July 3, 1923.

1460,545
P. E. HAYNEs ET All
PRODUCTION OF ETHYLENE
Filed March 9, 1918 2 Sheets-Sheet 1
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INVENTORS

ATTORNEYS
July 3, 1923. - 460,545
P. E. HAYNEs ET. A
PRODUCTION OF ETHYLENE.
Filed March 9, 1918 2 Sheets-Sheet 2
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NVENTORS

ATTORNEYS
 Patented July 3, 1923. 1,460,545
UNITED STATEs. PATENT office.
PIERRE E. HAYNES, OF BUFFALO, NEw York, AND GEORGE o. CURME, J.R., OF PITTs
BURGH, PENNSYLVANIA, ASSIGNORs TO THE LINDE AIR PRODUCTs company,
OF CLEVELAND, OHIO, ACORPORATION of oHIo.
PRODUCTION OF ETHYLENE.
... Application filed March 9, 1918. Serial No. 221,407.
To all whom it may concern. natural gas represented by the pipe 13. As 55
Beit known that we, PIERRE E. HAYNEs will be seen hereinafter, unmodified natural
and GEORGEO. CuRME, Jr., both citizens of gas is only a part of the fuel by which the .
the United States, residing, respectively, at engine is driven. To regulate the amount
5 Buffalo, county of Erie, and State of New of unmodified gas delivered to the holder
York, and at Pittsburgh, county of Alle ll the pipe 12 is provided with a fuel-make 60
gheny, and State of Pennsylvania, have in up valve 14. The engine 10 drives an elec
vented certain new and useful Improve tric generator 15, connected by leads 16, 17
ments in the Production of Ethylene, of to motors 18, 19, 20, 21, 22, which drive the
10, which the following is a full, clear, and compressors 23, 24, 25, 26, 27, respectively.
exact description. A suitable Supply of natural gas from the 65
This invention relates to the manufacture pipe 13 is accumulated and maintained in
of ethylene and its chief object is to pro the gasometer 28, whence it is withdrawn.
vide a simple and effective process or method through pipe 29 and compressed by the
ls by which the compound can be produced in natural gas compressor 23. Compressor 23
a high degree of purity from initially im and pipe 30 may be provided with suitable 70
pure ethane, as for example ethane contained drains (not shown) for the removal of any
in natural gas. A further object is to pro constituents (of the gas) that may be con
vide a continuous process for obtaining densed at this stage. From the compressor
20 ethane and from the latter, ethylene. TO the gas is delivered through the pipe 30 to
these and other ends the invention consists coil 31 of a suitable pre-cooler 32, which is 75
in the novel method hereinafter described. cooled by a 'suitable refrigerant, such as am
Suitable and convenient apparatus for monia or carbon dioxid, driven through coil
carrying out our invention in the preferred 33 by compressor 24. The coil 31 is prefer
25 the
manner is illustrated diagrammatically in
accompanying drawing, in which ably provided with a drain (not shown) for
Fig. 1 shows the first half and Fig. 2 the withdrawal of any substances condensing 80
the second half of the apparatus. at this stage, as for instance water, hexane,
The ethane required can be obtained from pentane, butane, propane, benzol, toluol, etc.
30 A duplicate precooler, not shown, may be
any source containing the same, as for ex rovided, for use in case the other should
ample natural gas. e clogged or choked by freezing. 85
When natural gas is the raw material The compressed and pre-cooled gas is now
used, the substances associated with the ready for the concentration of its ethane or
ethane should be removed. Such substances such part of its ethane as may be needed for
35
include water, carbon dioxide, hydrogen the purpose in hand. This concentration is
sulfide, benzol, toluol, propane, butane, hex in the present process effected by liquefac 90
ane, etc. Methods, and apparatus for re
moving such impurities are well known and tion, and is attained by the continuous ex
pansion of the gaseous mixture (in the
hence need not be described herein. Methane present instance natural gas or a mixture
40 and other substances boiling at lower tem derived therefrom) within the liquefier from
peratures than ethane should also be re a highy to a low pressure. Conservation of 95
moved and the manner of effecting this sepa "cold' is secured by means of a heat ex
ration will now be described. When other changer in which the mixture, (now sepa
gas mixtures are taken as raw material, the
ethane should first be isolated as in the case
rated into liquefied ethane plus liquefied con
stituents of the natural gas which have
of natural gas. . .. higher boiling points than ethane), and ..100
In the particular apparatus illustrated the a gaseous portion of the other con
energy required for the various steps of the stituents, are passed back, thus absorbing
process is derived from the natural gas from heat from the incoming compressed gas,
50 which ethylene is to be produced. For this which latter is advancing toward the ex
purpose an internal combustion engine 10 pansion
is provided, supplied with gas from a fuel. possible orifice or valve. liquefy
to economically In this ethane
way it inis
gas holder or gasometer 11, which is itself a mixture of ethane,
connected by a pipe 12 with the source of . gases of lower boilingmethane,
points, byandadjust
other
 9. 1,460,545

ment of the ratio of the pressure of the un ethane is decomposed at high temperatures
expanded to the pressure of the expanded into ethylene and lyrgy according to
gas, as will be readily understood by those the equation CH=CH-H. When the
skilled in the art. temperature is reduced the reaction proceeds
For the purpose of subjecting it to the in the direction of ethane formation, and in 7
treatment or step outlined above, the conn the direction of ethylene and hydrogen for
pressed and precooled gas is delivered mation when the temperature is increased.
through pipe 34 to coil 35 of the heat-ex It is also known that the equilibrium con
changer 36. Here the gas is further cooled, centrations of the various gases involved
10 by cold gases flowing counter-current in the are approximately constant at a given tem
coils 37,38, and then passes into coil 39 of perature and vary with change in tempera
the ethane liquefier and separator 40, where ture. Hence by proper choice of tempera
the gas gives up still more heat, this time ture and pressure conditions, and by using
to the liquid (ethane and perhaps other a suitable reaction vessel, the decomposition
5 gases) in which said coil, or at least the can be effected so as to give approximately
lower portion thereof, is immersed. Pass the theoretical yield of ethylene and hydro
ing through coil 39 the cooled gas issues gen. We prefer to treat the ethane at a
from the expansion valve 41. By adjust temperature exceeding 500° C. Above 685
ment of the ratio of the pressure of the un or thereabouts the ethylene formed may
20 expanded to the pressure of the expanded be decomposed to a slight extent, and such 85
gas a temperature is reached, by virtue of decomposition is greater at higher tenpera
the expansion, at which ethane is liquefied, tures. Hence the temperature should not
thus causing a separation of the emergent be higher than about 9(0°. It has also
mixture into a liquid portion containing been ond that the ethylene formed may
25 practically all the ethane, and a gaseous be decomposed if subjected to heat at the OO
portion containing lower boiling constitul higher temperatures for too long a time. In
ents which do not liquefy at the temperature general, the period of treatment should vary
produced by the expansion. From the spray inversely as the tenperature change. The
head 42 the uncondensed or gaseous portion most favorable pressure we have found to
30 passes through pipe 43 to coil 38 of the heat be slightly in excess of atmospheric. The
exchanger 36, where as already explained. material of the containing walls with which
it assists in cooling down the high-pressure the gases cole in contact during the heat
gas from the precooler 32. The aforesaid treatment is important in that it should
liquid portion, consisting chiefly of ethane, have no injurious catalytic effect on the 00
35 flows down over coil 39 and by absorption ethylene formed. Thus when certain metals,
takes heat from the incoming high-pressure such as iron, nickel, or platinum, are used.
gas, which absorption serves by evaporation an effect is observed which results in partial
or rectification to remove any remaining destruction of the ethylene. We find, how
traces of constituents boiling at tempera ever, that copper, porcelain and the common
40 ture lower than the boiling point of ethane. vitreous materials, do not have the property 105
Practically pure ethane in liquid form thus of acting injuriously at the temperatures
named. The method of heating the ethane
collects in the bottom of the separator cham.
is not, in general, important, but in the
ber, whence it is delivered by pipe 44 to coil
37 of heat-exchanger 36. Here the liquid present process the availability of a com:
45 is warmed and evaporated by the high bustible gaseous by-product makes the latter O
pressure gas flowing through coil 35. The a convenient source of heat. It is recog
gases emerging from coils 37 and 38 are nized, however, that some advantage is to
still at a temperature below that of the surbe had in electrically heated reaction tubes
rounding atmosphere, and if desired may be on account of the ease afforded for tempera
50 passed by suitable apparatus, not shown) ture control, and the possibility of more 15
in heat-exchanging relation to the high thorough heat insulation.
pressure gas in pipe 30 before such gas For carrying out the above step of our
reaches the precooler 32. Otherwise the process a furnace 47 is provided, heated by
gas from coil 38 is delivered hy way of pipegas burners 48 supplied by a small pipe 49
55 44 to the fuel-gas line 12 where it mingles leading from the fuel-gas line 12. From 20
with the natural gas flowing from pipe 13 the ethane gasometer 46 the gaseous ethane
to the gasometer 11, while the gas (prac is withdrawn by the compressor 25 and de
tically pure ethane) from coil 37 passes by livered through pipe 50 to the inner pipes
way of pipe 45, to the ethane gasometer 46 51 inside the furnace 47. The pipes 51 are
60 for storage. connected “in parallel' to pipe 50 and are 25
The ethane or a mixture rich in ethane, enclosed by the outer or return pipes 52
obtained and isolated as above described. is which are connected to the heat-exchanger
now ready for treatment to produce ethyl 53 so that the incoming ethane, which is rel
ene. This is essentially a heat treatment, atively cool, can absorb heat from the out
and is based upon the known fact that going hot ethylene, in accordance with 3.
 1460,545 &

what we have said in the preceding para less methane (if any of the latter be present
graph, the heating pipes or reaction cham in the mixture) are condensed and run back
bers, and any other parts with which hot into vessel 64, while hydrogen and the rest
ethylene may come in contact, are composed of the methane pass on through the con
of or surfaced with an inert material, pref denser and are delivered to pipe 91. The O
erably copper. gases (ethane, ethylene and methane) con
From the heat-exchanger 53 the ethylene densed in the condenser 65 collect in vessel
is led by way of pipe 54 to the crude ethyl 64 and thence pass through pipe 78 and are
ene gasometer 55. delivered to a suitable point in the rectify
O The ethane-conversion product or reac ing tower or column 79 between vessels 74 75
tion product obtained in the above manner and 84. The more easily evaporated con
is rich in ethylene, mixed with hydrogen, stituents (ethylene and methane) of the
methane, unchanged ethane, and possibly liquefied mixture pass up the tower in gase
other impurities. Any carbon, tar, or like
5 substances present can be removed by any
ous form and through the opening 80 into
the condenser 81 in vessel 64, cooled by the 80
convenient method, not shown. ethane, ethylene and methane liquefied in
To isolate the ethylene the gaseous mixture the condenser 65 as explained above. In the
containing the same is taken from gasome condenser 65 the said ethane, ethylene and
ter 55 by pipe 56 to compressor 26, by which
20 it is compressed. Passing through pipe 57
methane are not only liquefied but are also
supercooled, and it is therefore possible to
to coil 58 of heat-exchanger 59 the com maintain the liquid (in vessel 64) at a tem
pressed gas is cooled by cold gases flowing perature considerably below the boiling
counter current in coils 60, 61, 62, 92, as points of ethane and ethylene, thus cooling
hereafter described. From coil 58 the the condenser 81 to a point insuring conden
25 cooled mixture flows through pipe 63 to sation of the ethylene rising therein from 90
vessel 64 and thence passes into condenser the tower 79; but at the same time the pres
65, which is partly immersed in a refriger Sure, in the tower 79 is kept at such point
iting bath, preferably liquid methane, con that the methane rising therefrom will not
tained in vessel 66. The liquid methane is be condensed in coil 81 and will therefore
30 obtained by the expansion of previously pass on through pipe 82 to pipe 68 leading
cooled high-pressure methane at the expan to coil 62 of the heat exchanger 59. Thus
sion valve 67. The methane evaporated in the methane coming into vessel 64 as an im
vessel 66 passes therefrom by way of pipe 68 purity in the crude ethylene is added to the
to coil 62 of heat-exchanger 59 where it serves methane which is used as a refrigerating
to cool down the previously compressed agent to cool, the condenser 65. The con OO
warm gases flowing counter-current in coils densible constituents of the gaseous mixture
58 and 69. Thence the methane, now warmed, rising into coil 81 drop down upon the baffle
goes through pipe 70 to the methane storage 83 and are shed thereby into the annular
someter 71. From the latter it is drawn trough or vessel 84 at the top of the recti
40 y compressor 27 and is delivered to the fying tower. The liquid thus collected over 05
pipe 72 leading to the aforesaid coil 69 of flows into the opening 80, thereby washing
the heat-exchanger. In this coil the gas or lixiviating the gases rising in the tower.
gives up heat to the cold gases flowing coun These gases, being evaporated from the
ter-current in coils 60, 61, 62 and 92, and liquefied crude ethylene delivered by pipe
passes then to coil 73 which is immersed in 78, and being therefore chiefly ethylene, O
liquefied ethane and ethylene in the vessel pass on and up into the condenser
74. This mixture of liquefied ethane and coil 81 and there the ethylene is con
ethylene is boiled by the high-pressure densed while the gaseous methane con
methane, and the latter is reciprocally tent escapes by way of pipe 82 as
cooled by the heat-exchange. From coil 73 already described. The gaseous ethane
the methane passes through pipe 75 to coil content is absorbed or liquefied by the lixi
76, which is immersed in the liquefied viating liquid and runs back into vessel 74
methane, previously mentioned, in vessel at the bottom of the tower where it adds it
66. Here the high-pressure methane re self to the liquid ethane in which coil 73 is
ceives its final cooling before reaching the immersed. As the operation continues, less O
expansion valve 67, which is connected to and less gas of higher boiling point than
the aforesaid coil 76. The refrigerating ethylene escapes from the rectifying tower
agent (methane) thus flows continuously through opening 80, until eventually none
through a closed circuit, in which it is con or practically none escapes at all and the
CO tinuously liquefied and evaporated alter liquid condensed in condenser 81 and col
nately, lected in vessel 84 is then pure or substan
The gaseous mixture (or crude ethylene) tially pure ethylene. At the same time
delivered to vessel 64 by pipe 63, as stated practically all the liquid ethylene overflow
above, rises into the condenser 65 and is ing into the rectifying tower and evaporat
65 there cooled. Ethane, ethylene, and more or ing therein is recondensed in the condenser 130
 4. 1,460,545
81 and is added to the pure ethylene in ves the latter pipe they pass with the other 30
sel 84. From the latter, ethylene is with gases therein to the storage gasometer 11.
drawn continuously by pipe 85 and passed It is to be understood that the invention
through coil 61 of the heat-exchanger 59 is not limited to the specific apparatus and
where it absorbs heat from the relatively procedure herein specifically described but
warm gases in coils 58 and 69 and then can be carried out in other ways without de 35
passes on through pipe 86 to the pure ethyl parture from its spirit. For example, the
ene gasometer 87. From the latter the gas preferred procedure is, as is seen from the
10
is withdrawn as needed through pipe 88. foregoing description, continuous, but we
The ethane delivered to the rectifying do not limit ourselves to a continuous
tower 79 collects in vessel 74, usually with method. . 40
some ethylene, and is withdrawn by pipe 89 We claim:
through coil 60 of heat-exchanger 59, where 1. A process of forming ethylene from
it absorbs heat from the warmer gases in
5 coils 58 and 69, and passes thence through gaseous hydrocarbon mixtures containing
pipe 90 to pipe 45 where it mingles with ethane, which comprises the steps of isolat
ethane from the liquefier 40 and goes onto ing ethane from the mixture in a state of 45
the ethane storage gasometer 46, from substantial purity and heat treating the
which, as before described, ethane is de ethane under substantially optimum condi
20 livered to the reaction chambers in fur tions for the production of ethylene.
nace 47. - 2. Process according to claim 1, wherein
The uncondensable gases (chiefly if not ethylene and residual ethane are isolated 50
entirely methane and hydrogen) delivered from the product of the heat-treatment, and
to the condenser 65 are discharged through the ethane is returned to the cycle at a
25
pipe 91 and conducted to coil 92 of the heat point preceding the heat-treatment.
exchanger 59, where they serve to cool the In testimony whereof we hereunto affix
our signatures.
relatively warm gases flowing counter-cur
rent in coils 58 and 69, and are led thence PIERRE E. HAYNES.
by pipe 93 to the fuel-gas line 12. Through GEORGE O. CURME, Jr.