July 6, 1965 R. P.

CAHN 3,192,732
LOW TEMPERATURE REFRIGERATION IN ETHYLENE PLANTs
Filed April 24, 1961
X)J.
HYDROGEN, 3O 3 EXPANSION WALWE
32-METSANE sta" 50 49
24 26 48 4O

23 Sté 33
25 27 as N r\
*(
-
) lu ?' 5 ETHYLENE
a PROPYLENE
3
N 2O DISTILLATION
TOWER

bar
is 7- 38
-37

G 4
6 N 45

3 2 Na Q 44
ABSORPTION 47 (N
TOWER 7 0.

6
ETHANE
4- (N
9

8 DEETHANIZER

IO- N
PROPYLENE--4

Robert P. Cohn NVENTOR

RY 7-7 at-4 a 64----ele

PATENT ATTORNEY
United States Patent Office 3,92,732
Patiented July 6, 1965
2
the low temperature refrigeration capacity of the evapo
3,923, rating ethane.
LOW TEMPERATURE REFREIGERATION IN For example, if 100 lb. moles of liquid ethane is mixed
ETHYLENE PLANTS
a 3- with 1000 moles of cold tail gas at 50 p.s.i.g., -120 o F.,
Robert P. Caan,ingviibara,
aad Eagi (C N.J., assignor to Esso Research 5 the following refrigeration will be available at the -120
"ge;E.; Scies: AERelaware F. level or lower due to the evaporating ethane:
Claims. (C. 62-7)
Refrigeration. Available
The present invention relates to an improved method Temperature of EaBefore Flashing into East ME
for utilizing at low temperatures the refrigeration avail- 0 20 E. Tai Gas E. EE
able in a high pressure liquid ethane stream. More par- -
ticularly, this invention relates to cooling the said liquid B.t.a.
ethane stream to a temperature below 0° F., followed by 3:33
eXpanding it into a large volume of a colder light gaseous 35,666
Stream to thereby obtain vaporization of the liquid stream E. 9.
and further cooling of the combined stream. Most par
ficularly, in a preferred embodiment, this invention re
lates to an improved light ends system for recovering The amount of heat which has to be abstracted from the
propylene and ethylene from a C- stream from steam liquid ethane prior to flashing is egal to that gained by
cracking. In this system comprising a first demethaniza. 20 the refrigeration capacity below. 120F. Howeyers this
tion by absorption followed by successive fractionations preceding is at a much higher temperature level than the
the liquid ethane stream from the ethylene-ethane splitter -120° F. refrigeration increase, so that a net gain is
is cooled to a temperature below -20° F. and is flashed achieved resulting in appreciable power savings.
in the presence of the expanded cold -110 to -140° F. The principal and preferred use of this system, is in the
tail gas from the absorber demethanizer to provide addi-
tional low temperature refrigeration for the process.
25 Separation of valuable ethylene from a gas sing
ethylene in combination with methane and hydrogen.
According to the present invention it has now been dis- Thus, effluent gases from hydrocarbon i. sing
covered that large savings in requirements for low tem- processes,
perature refrigeration, i.e. refrigeration at -100 to -150
e.g. C3 streams can be nore Sticity, SE
rated according to the present invention. Specifically, the
F., may be obtained by cooling the liquid ethane product 30 present
to a temperature below 0. F., preferably below -20° F.
invention aids in the recovery of propylene and
other light hydrocarbons from the hydrogen-methane tail
and fashing this ethane in the presence of a large amount gas without the need for expensive equipment such as
of a lighter gas. Preferably, this gas is the cold tail gas turbo-expanders O ethylene refrigeration.
from a demethanizer containing mainly methane and It is known that in the separation of ethylene from
hydrogen. This gas is conventionally combined with the 35 gaseous mixtures containing hydrogen, methane, ethane
ethane and burned as a fuel gas so that no disadvantage and/or ethylene, propane and/or propylene in compil
is incurred in combining the two streams. it should be tion with higher boiling hydrocarbons, the principal dif:
noted that at these low temperatures in the absence of ficulty of separation lies in the elimination of methane and
the additional light gases expansion to 50-100 p.s.i.g. (fuel hydrogen from said mixture. In the prior art it has been
gas pressure) would not produce vaporization of ethane 40 found advantageous to concentate the C components,
since the vapor pressure of ethane at these temperatures which are mainly propylene, e.g. 95 mol percent propylene,
is lower than these pressures. 5 mol percent propane, and to utilize this stream as a sol
Ethane vapor pressures at various temperatures are wet for the C2 components, such as ethane and ethylene.
listed below: In this manner the separation between methane and the C2
45 hydrocarbons is facilitated. However, in order to accom
Temp. F.: Vapor preS., p.S.i.a. plish such separation, low temperature refrigerant is re
0--------------------------------------- 220 quired in the distillation-absorption process. Thus, the
-50------------------------------------ 93 temperature at the top of the demethanizer, in such a proc
-100 ----------------------------------- 31 ess will ordinarily be of the order of -112 F. Such low
150----------------------------------- 7 so temperatures are required in order to avoid an excessive
By the present expedient the effective pressures are re- loss of Ca hydrocarbons in the effluent gas and to attain
duced in accordance with Dalton's Law as follows: partial these temperatures, ethane or ethylene refrigeration rather
pressure of ethane = total pressure X mol fraction of than only propylene refrigeration is required. Alternative
ethane. It can be seen that for practical expansion, vapor ly, according to the prior art the temperature at the top of
ization of liquid ethane to pressures of 50-150, preferably 55 the demethanizer may be maintained at about 0 to -20°
F., but at these temperatures large quantities of propylene
50-100 p.s.i.g., the relative proportion of the light gases
should be 1:1 to 25:1, preferably 2:1 to 20:1, e.g. 6:1 are taken overhead. In the latter prior art system to
mols of light gas per mol of liquid ethane. At these dilu reduce this propylene loss with the overhead gas, the
tions, ethane can be evaporated at 50-100 p.s.i.g. at tem overhead stream must be processed in either of two ways:
peratures of -100 F. to -150 F., thus making refrig- 60 ethylene (1) the gas may be separately cooled with ethane or
eration available at these low temperatures equal to the refrigeration to condense the propylene, or (2)
latent heat of the ethane evaporated. Without the diluting the gas may be cooled by refrigeration provided by send
gas, ethane would evaporate at only -68 F. to -38 ing the overhead gas through turbo expansion engines and
F., corresponding to 50 and 100 p.s.i.g., seriously degen- using merely recycled propylene refrigeration.
erating the available refrigeration to a less attractive level. 65 In the present process additional refrigeration at the
A particularly advantageous arrangement is to precool necessary low temperatures is made available from the
the liquid ethane to as low a temperature as possible by liquid ethane from the ethylene splitter thus reducing the
heat exchange prior to mixing with the cold light gas requirement for either (1) extraneous ethane or ethylene
stream. Thus, if the ethane is to be flashed into a -100 refrigeration, or (2) turbo expander refrigeration.
to -150° F. gas stream, it is most advantageous to pre- 70 The present invention will be more clearly understood
cool the ethane as near as possible to the -100 F. to from a consideration of the accompanying drawing where
-150 F. range. This will make the maximum use of in a preferred process for carrying out the invention is
 ar
3,192,732
4.
diagrammatically illustrated. A feed stream of C and to expansion valve 50. Here the liquid is vaporized and
ligher components obtained for example from steam expanded in line 3 to a pressure of 50 to 150 p.s.i.g.,
cracking is supplied at a temperature of -35 F. to 0. F., e.g. 100 p.s.i.g., in the presence of overhead vapors, from
e.g. -25 F. through line 1 to the middle part of the the Joule-Thompson recovery drum 28, supplied through
absorber 2 operated at 300 to 600 p.s.i.a., specifically 420 line 30 as previously described.
p.s.i.a. This feed stream may contain, for example, 224 It should be noted that by the present invention process
mols/hr. H, 365 mols/hr. CH4, 428 mols/hr. ethylene, it is possible to either (1) cool the vapors to lower tem
104 mols/hr. ethane, 282 mols/hr. propylene, 21 mcls/hr. peratures thus recovering more propylene in Joule-Thomp
propane, 0.5 mols/hr. CO. A propylene lean oil stream Soil recovery drum 28 or (2) reduce the requirement for
supplied from a deethanizer as will be described is intro 10 eXtraneous low temperature refrigeration required in the
duced at a temperature of -15 to -35 F., e.g. -20 F. refinery. Thus, alternatively to utilizing all the low tem
through line 3 to the overhead stream from the absorber. eratuie refrigeration in cooler 24 it may be utilized in
The amount of this lean oil stream may be for the above other cooling operations in the refinery.
example, 650 lb. mois/hr. From the bottom of the tower An example of the improvement obtained by the pres
the dennethanized C3-stream is removed through line 4, 5 ent process can be seen from a comparison of a prior
a part of said stream being supplied through line 5, art processing scheme with that of the present inven
reboiler 6 and line 7 back to the tower and the remainder tion. in a prior art scheme refrigeration is recovered out
being passed through line 8 at a temperature of 60 to 90 of the spent ethane in an ethylene recovery plant by
F., e.g. 80 F. to deethanizer 9. This deethanizer is op flashing the ethylene/ethane splitter bottoms down to
erated at a pressure of 300 to 600 p.s.i.g., e.g. 370 p.s.i.g. 20 fuel gas pressure (50-75 p.s.i.g.), exchanging the latent
From the bottom of the deethanizer a propylene stream heat (at -50 F.), and then heating the gas by exchange
(containing also the small amounts of propane present up to 10 to 30 F. before mixing with the tail gas. In
in the C3- cut) is passed through line 10, part of the the present scheme the liquid ethane and the cold (-110
stream being passed back to the column through line , or - 140. F. or lower) absorber-demethanizer tail gas
reboiler 2 and line 13, and of the remainder, part being 25 are mixed at fuel gas pressure, and then the mixture is
passed back to column 2 and the remainder being taken exchanged. Thus, all the latent heat of the ethane prod
off as product through line 14. The liquid propylene uct is available as refrigeration at the lowest ethylene
passed back to absorption tower 2 is passed through line refrigeration level (say - 140 F. or so), since ethane will
15 to cooler 16 where its temperature is reduced to 0 to evaporate into the tail gas at that temperature (its partial
-20° F., e.g. -5 F. From the cooler the liquid propyl 30 pressure is 10-15 p.s. i.).
ene is passed through line 7 to join the vapors taken The refrigeration recovered in the two processing
overhead from tower 2 through line 3. The combined Schemes is compared below.
stream is passed through line 9 to condenser 23 where
the temperature is reduced to -15 to -35 F., e.g. -20 Recoverable refrigeration, mm. B.t.u./Hr.
F. The cooled stream is passed through line 2i to sepa (Based on 140 mols/hr. ethane flashed into cold tail gas)
rator 22 and the separated liquid is recycled to the column
through line 3. The overhead gases from separator 22 are Prior Art Present Invention
passed through line 23 to cooler 24, where the tempera Temp. Range, F.
ture of the gas is reduced to -80 to -120 F., e.g. From
T.G.
From
C. Total
Fron
T.G.
To
C* Total
-105 F. From cooler 24 the gases are supplied through 40 --C,
line 25 to Joule-Thompson expansion valve 26 where the
pressure is reduced to 50 to 150 p.s.i.g., e.g. 100 p.s.i.g. -161 to -140 0.53 0.3 0.40
Reduced pressure and liquid gas at a temperature of -100 -140 to -110
-110 to -54
0.86
0.60
0.23
0.5
0.83
0.45
to -150 F., e.g. -130 F. are supplied through line 27 -54 to -32--------- 0.39 0.04 0.14
to Joule-Thompson recovery drum 28 where liquid propyl 45 -32 to --9--------- 0.35 0.09 0.26
ene is recovered through line 29. The overhead gases 1.88
are passed through line 30 where they are further cooled
to a temperature of -110 to -160° F., e.g. -135 F. Part of the refrigeration available from the combined tail gas --C,
by the vaporization of a liquid ethane stream supplied strean
mixing iswith
usedtheto cold
cool the
tail splitter
gas. bottoms from 33° F. to -150°F. prior to
through line 3 as will be described. The combined 50
gaseous or gas-liquid stream is supplied through line 32 A particularly attractive alternate is to use the liquid
back to cooler 24 where these low temperature gases or propylene from the Joule-Thompson recovery drum28,
gas-liquid mixture are utilized to provide refrigeration. i.e. line 29, to cool the liquid ethane prior to flashing
The gases leave cooler 24 through line 33. These heat through valve 50. In the present example, the stream
exchange gases in line 33 are now at a temperature of 55 in line 29 is at -130 F. and the ethane fed to valve
-25 to -45 F., e.g. -30 F. Alternatively to a single 56 at -23 F. By suitable heat exchange between these
cooler a number of staged coolers may be used as is con two streams, the temperaure of the liquid ethane fed to
ventional in the art. valve 50 can be lowered to -100° F. to -110° F. For
Returning now to the deethanizer 9 the C stream is the quantities indicated (140 lb. mols/hr. of ethane),
this will make an additional 230,000 B.t.u./hr. of low tem
passed through line 34 to condenser 35, a part of the 60 perature
stream being refluxed back to the column through line 35 refrigeration available in the -100° F. to -130°
and the remainder being passed through line 37 to ethyl F. temperature range.
ene separation column 38. This column may operate in The foregoing description contains a limited number
the range of 75 to 400 p.s.i.g. From this column the of embodiments of the present invention. It will be
ethylene stream is passed overhead through line 39 to con 65 understood that this invention is not limited thereto since
denser 40, a Suitable reflux stream being returned through numerous variations are possible without departing from
line 41 and the remainder being passed to product through the scope of the following claims.
line 42. From the bottom of the column a part of the What is claimed is:
ethane stream after return of a reboil stream through line i. An improved process for utilizing at low temper
43, reboiler 44 and line 45 is passed through line 45 as 70 atures the refrigeration available in a high pressure liq
a product to fuel gas or to various uses such as feed uid ethane stream which comprises flashing the liquid
material for steam cracking and the remainder of the ethane stream at a temperature in the range of 0 to -150°
stream at temperature of -20 to 30 F., e.g. 25 F. is F. and from a pressure in the range of 75 to 400 p.s.i.g.
passed through line 47, cooled in exchanger 48 to 0° F. to a pressure in the range of 50 to 150 p.s.i.g. in the pres
to -150 F., e.g. -23 F. and is passed through line 49 75 ence of a cool lighter gaseous stream supplied at a tem
 3,192,732
S 6
perature below -80 F. and utilizing the combined stream 8. The process of claim 5 in which the liquid ethane
to effect refrigeration of another stream. and the liquid propylene lean oil are separately obtained
2. The process of claim in which the relative propor from the liquid propylene oil containing absorbed ma
ion of the lighter gaseous stream is in the range of 1:1 terials heavier than methane by fractionation.
to 20:1 mols of the lighter stream per mol of the liquid 9. The process of claim 5 in which liquid propylene
ethane stream. is separated by distillation from the liquid propylene oil
3. The process of claim 1 in which the lighter gas containing absorbed materials heavier than methane, a
eous stream comprises essentially hydrogen and meth part of the liquid propylene separated is passed back to
the absorption tower as the propylene lean oil supplied to
4. The process of claim 1 in which the initial pressure 10 said tower, liquid ethane is separated by distiilation from
of the liquid ethane is in the range of 150 to 350 p.s.i.g. the overhead vapors from said distiliation separation of
5. An improved demethanization process which com liquid propylene, and at least a major part of the liquid
prises passing a C8- stream containing hydrogen and ethane separated is passed to the liquid ethane expansion.
methane to an absorption tower operated at a pressure of 10. The process of claim 5 in which the expanded
300 to 600 p.s.i.g. supplying a liquid propylene lean oil 5 overhead stream from the absorption tower is further
to the top of said tower to absorb materials heavier than cooled to -100 F. to -150 F. prior to being passed
methane from said Ca- stream, expanding the overhead to the liquid ethane expansion vaporization.
stream from said tower to a pressure in the range of 50 to 1. The process of claim 5 in which the liquid ethane
150 p.s.i.g. to effect cooling of said stream, further cool is precooled before flashing to a temperature in the range
ing said expanded stream to a temperature below -80 20 of 70 to -130 F.
F., and expanding a liquid ethane stream at a temperature
of 0 to -150 F. in the presence of the cooled expanded References Cited by the Examiner
overhead vapor stream from said tower from a pressure in UNITED STATES PATENTS
the range of 75 to 400 p.s.i.g. to a pressure in the range 1,325,667 12/19 Crawford -------------- 62-114
of 50 to 150 p.s.i.g. to effect vaporization of the liquid 25
2,028,432 1/36 Barton -------------- 62-17 X
ethane stream and further cooling of the combined stream 2,573,341 10/51 Kniel ---------------- 62-17 X
and utilizing the combined stream to effect refrigeration 2,731,810 1/56 Hachmuth ----------- 62-31 X
of another stream.
6. The process of claim 5 in which the relative propor 2,777,305 1/57 Davidson --------------- 62-17
tion of the cooled overhead stream from the tower to the 30
2,804,488 8/57 Cobb ---------------- 62-17 X
liquid ethane stream is in the range of 1:1 to 20:1 mois 2,813,920 1 1/57 Cobb ------------------ 55-51
of the former per mol of the latter. 2,915,881 12/59 Irvine ------------------ 62-17
7. The process of claim 5 in which the C3- stream is NORMANYUDKOFF, Prinary Examiner.
obtained by fractionation from a product stream from
steam cracking. 35 ROBERT A. O'LEARY, Examiner.