG. 3 is a flow diagram from companion applica 65 at the top and flows from a chimney tray (not shown) as
tion, Ser. No. 698,065, illustrating one technique by top feed to the column 19.
means of which high-pressure liquid feed gas can be It should be noted that in certain embodiments low
pre-cooled prior to expansion; pressure separator 18 may be included as part of de
 5
4,157,904 6
methanizer 19, occupying the top section of the column. TABLE II-continued
In this case, the expander outlet stream enters above a RECOVERIES
chimney tray at the bottom of the separator section, -
located at the top of the column. The liquid then flows Ethane 79.0% 17,355 GAL/DAY
Propane 98.2% 8,935 GAL/DAY
from the chimney tray as top feed to the demethanizing 5 COMPRESSEONHORSEPOWER
section of the column. Refrigeration O BHP
As liquid fed to demethanizer 19 flows down the Recompression 1180 BHP
column, it is contacted by vapors which strip the meth Total 1180 BHP
ane from the liquid to produce a demethanized liquid
product at the bottom. The heat required to generate 10
In the prior art cases discussed with respect to FIG.
stripping vapors is provided by heat exchangers 12 and 1 and FIG. 2 above, recoveries of ethane are 73% for
15.
The vapors stripped from the condensed liquid in the case of the rich gas feed and 79% for the lean gas
demethanizer 19 exit through line 27 to join the cold 15 feed. It is recognized that some improvement in yield
may result by adding one or more cooling steps foll
outlet gas from separator 18 via line 28. The combined lowed by one or more separation steps, or by altering
vapor stream then flows through line 29 back through the temperature of separator 16 or the pressure in sepa
heat exchangers 14 and 10. Following these exchangers, rator 18. Recoveries of ethane and propane obtained in
the gas flows through compressor 21 driven by expan this manner, while possibly improved over the cases
der 17 and directly coupled thereto. Compressor 21 20 illustrated by FIG. 1 and FIG. 2, are significantly less
compresses the gas to a discharge pressure of about 305 than yields which can be obtained in accordance with
psia. The gas then enters a compressor 22 and is com the process of the present invention. By way of illustra
pressed to a final discharge pressure of 900 psia. tion the process conditions of FIG. 2 can be altered by
Inlet and liquid component flow rates, outlet liquid reducing column pressure to 225 psia. At the lower
recoveries and compression requirements for this prior 25 pressure ethane and propane recoveries are somewhat
art process shown in FIG. 1 are given in the following increased (to 82.96% and 98.66%, respectively); how
table:
ever, the lower operating pressure requires a substantial
TABLE I increase in the horsepower requirements of the process
(FIG. 1) to 1353 BHP.
STREAM FLOW RATE SUMMARY - LB. MOLES/HR. 30 FIG. 3 shows one means, as described in the above
METH- ETH- PRO identified applications, Ser. No. 698,065, Ser. No.
STREAM ANE ANE PANE BUTANES- TOTAL 712,825, and Ser. No. 728,962, for pre-cooling the high
23 1100 222 163 130 1647 pressure liquid feed. In the process of FIG. 3, the par
24 795 202 157 129 1300 tially condensed feed gas 33a at -67 F. and 900 psia is
25 16 10 5 32
26 3 162 157 130 453 35 obtained as described in FIG. 2. The feed gas was as
RECOVERIES sumed to be a lean feed gas of the composition of stream
Ethane 72.9% 29,296 GAL/DAY 33 in FIG. 2. The partially condensed gas 33a enters a
Propane 96.2% 39,270 GAL/DAY high-pressure separator 16 where liquid and vapors are
COMPRESSION HORSEPOWER separated.
Refrigeration 256 BHP Following first the vapors 113 leaving separator 16,
Recompression 892 BHP the vapors enter a work expansion engine 17 in which
Total 1148 BHP
mechanical energy is extracted from the vapor portion
of the high pressure feed. As the vapor is expanded
In FIG. 2 a typical lean natural gas stream is pro from a pressure of about 900 psia to a pressure of about
cessed and cooled using a prior art process similar to 45 250 psia, work expansion cools the expanded vapor 113
that shown in FIG.1. The inlet gas stream 33 is cooled to a temperature of approximately - 153' F. The ex
to -69' F. and flows to high pressure separator 16 as panded and partially condensed vapor 113 is supplied as
stream 33a where the liquid contained therein is sepa a feed to demethanizer 19, wherein the vapor portion
rated and fed on level control through line 34 and ex rises and forms part of demethanizer overhead 117.
pansion valve 30 to demethanizer 19 in the middle of the 50 Demethanizer overhead 117 at a temperature of -156
column. F. combines with vapors 116 from flash vaporization
Cold gas from separator 16 flows through expander described below to form residue gas stream 118. The
17 where because of work expansion from 900 psia to combined, cold residue gas stream 118 then passes
255 psia, the gas is chilled to -160' F. The liquid con through heat exchanger 119. The warmed residue gas at
densed during expansion is separated in low pressure 55 -125 F. leaving heat exchanger 119 then returns to the
separator 18 and is fed on level control through line 35 preliminary cooling stages as illustrated, for example, in
to the demethanizer 19 as top feed to the column. FIG. 2, wherein further refrigeration contained in the
The data for this case are given in the following table: still cold vapor stream is recovered, and the vapor is
compressed, via compressor 21 (see FIG. 2) which is
TABLE II 60 driven by work expansion engine 17, and then further
compressed to a line pressure of 900 psia by supplemen
(FIG. 2) tary compressor 22.
STREAM FLOW RATE SUMMARY - LB. MOLES/HR.
METH- ETH- PRO Turning to the liquid 34 recovered from separator 16,
STREAM ANE ANE PANE BUTANES+ TOTAL liquid 34 passes through heat exchanger 119 in heat
33 1447 90 36 43 1647 5 exchange relation with the cold residue gas 118. This
34 280 42 25 39 391 results in a pre-cooling of the liquid portion of the par
35 133 35 4. 186 tially condensed high pressure feed gas. The sub-cooled
36 2 71 36 43 155 liquid is then expanded through an appropriate expan
 4,157,904 8
7
sion device, such as expansion valve 120, to a pressure TABLE III-continued
of approximately 250 psia. During expansion a portion 16 29 0 O 0 30
of the feed will vaporize, resulting in cooling of the 18 1445 O 0 1483
remaining part. In the process as illustrated in FIG. 3, 125 2 80 35 43 164
the expanded stream leaving expansion valve 120 5 RECOVERIES
reaches a temperature of -158' F. and enters a separa Ethane 89.1% 19,656 GAL/DAY
tor. The liquid portion is separated and supplied as Propane 97.7% 8,894 GAL/DAY
COMPRESSION HORSEPOWER
stream 115 to the fractionation column 19 as top feed. It Refrigeration 0 BHP
may be noted that by comparison with FIG. 2, the Recompression 177 BHP
expanded liquids through line 34 entering the demeth 10 Total 1177 BHP
anizer column only achieve a temperature of -134' F.
Because stream 115 of FIG. 3 is substantially cooler, it For purposes of further comparison with the present
may be used as top feed to the demethanizer to recover invention in the examples set forth below, a second base
ethane in the stream 113. The ethane recovered is with
drawn in the demethanizer bottoms 125. Demethanizer 15 case was calculated following the flow plan of FIG. 3
bottoms 125 are heat exchanged with incoming feed to and employing the same lean feed gas. In the modified
recover refrigeration therein as generally illustrated in flow plan, the feed gas to the process at 120 F. and 910
FIGS. 1 and 2. psia was cooled to -68 F. in the feed pre-coolers (for
In connection with FIG. 3, it should be noted that for example, exchangers 10, 11, 12, 14 and 15 of FIG. 2)
purposes of heat economy there will be one or more 20 rather than -67 F. and the column was operated at
demethanizer reboilers which exchange heat to cool slightly lower pressure, i.e., 240 psia rather than 250
incoming feed (not shown in FIG. 3) as illustrated gen psia. The result was a slight increase in recovery of
erally in FIGS. 1 and 2. For purposes of the illustrated ethane and propane, together with an increase in horse
process calculations appearing in FIG.3 and set forth in power requirements for the process. A summary of the
the table below, two such reboilers have been included 25 modified flow conditions and flow rates for the alter
as shown in FIG. 2. The reboilers are significant to the nate base case is set forth in Table IV below:
TABLE IV
(FIG. 3)
STREAM FLOW RATE SUMMARY - LB. MOLES/HR
STREAM METHANE ETHANE PROPANE BUTANES - TOTAL CONDITIONS
33a 1447 90 36 43 647 -68 F.; 900 psia
34 308 44 26 39 424 -68 F.; 900 psia
34a 308 44 26 39 424 - 153 F.; 900 psia
34b. 308 44 26 39 424 -161 F.; 240 psia
113 139 46 10 4. 1223 -68 F.; 900 psia
113a 1139 46 10 4. 1223 -153 F.; 240 psia
115 278 44 26 39 292 -161 F.; 240 psia
18 1446 8 O 1479 -160 F.; 240 psia
18a. 1446 8 1 O 1479 - 125 F.; 240 psia.
125 1 82 35 43 168 36 F.
RECOVERIES
Ethane 90.66% 19,907 GAL/DAY
Propane 98.08% 8,928 GAL/DAY
COMPRESSION HORSEPOWER
Refrigeration 0 BHP
Recompression 1258 BHP
Total 1258 BHP

overall heat economy of the process. Sub-cooling of the EXAMPLE

liquid stream 34 by overhead vapors 118 reduces the 50 The present invention is illustrated by the following
available refrigeration remaining in stream 118 for feed example which should be considered in conjunction
cooling purposes. However, the increased loading of with FIG. 4. FIG. 4 is a fragmentary flow diagram
demethanizer 19 with liquid stream 115 cooled in accor wherein a lean feed gas 33a at 900 psia is cooled to -67
dance with FIG. 3 provides additional available refrig F. and supplied to separator 16. The feed gas is cooled
eration in the reboilers. Accordingly, the overall heat 55 and partially condensed by heat exchange with various
balance of the process remains substantially unaffected. process streams (these heat exchangers not being
Inlet and liquid component flow rates, outlet recov shown), including side reboilers on the demethanizer
ery efficiencies, and expansion/compression require column 19 (side reboilers now shown), heat exchange
ments for the process illustrated in FIG. 3 are set forth with demethanizer bottoms and product gas as de
in the following table: 60 scribed in FIG. 2. If necessary, as indicated in FIGS. 1
TABLE III and 2, supplementary external refrigeration may also be
(FIG. 3) provided. The process conditions described in FIG. 4
STREAM FLOW RATE SUMMARY - LB. MOLES/HR and the flow rates set forth in Table V below, corre
STREAM
METH-
ANE
ETH- PRO spond to the process of a lean feed gas of the composi
ANE PANE BUTANES - TOTAL 65 tion set forth in Table II and FIG. 2.
33a
34
1447
280
90
42
36
25
43
39
1647
391
Following the process of FIG. 4, the partially con
13 1167 48 11 4. 1256 densed gas 33a containing a liquid portion and a vapor
115 251 42 25 39 361 portion, enters high pressure separator 16 where the
 4,157,904
10
liquid portion is separated. The liquid from separator 16 cess was not simply the result of increasing the horse
(stream 34) is combined with a portion of the vapor power requirements. To the contrary, Table IV shows
from separator 16, (stream 169). The combined stream that even when the process conditions of the base case
then passes through heat exchanger 154 in heat ex were altered to supply the demethanizer at a lower
change relation with the overhead vapor stream 1585 pressure, thus increasing horsepower requirements of
from the demethanizer resulting in cooling and conden the base case to 1258 horsepower, ethane and propane
sation of the combined stream. The cooled stream is recovery increased only to 90.66% and 98.08%, respec
- 152 F. is then expanded through an appropriate ex tively. When the present invention was employed, as in
pansion device, such as expansion valve 155, to a pres Example 1, ethane and propane recoveries increased
sure of approximately 250 psia. During expansion a 10 over those set forth in the alternate base case, even
portion of the feed will vaporize, resulting in cooling of though somewhat less horsepower was actually re
the remaining part. In the process illustrated in FIG. 4, quired.
the expanded stream 157 leaving expansion valve 155 From a preferred design standpoint in the practice of
reaches a temperature of -162 F., and is supplied to this invention, particularly for leaner gases, all of the
the fractionation column 19 as top feed. 15
liquid from separator 16 will be combined with some
The remaining vapor from separator 16 (stream 170) portion of the vapor from separator 16. The combined
enters a work expansion engine 17 in which mechanical
energy is extracted from this portion of the high pres stream will then be cooled and expanded as described.
sure feed. As that vapor is expanded from a pressure of The amount of vapor employed in the combined stream
about 900 psia to a pressure of about 250 psia, the work 20 will be sufficient that the combined stream will provide
expansion cools the expanded vapor 153 to a tempera the cooling duty and temperature needed to control the
ture of approximately -153 F. The expanded and top temperature of the demethanizer. The liquids from
partially condensed vapor 153 is supplied as feed to separator 16, when added to the vapor forming the top
demethanizer 19 at an intermediate point. column feed, increase the surface tension of the feed at
It may be noted that by comparison with the first base 25 column condition, thereby minimizing the formation of
case of FIG. 3 the liquid 115 of said FIG. 3 entering the small liquid particles which are difficult to separate
demethanizer column achieves a temperature of about from the top vapor stream.
- 158' F. To achieve a lower temperature of -161 F. For richer gases, where there is more liquid from
at the column top in the alternate base case, a reduced separator 16 than required to maintain the column top
column pressure was necessary. The reduced column 30 condition, it may be more economical from a design
pressure increased horsepower requirement, but only standpoint to divide the liquid from separator 16, and to
slightly improved yield. In FIG. 4, as a result of com expand a portion directly into the tower, or possibly
bining the liquid 34 from separator 16 with a portion of after some sub-cooling. This may make possible savings
the high pressure feed vapor 169 prior to sub-cooling in in heat exchange requirements and higher recovery.
heat exchanger 154, the colder demethanizer top feed of 35 As set forth in the above-mentioned applications, Ser.
- 162 F. can be realized without lowering the demeth No. 698,065, Ser. No. 712,825, and Ser. No. 728,962,
anizer pressure. there are a variety of modified flow plans characterized
Inlet and liquid component flow rates, outlet recoverby sub-cooling of some or all of the liquid feed obtained
ies, and expansion/compression requirements for the from separator 16 to which the present invention is
process of Example 1 are set forth in the following 40 applicable. Two or more of these techniques may be
Table V. used concurrently. Among these flow plans are the
TABLE V following:
(FIG. 4) 1. Uncondensed vapors leaving separator 16 may be
STREAM FLOW RATE SUMMARY - LB, MOLES/HR. expanded such as in a work expansion engine to pro
METH- ETH- PRO- 45 duce a cold partially condensed liquid and gas. The
STREAM ANE ANE PANE BUTANES -- TOTAL liquids are separated and supplied to the demethanizer
33a
34
447
280
90
42
36
25
43
39
1647
391
column. All or a portion of the liquid thus separated
157 444 48 27 40 567
may be used as a source of refrigeration for sub-cooling
158 1445 7 1 0 1476 liquid condensate 34 recovered in separator 16. Alterna
159 2 83 35 43 17 SO tively, all or a portion of the entire expanded vapor
169
170
164
003
6
42
2
9
1
3
176
1080
stream may be used. Additionally, side demethanizer
RECOVERIES reboilers may be used to provide sub-cooling of conden
Ethane 92.2% 20,261 GAL/DAY sate 34 from separator 16. In accordance with the pres
Propane 98.3% 8,949 GAL/DAY ent invention, flow plans can be modified by combining
COMPRESSION HORSEPOWER 55 liquid condensate from separator 16 with a portion of
Refrigeration O BHP the vapors from that separator prior to sub-cooling and
Recompression 1221 BHP flashing of the liquid condensate.
Total 221 BHP 2. Liquid condensate from separator 16 may be di
rected through a sub-cooling heat exchanger and thence
Comparison of the ethane and propane recoveries as 60 to an expansion valve wherein it is expanded from line
between Tables III and V shows that in the absence of pressure (e.g.,900 psia as in FIGS. 1-4) to demethanizer
enriching the liquids from separator 16 ethane recovery column operating pressure. This will result in a vapor
is 89.1% and propane recovery is 97.7%. Enrichment of liquid mixture which can be separated either in a sepa
the separator liquids in accordance with Example 1 (see rate low pressure separator or may be fed directly to the
FIG. 4) increases ethane and propane recoveries to 65 demethanizer column with column internals designed to
92.5% and 98.3%, respectively. effect the necessary vapor-liquid separation. The flash
Comparison of Tables IV and V further shows that ing results in further cooling of the feed to the column.
the improvement in yields obtained in the present pro A portion of the further cooled liquid thereby obtained
 4,157,904 12
11
is employed as the coolant in heat exchange with the porization as the pressure is reduced from about 900 to
high pressure condensate from separator 16 and then 290 psia. The cold stream from expansion valve 182
supplied to the demethanizer column as a second feed at then flows through exchanger 184 where it is used to
an intermediate point in the column. In accordance with sub-cool the liquids from separator 16. From exchanger
the present invention, such a process can be improved 184, the stream flows to demethanizer 19 as its lowest
by enriching the liquid condensate leaving separator 16 feed at -67 F.
with a portion of the vapors from that separator prior to The remaining liquid portion 179 from exchanger
sub-cooling and flashing of the liquid condensate. 184, still at high pressure, combines with a portion 177
3. The uncondensed vapor leaving separator 16 may of the vapor stream from separator 16. The combined
be expanded such as in a work expansion engine from a 10 stream then flows through heat exchanger 185 where it
high pressure (e.g., 900 psia as in FIGS. 1-4) to the is cooled to approximately - 140 F. by heat exchange
operating pressure of the demethanizer and the entire with column overhead stream 180. At this temperature,
cooled gas-liquid mixture resulting from expansion may the combined stream is substantially condensed. The
be usd to sub-cool the condensate recovered in separa condensed stream then enters expansion valve 183
tor 16. The sub-cooled condensate is thereafter flashed 15 where it undergoes expansion and flash vaporization as
and is supplied to the demethanizer as a feed. This em the pressure is reduced from 895 psia to 290 psia. From
bodiment may be improved by enriching the liquid expansion valve 183 the cold stream proceeds to de
condensate recovered from separator 16 with a portion methanizer 19 as its top feed.
of the vapors leaving that separator prior to sub-cooling Inlet and liquid component flow rates, outlet recov
and flashing of the liquid condensate. 20
ery efficiencies, and expansion/compression require
In lieu of or in addition to the foregoing additional ments for the embodiment of this invention as illustrated
external refrigeration may be provided if increased
yields are required; however, one of the advantages of in FIG. 5 are given in the following table:
the invention described in said applications Ser. No. TABLE V
698,065, Ser. No. 712,825, and Ser. No. 728,962 is that 25 (FIG. 5)
- where the condensate is sub-cooled, improved yields STREAM FLOW RATE SUMMARY - LB, MOLES/HR.
frequently may be obtained without the necessity of METH- ETH- PRO
increasing process horsepower requirements. STREAM ANE ANE PANE BUTANES - TOTAL
Still another embodiment of the present invention is 174 304 162 80 54 1647
set forth in the following example, which should read in 30 175
176
486
723
109
47
66
12
51
2
723
817
conjunction with related FIG. 5. 177 95 6 2 1 107
EXAMPLE 2 178 243 54 33 26 361
179 243 55 33 25 362
FIG. 5 is a fragmentary flow process diagram for 180
181
301
3
14
48
1
79
0.
54
1362
285
recovery of ethane and heavier components from a 35
RECOVERIES
hydrocarbon feed gas containing methane, ethane and Ethane 91.47% 36,039 GAL/DAY
heavier hydrocarbons. As illustrated in FIG. 5, a par Propane 98.38% 19,732 GAL/DAY
tially condensed high-pressure feed gas 174 is provided HORSEPOWER REQUIREMENTS
to a separator 16 at -55 F. and 900 psia. Cooling of the Refrigeration 130 BHP
feed gas to -55 F. may be provided as shown, for Recompression 987 BHP
example, in FIGS. 1 and 2 by heat exchange to the feed Total 1117 BHP
gas with residue methane gas and other process streams
such as demethanizer side reboilers and bottom streams
(these heat exchangers not being shown), and, if neces It is noted that in addition to the procedure outlined
sary, with appropriate external refrigeration. For pur 45 in FIG. 5 for handling the cooled liquid 175 from sepa
rator 16, other alternate procedures may be used in
poses of calculations on which this example is based, some situations to advantage. One alternate procedure
two demethanizer reboilers have been assumed. How
ever, in contrast to FIGS. 1 and 2, the process calcula involves carrying a portion of the cooled liquid 179
tions (e.g., temperature, pressure and flow rates have directly from the separator through another expansion
been based on an assumed gaseous feed intermediate in 50 valve directly into the demethanizer column 19 at inter
composition between the lean and rich case gases set mediate In a
level.
second alternate procedure, the liquid 175 from
forth in FIGS. 1 and 2 and Tables I and II.
As indicated in accompanying FIG. 5, the liquid and separator 16 can be sub-cooled by residue gas instead of
vapor portions of the partially condensed feed 174 are auto refrigeration as illustrated in FIG. 5. In this alter
separated in separator 16. The vapor from separator 16 55 nate, high pressure condensate may be cooled in two
is divided into two portions. The first portion 176 flows successive heat exchangers, each employing residue gas
through expander 17 where, because of work expansion as one refrigerant. After passage through the first ex
from 900 to 290 psia, it is cooled to -133° F. From changer, partly cooled high pressure condensate is di
expander 17 the chilled vapor flows to demethanizer 19 vided into two parts. The first part is expanded through
as its middle feed. The second vapor portion 177 is an expansion valve and supplied to the demethanizer
combined with a portion of the sub-cooled liquid from column 19 as an intermediate feed. The second part of
heat exchanger 184 as it flows to heat exchanger 185. the partly cooled condensate continues through the
The liquid 175 from separator 16 flows through ex second exchanger where it is further cooled and then
changer 184 where it is sub-cooled to -130' F. by heat combined with vapor from separator 16. The combined
exchange with the cold stream from expansion valve 65 stream is then further cooled and expanded whereafter
183. The sub-cooled liquid is then divided into two it is supplied to the column 19 as top feed. Alternatively,
portions. The first portion 178 flows through expansion vapor from separator 16 could be added to the second
valve 182 where it undergoes expansion and flash va part of the partly cooled liquid stream before entering
 13
4,157,904 14
the second exchanger, thus eliminating the need for -continued
subsequent cooling of the combined stream. Feed Gas Composition
In still another modification of the present invention,
the flash-expanded stream, such as stream 186 of FIG. 5, N2 57
may be directed into heat exchange relation with the
work expanded vapor stream 187, thus cooling stream The principal operating conditions for the process
187 and warming stream 186. If stream 187 is thus were the following:
cooled sufficiently, it may be advantageous to employ
stream 187 as the top feed to the demethanizer and 10 Pressure in high-pressure separator 16 895 psia
stream 186 as an intermediate feed since, as is evident Temperature of high-pressure separator 16 0 F.
from the process flow plan of FIG. 5, stream 186 is % of feed condensed in separator 16 44%
richer in heavier components, i.e., C2--, and stream 187 % of gas from separator 16 to expander 17 60%
contains more lighter components, e.g., methane and Temperature of combined stream to expansion
valve 155 - 120 F.
uncondensed gases. 15 Temperature of expansion valve outlet - 147 F.
Other alternate procedures for obtaining the cooled Column overhead temperature - 145 F.
liquid 175 are described in aforementioned applications Temperature of gas from expander 17
Pressure in demethanizer
-83 F.
360 psia
Ser. No. 698,065, Ser. No. 712,825, and Ser. No. % ethane recovery 87.33%
768,962. These alternate procedures may be used in % propane recovery 97.05%
various combinations, when appropriate. Also, these 20 Horsepower:
various schemes may be used in place of or in conjunc Recompression 3194 BHP
Refrigeration 0 BHP
tion with cooling provided by residue gas to the en Total 3194 BHP
riched stream, prior to its use as top feed to the column
19.
These alternate procedures are particularly useful 25 For base-case purposes the same feed gas was treated
when, because of the richness of the feed to the process, also in accordance with the process of FIG. 2. How
the cooling capacity of the overhead gas stream 180 is ever, for more efficient utilization of available heat
insufficient to cool the entire volume of liquid recov duty, the feed pre-cooling exchangers prior to the high
ered through line 175 to the desired low temperature. pressure separator were slightly rearranged. The princi
As is well known, natural gas streams usually contain 30 pal operating parameters were the following:
carbon dioxide, sometimes in substantial amounts. The
presence of carbon dioxide in the demethanizer can lead Pressure in high-pressure separator 16 895 psia
to icing of the column internals under cryogenic condi Temperature in high-pressure separator 16 -70 F.
tions. Even when feed gas contains less than 1% carbon % of feed gas condensed in separator 16 2.95%
dioxide, it fractionates in the demethanizer and can 35 Temperature
expander 17
of expanded gases leavin
- 136 F.
build up to concentrations of as much as 5% to 10% or Temperature of expanded liquid leaving
more. At such high concentrations, carbon dioxide can flash valve 30
Temperature of demethanizer overhead vapor
- 116 F.
-134 F.
freeze out depending on temperatures, pressure, Pressure of demethanizer 360 psia
whether the carbon dioxide is in the liquid or vapor % ethane recovery 60.55%
phase, and the liquid phase solubility. % propane recovery 90.58%
In the present invention it has been found that when Horsepower:
the vapor from the high-pressure separator is expanded Recompression 3074 BHP
Refrigeration 0 BHP
and supplied to the demethanizer below the top column Total 3074 BHP
feed position the problem of carbon dioxide icing cabe
substantially mitigated. The high-pressure separator gas 45
typically contains a large amount of methane relative to Plots were made for each of these cases of CO2 con
the amount of ethane and carbon dioxide. When sup centration as a function of temperature in the demeth
plied at a mid column feed position, therefore, the high anizer, as shown in FIGS. 6A and 6B. Also shown on
pressure separator gas tends to dilute the carbon dioxide 50 these figures are the liquid-solid and vapor-solid equilib
concentration, and to prevent it from increasing to icing ria. The equilibrium data given in FIGS. 6A and 6B are
levels. - for the methane-carbon dioxide system. Warren E.
White, Carl M. Ferunczy and Ned P. Baudat, "Short
EXAMPLE 3 Cut to CO2 Solubility", Hydrocarbon Processing, August
The advantage of the present invention can be readily 1973. These data are considered generally representa
seen by plotting carbon dioxide concentration and tem
55 tive for the methane and ethane systems. If the CO2
perature for various trays of the demethanizer. To illus concentration at a particular temperature in the column
trate the preparation of such a chart the flow process is at or above the equilibrium line at that temperature,
icing can be expected. For practical design purposes,
illustrated in FIG. 4 was applied to the treatment of the engineer usually requires a margin of safety, i.e., the
6588 moles/hr of a feed gas of the following composi 60 actual concentration should be less than the "icing"
tion: concentration by a suitable safety factor.
FIG. 6A shows that in the process of FIG. 2 the
Feed Gas Composition carbon dioxide concentration in the demethanizer rose
Methane 93.82 well above the tolerable level. Such a gas could not be
Ethane 3.6
65 used in a conventional process, therefore, without pre
Propane 1.06 treating it to remove a substantial amount of the carbon
Butane--. .80. dioxide. By contrast, FIG. 6B shows that when the
CO2. 59 expanded vapors are employed as a mid column feed in
 4,157,904 16
15
accordance with the present invention, the CO2 concen in the above-mentioned application Ser. No 728,962 of
tration is reduced in the demethanizer to a point well Oct. 4, 1976).
below the “icing” level. The importance of utilizing at least a portion of the
It should be noted in connection with the foregoing high-pressure vapor stream in a work expansion engine
that when designing demethanizer columns for use in may be seen by the following illustrative case, in which
the present invention, the designer will routinely verify the feed gas of Example 3 is processed. In the illustra
that icing in the column will not occur. Even when tive case, all of the high-pressure vapor is recombined
vapor is fed at a mid-column position it is possible that with the high-pressure liquid condensation prior to flash
icing may occur if the process is designed for the high expansion of the latter to the fractionation column.
est possible ethane recovery. Such designs normally call 10 In explaining this illustrative case, reference will be
for the coldest practical temperature at the top of the made to FIG. 7. As shown in FIG. 7, incoming feed is
column. This will result in the carbon dioxide concen cooled by heat exchange with product liquid (ex
tration shifting to the right on the plots of FIGS.6A and changer 191), demethanizer reboiler (exchanger 192)
6B. Depending on the particular application, the result and partially warmed residue gas (exchanger 193). The
can be an objectionably high concentration of carbon 15 feed is further cooled by external propane refrigeration
dioxide near the top of the column. For such circum to - 14 F. (exchanger 194). Additional cooling is ex
stance, it may be necessary to accept a somewhat lower tracted from residue gas (exchanger 195) and from de
ethane recovery to avoid column icing, or to pre-treat methanizer column liquids in a side reboiler (exchanger
the feed gas to reduce carbon dioxide levels to the point 196). In this manner, the major portion of the incoming
where they can be tolerated in the demethanizer. In the 20 feed gas is cooled and supplied to separator 197 at -79
alternative, it may be possible to avoid icing in such a F. and 895 psia. Liquid from separator 197 is further
circumstance by other modifications in the process cooled in heat exchanger 198, and then recombined
conditions. For instance, it may be possible to operate with vapor therefrom. Separate cooling of the liquid
the high-pressure separator at a higher temperature, to permits advantageous design of the liquid-liquid heat
increase the relative amount of gas from the high-pres 25 exchanger (see, for example, the discussion of this in
sure separator which is expanded through expander 17, U.S. Pat. No. 3,874,184 to Harper et al.) The recom
or to expand a part of the vapors from the high-pressure bined stream is further cooled in exchanger 199 to -94.'
separator through an isenthalpic expansion valve. If F., flash expanded to the demethanizer pressure of 250
such alterations can be made within the limitations of psia in flash valve 200 and supplied as the top column
the process heat balance, icing may be avoided without 30 feed to demethanizer 19 at -145 F.
losing ethane recovery. Inlet and liquid component flow rates, outlet recov
In connection with the process described above, it ery and expansion/compression requirements for the
should be noted that in some instances the feed to the process of FIG. 7 is shown in the following Table VIII:
top of the demethanizer is a liquid which is expanded
from a high pressure to the pressure of the demethanizer 35 TABLE VIII
(see, for example, FIGS. 4 and 5). In such cases, it may
be desirable to autocool the top column liquid feed. This (FIG. 7)
is accomplished by dividing the top column liquid feed STREAM FLOWPLAN SUMMARY - LB, MOLES/HR
METH- ETH- PRO
into two streams either before or after expansion. (Both STREAM ANE ANE PANE BUTANE-- TOTAL
streams are expanded if the top column feed is divided 33 6181 208 71 123 6588
before expansion). One of the two expanded streams 20 3819 84 14 6 3972
thus obtained is directed into a heat exchange relation 202 2362 124 57 117 266
with the top column feed prior to expansion. 203 677 25 3 6263
In carrying out the present invention, it is important 204 4. 183 68 122 325
that at least part of the high-pressure vapor remaining 45 RECOVERIES
after cooling and partial condensation of the feed be Ethane 87.6% 20,243 GAL/DAY
Propane 95.8% 8,982 GAL/DAY
expanded in a work expansion engine to the demeth HORSEPOWER REQUIREMENTS
anizer and supplied as a mid-column feed. There are Recompression 3792 BHP
two reasons for this: Refrigeration 261 BHP
(1) Extraction of work energy from the high-pressure 50 Total 4053 BHP
vapor stream by expansion in a work engine provides a
significant amount of refrigeration to the process. If As can be seen by comparing the foregoing with
work is not extracted from this stream, it is necessary to Example 3, to achieve essentially the same recovery of
supply external refrigeration and, because of the low 55 ethane a great increase in horsepower is required. The
temperatures required, providing that refrigeration may increase in horsepower arises not only because of the
become uneconomic. Additionally, recompression re unavailability of expansion work through expansion of a
quirements are increased, since if the high pressure portion of the high-pressure vapor stream, but also
vapor is work expanded to cool it the energy extracted because external refrigeration was required to achieve
is available to supply some of the recompression re the temperature level needed to obtain the desired eth
quirements of the process. ane recovery.
(2) The vapor supplied to the mid-column feed posi It is also important to note that by expanding a por
tion serves to dilute the carbon dioxide present in the tion of the high-pressure vapor and providing it as a
liquids supplied to the top of the column. If the carbon mid-column feed, the carbon dioxide level in the col
dioxide is not diluted, it will tend to accumulate in the
upper stages of the column and cause CO2 icing: 65 umn is reduced, and column icing conditions are
(It should be noted that where rich gases are pro thereby avoided. This is best seen by constructing car
cessed, the liquifaction temperature may be sufficiently bon-dioxide-temperature diagrams in the same manner
high that total condensation can be practical, as shown as FIGS. 6A and 6B were constructed. When following
 4,157,904
17 18
the process of the prior art, serious carbon dioxide icing 4. The improvement according to claim 3 wherein
problems are encountered in both liquid phase (line 205 said liquid portion (a) is cooled to a temperature below
of FIG. 8) and vapor phase (line 206 of FIG. 8). How its bubble point prior to being combined with said pro
ever, when the process of the present invention is used, CeSS Stream.
the carbon dioxide icing is avoided, see FIG. 6B. 5 5. The improvement according to claim 4 wherein
In the practice of the present invention, it will be said process stream (1) is cooled prior to being com
recognized that the amount of vapor which is work bined with said liquid portion.
expanded and supplied to the mid-column feed position 6. The improvement according to claim 3 wherein
will depend upon the amount of refrigeration which can said combined stream is cooled prior to expansion.
be economically extracted from it balanced against the O 7. The improvement according to claim 6 wherein
advantage of a reduced column overhead temperature said process stream (a) is cooled prior to being com
which can be obtained by using that same gas to enrich bined with said liquid portion.
the high-pressure liquid which is flash expanded to 8. In a process for separation of a feed gas into a
supply the top column feed. Selection of the amount of 15 volatile residue gas and a relatively less volatile frac
vapor work expanded and supplied to a mid-column tion, said feed gas containing hydrocarbons, methane
feed position will also take into consideration the and ethane together comprising a major portion of said
amount of vapor which must be supplied to the mid feed gas, wherein
column position in order to avoid carbon dioxide icing. (a) said feed gas under pressure is cooled sufficiently
As a general rule of thumb, we have found that for best 20 to partially condense said gas, forming thereby a
results at least about 25% of the gas should be work liquid portion of said feed gas and a vapor feed gas;
expanded and supplied to the mid-column feed position (b) at least some of said liquid portion is expanded in
and, for lean gases, about 50% or more of the gas should an expansion means to a lower pressure, whereby a
be work expanded. part of said liquid portion vaporizes to cool the
We claim: expanded liquid portion to a refrigerated tempera
1. In a process for separation of a feed gas into a 25 ture; and
volatile residue gas and a relatively less volatile frac (c) at least some of the expanded liquid portion is
tion, said feed gas containing hydrocarbons, methane subsequently treated in a fractionating column to
and ethane together comprising a major portion of said separate said relatively less volatile fraction,
feed gas, wherein 30 the improvement comprising
(a) said feed gas under pressure is cooled sufficiently (1) dividing at least part of the liquid portion resulting
to partially condense said gas forming thereby a in step (a) into a first stream and a remaining
liquid portion of said feed gas and a vapor feed gas; stream;
(b) at least some of the liquid portion is expanded in (2) expanding said first stream to said lower pressure,
an expansion means to a lower pressure whereby a 35 whereby a portion thereof vaporizes to cool the
part of said liquid portion vaporizes to cool the expanded first stream;
expanded liquid portion to a refrigerated tempera (3) directing said expanded first stream into heat ex
ture; and change relation with the remaining part (1) of said
(c) at least some of the expanded liquid portion is liquid portion;
subsequently treated in a fractionation column to (4) combining said remaining part with a process
separate said relatively less volatile fraction; stream having a bubble point below the bubble
the improvement comprising point of the liquid portion from step (a), thereby to
(1) combining at least part of liquid portion (a) with a form a combined stream;
process stream having a bubble point below the (5) supplying said combined stream to an expansion
bubble point of said liquid portion (a), to form 45 means at a temperature which is below the bubble
thereby a combined stream; point of said liquid portion (a);
(2) supplying said combined stream to said expansion (6) expanding said combined stream to said lower
means at a temperature which is below the bubble pressure, whereby the refrigerated temperature
point of said liquid portion (a); achieved in said expansion is lower than the refrig
(3) expanding said combined stream to said lower 50 erated temperature achieved in step (2);
pressure, whereby the refrigerated temperature
achieved in expansion step (b) is reduced; (7) thereafter supplying at least some of said ex
(4) thereafter supplying at least some of said ex panded combined stream to said fractionation col
panded combined stream to said fractionation col umn at a first feed position; and
umn at a first feed position; and 55 (8) expanding at least 25% of the vapor feed gas
(5) expanding at least a portion of said vapor feed gas resulting from step (a) in a work-expansion engine,
in a work expansion engine to said lower pressure, and supplying the expanded vapor to the fraction
and supplying the expanded vapor to the fraction ation column at a second feed point, and said sec
ation column at a second feed point, said second ond feed point being at a lower column position
feed point being at a lower column position than than said first feed point, the amount of said feed
said first feed point. gas vapor which is work expanded being sufficient
2. The improvement according to claim 1 wherein at to reduce the risk of carbon dioxide icing in the
least 25% of the vapor feed gas is expanded to said fractionation column.
lower pressure by work expansion. 9. In a process for separation of a feed gas into a
3. The improvement according to claim 2 wherein 65 volatile residue gas and a relatively less volatile frac
the amount of feed gas vapor which is work expanded tion, said feed gas containing hydrocarbons, methane
is sufficient to reduce the risk of carbon dioxide icing in and ethane together comprising the major portion of
the fractionation column. said feed gas, wherein
 4,157,904
19 20
(a) said gas under pressure is cooled sufficiently to expand it to a lower pressure, whereby it is further
partially condense said gas forming thereby a liquid cooled; and
portion of said feed gas and a vapor feed gas; (c) a fractionation column connected to receive at
(b) the liquid portion at a temperature below its bub least a portion of the expanded feed gas from said
ble point is expanded in an expansion means to a 5 expansion means (b), said distillation means being
lower pressure whereby a part of said liquid por adapted to separate said relatively less volatile
tion vaporizes to cool the expanded liquid portion fraction,
to a refrigerated temperature; the improvement which comprises
(c) at least some of said expanded liquid portion is (i) means for combining at least part of the liquid
subsequently treated in a fractionation columm to O portion obtained from said cooling means (a) with
separate said relatively less volatile fraction; a process stream having a bubble point below the
the improvement comprising bubble point of said liquid portion (a) to form
(1) combining a portion of said vapor feed gas and at thereby a combined stream;
least a part of the liquid portion (a) prior to expan (ii) cooling means for cooling at least one of said part
sion thereof to form thereby a combined stream; 15 of said liquid portion, said process stream and said
(2) supplying said combined stream to said expansion combined stream sufficiently that said combined
means at a temperature below the bubble point of stream has a temperature below the bubble point of
said liquid portion (a); said liquid portion (a);
. (3) expanding said combined stream to said lower (iii) means connecting said expansion means (b) to
pressure whereby the refrigerated temperature 20 receive said combined stream at a temperature
achieved in expansion step (b) is reduced; below the bubble point of said liquid portion (a),
(4) thereafter supplying at least some of said ex wherein said combined stream is expanded to said
panded combined stream to said fractionation col lower pressure;
umn at a first feed point; and (iv) means connecting said expansion means (b) to
(5) expanding the remaining portion of the vapor feed 25
said fractionation column to supply at least a por
gas in a word expansion and supplying the ex tion of the expanded combined stream as a feed to
panded remaining portion to said fractionation said fractionation column at a first feed point; and
columm at a second feed point, said second feed (v) work expansion means connected to said cooling
point being at a lower column position than the means (a) to receive at least some of the vapor feed
first feed point. 30
gas and to expand said lower pressure, said work
10. The improvement according to claim 9 wherein at expansion means being further connected to supply
least 25% of said vapor feed gas is work-expanded to the expanded vapor feed gas to said fractionation
said lower pressure.
11. The improvement according to claim 10 wherein column at a second feed point, said second feed
the amount of vapor feed gas work expanded to the 35 point being at a lower column position than said
lower pressure is sufficient to reduce the risk of carbon first feed point.
dioxide icing in the fractionation column. 18. The improvement according to claim 17 wherein
12. A process according to claim 11 wherein at least the work expansion means (v) is adapted to expand at
part of the combined stream after expansion thereof is least 25% of the feed gas vapor.
19. The improvement according to claim 18 wherein
supplied to said fractionation column as the top column the work expansion means (v) is adapted to expand a
feed.
13. A process according to claim 11 wherein the sufficient amount offeed gas vapor to reduce the risk of
combined stream is cooled prior to expansion by direct carbon dioxide icing in the fractionation column.
ing said stream into heat exchange contact with at least 20. The improvement according to claim 19 wherein
a part of the residue gas. 45 said cooling means (ii) comprises means to cool part of
14. A process according to claim 13 wherein at least said liquid portion (a) to a temperature below its bubble
some of said vapor feed gas portion is cooled prior to point prior to combination of said liquid portion with
combining it with said liquid portion. said process
15. A process according to claim 11 wherein at least 21. The improvement according to claim 20 wherein
a portion of said liquid portion is sub-cooled prior to 50 said cooling means further includes means for cooling
combining it with said vapor feed gas portion. said process stream prior to combination thereof with
16. A process according to claim 11, wherein said said liquid portion.
combined stream is cooled by directing said combined 22. The improvement according to claim 19 wherein
stream into heat exchange contact with the expanded said cooling means (ii) comprises means for cooling said
remaining portion of the feed gas vapor before said 55 combined stream prior to expansion thereof.
expanded remaining portion is supplied to the fraction 23. The improvement according to claim 21 wherein
ation column. said cooling means (ii) further includes means for cool
17. In an apparatus for the separation of a feed gas ing said process stream prior to combination thereof
into a volatile residue gas and a relatively less volatile with said liquid portion.
fraction, said feed containing hydrocarbons, methane 24. An apparatus for the separation of a feed gas into
and ethane comprising the major portion of said feed a volatile residue gas and a relatively less volatile frac
gas, said apparatus having tion, said feed gas containing hydrocarbons, methane
(a) cooling means to cool said gas under pressure and ethane together comprising the major portion of
sufficiently to partially condense said gas and form said feed gas, said apparatus having
thereby a liquid portion of said gas and a vapor 65 (a) cooling means to cool said gas under pressure
feed gas; sufficiently to partially condense said gas and form
(b) expansion means connected to said cooling means thereby a liquid portion of said gas and a vapor
to receive said partly condensed feed gas and to feed gas;
 21
4,157,904 22
(b) expansion means connected to said cooling means tion vaporizes to cool the expanded liquid portion;
to receive said partially condensed feed gas and to and
expand it to a lower pressure whereby it is further (c) a fractionation column connected to receive at
cooled; and - - - least some of said expanded liquid portion and to
(c) a fractionation column connected to receive at 5 separate said relatively less volatile fraction,
least a portion of the expanded feed gas from said the improvement wherein said exchange means includes
expansion means (b), said fractionation column (i) means connected to said cooling means (a) for
being adapted to separate said relatively less vola combining a portion of said vapor feed gas and at
tile fraction, least part of said liquid portion prior to expansion
the improvement which comprises 10 thereof to form thereby a combined stream;
(i) dividing means connected to receive at least part (ii) means for cooling at least one of said liquid por
of said liquid portion (a), and to divide said part tion, said vapor feed gas and said combined stream
into a first stream and a remaining part; sufficiently that said combined stream has a tem
(ii) expansion means connected to said dividing means perature below the bubble point of said liquid por
to receive said first stream and to expand it to a 15 tion (a) prior to expansion thereof;
lower pressure, whereby a portion thereof vapor (iii) means connecting said expansion means (b) to
izes to cool the expanded first stream; receive said combined stream at a temperature
(iii) heat exchange means connected to said expansion below the bubble point of said liquid portion (a),
means to receive the remaining part of said liquid wherein said combined stream is expanded to said
portion, said heat exchange means further being 20 lower pressure;
connected between said cooling means (a) and said (iv) means connecting said expansion means (b) to
dividing means (i) to direct the expanded first seid fractionation column to supply at least a por
stream into heat exchange relation with said re tion of the expanded combined stream to the frac
maining part of said liquid portion; tionation column at a first feed point; and
(iv) means connected to said dividing means to re 25 (v) work expansion means connected to said cooling
ceive said remaining part and to combine said re means (a) to receive the remaining portion of the
maining part with said process stream havung a vapor feed gas and to expand it to said lower pres
bubble point below the bubble point of said liquid sure, said work expansion means being further
portion (a) to form said combined stream having connected to supply the expanded remaining part
(v) heat exchange means connected between said 30 to the fractionation column at a second feed point,
means (iv) and said expansion means (iii) adapted to said second feed point being at a lower column
further cool said combined stream prior to expan position than the first feed point.
sion thereof sufficiently that said combined stream 26. The improvement according to claim 25 wherein
has a temperature below the bubble point of said said work expansion means is adapted to expand at least
liquid portion (a); 35 25% of the vapor feed gas to said lower pressure.
(vi) means connecting said expansion means (b) to 27. The improvement according to claim 26 wherein
receive said combined stream at a temperature the work expansion means is adapted to expand a suffi
below the bubble point of said liquid portion (a), cient amount of said vapor feed gas to said lower pres
wherein said combined stream is expanded to said sure to reduce the risk of carbon dioxide icing in said
lower pressure; column.
(vii) means connecting said expansion means (b) to 28. In the improvement according to claim 27, the
said fractionation column to supply at least a por further improvement including means connected to
tion of the expanded combined stream as a feed to supply said combined stream after expansion thereof to
said fractionation column at a first feed point; and said fractionation column as the top column feed.
(viii) work expansion means connected to said cool 45 29. In the improvement according to claim 27, the
ing means (a) to receive at least 25% of the feed gas further improvement wherein said cooling means (ii)
vapor and to expand it to said lower pressure, said includes means for cooling said combined stream prior
work expansion means being further connected to to expansion thereof connected to direct said combined
supply the expanded vapor feed gas to said frac stream to heat exchange contact with at least part of
tionation column at a second feed point, said sec SO residue gas produced by said apparatus.
ond feed point being at a lower column position 30. In the improvement according to claim 29, the
than the first feed point, said work expansion means further improvement wherein said cooling means (ii)
further being adapted to expand a sufficient amount includes means for cooling said vapor feed gas portion
offeed gas vapor to reduce the risk of carbon diox prior to combining it with said liquid portion.
ide icing in the fractionation column. 55 31. In the improvement according to claim 27, the
25. In an apparatus for the separation of a feed gas further improvement wherein said cooling means (ii)
into a volatile residue gas and a relatively less volatile includes means for cooling said liquid portion prior to
fraction, said feed gas containing hydrocarbons, meth combination of it with said vapor feed gas portion.
ane and ethane, together comprising the major portion 32. In the improvement according to claim 27, the
of said feed gas, further improvement including
said apparatus having (1) dividing means connected to said cooling means
(a) cooling means to cool said gas under pressure (a) to receive said vapor feed gas and to divide it
sufficiently to partially condense said feed gas and into a first part and a second part;
to form thereby a liquid portion of said feed gas and (2) means connecting said dividing means (1) to said
a vapor feed gas; 65 combining means (i), whereby said first part of said
(b) expansion means connected to said cooling means vapor feed gas is combined with at least a portion
to receive said liquid portion and expand it to a of said liquid portion (a) prior thereof to form said
lower pressure, whereby a part of said liquid por combined stream;
 4,157,904
23 24
(3) expansion means connected to said dividing means cooled vapor stream and further being connected
(1) to receive said second part of said vapor feed between said combining means (i) and said expan
gas and to expand said second part to said lower sion means (iii) to direct said cooled vapor stream
pressure to produce thereby a cooled vapor stream; into heat exchange contact with said combined
and 5 stream, thereby to cool said combined stream.
(4) heat exchange means connected to receive said k . . . .

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p UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 4, 157, 904 Dated June 12, 1979

Inventor(s) Roy E. Campbell et al.

It is certified that error appears in the above-identified patent
and that said Letters Patent are hereby corrected as shown below:
Col. 9, line 7, "stream is" should read -- stream at--;
ua-in-a-a-a-a-a-a-a-

Col. 11, line 58, "-133°F. " should read --about -133°F. --
tream-tomim-minimirorumm-arawam--a
Col. 13, line 44, "ca be" should read --can be--;
re-mailim-woma-aaraaman-mamm--a
Col. 14, line 39, "60.55%" should read -- 60.92%--;
urr-i-m-immurma-mason--a
Col. 18, line ll, "(a)" should read -- (l)--;
unr-me-mimimamaha-to-v--
Col. 19, line 26, "Word" should read --work-- ;
mammon-amm-mura-a-a-
Col. 20, line 48, after "process", insert -- stream. --;
tri-immammarymimi-amirpur-as
ol. 20, line 56, "claim 21" should read --claim 22--; and
immuramaaaaa-harman-a-a-a-am-ne
Col. 2l, line 27, "havung" should read --having--.
eigned and sealed this
Sixteenth Day of October 1979
SEAL
Attest:

LUTRELLE F. PARKER
RUTH C. MASON
Attesting Officer Acting Commissioner of Patents and Trademarks