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Патент USA US2123960

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H. c. PENNRICH
2,323,960
METHOD OF CRACKING HYDBOCÀRBON OILS
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Filed Aug. 29, 1935
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Henry C. Pennrlch.
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2,123,960
Patented July 1.9, 1938
NITED STATES PATENT OFFICE
2,123,960
METHOD 0F CRACÉKIÈG HYDROCARBON
Henry C. Pennrlch,-Brussels, Belgium
Application August 29, 1935, Serial No. 38,362
5 Claims.
This invention relates to the cracking of hydro
carbon oils and it refers more particularly to the
production of motor fuels having high antiknock
values.
»
In my former applications, Serial No. 610,346,
originally ñled May 10, 1932 and Serial No.
633,551, ñled September 17, 1932, a method of
cracking hydrocarbon oils is disclosed, in which
normally incondensable hydrocarbon gases, ob
10 tained as a byproduct of the cracking and fol
lowing distillation of hydrocarbon oils, are sub
jected to high pressure and temperature and are
admixed to the fresh charge oil to be cracked
under conditions wherein the reaction time and
temperature of the oil cracking process are care
fully controlled. An improved gasoline is thus
produced at a distinctly higher yield and with
considerably lower gas formation.
Under the above conditions, many of the com
20 pounds present in the cracked gases undergo
conversion and form normally liquid hydrocar
(Cl. 196-9)
ucts from these and the fresh hydrocarbon oil
products with which they are mixed. In gen
eral, the results of this process are a greater
gasoline yield, less gas formation and a smoother
reaction and performance of the cracking proc- 5
ess; this may in part also be attributed to the'
greater amount of heat available due to the
exothermic character of the reaction of poly
merization and the more highly concentrated
10
gas mixture.
'I'he method of 'separating the low molecular
or fixed gas constituents from the cracked gases'
can be carried out in a variety of ways but in
practice the following process was found to be
most convenient and economical. A mixture of 15
vgasoline and cracked gases obtained by distilla
tion is brought toa pressure of about 150 pounds
per square inch and a temperature at which the
gasoline is completely liquefied. Under these
conditions, the higher boiling gas constituents
are dissolved while a gas 4rich in methane and
hydrogen remains unabsorbed and `is removed.
the polymerization of unsaturated hydrocarbons , The solution is then heated whereby the dissolved
present or formed from saturated constituents gas constituents are again set free. They are
compressed, heated and passed on into the prin 25
25 by the cracking reaction. These normally in
condensable gases, obtained coincident with the cipal cracking unit.
One example of a practical unit embodying` the
cracking operation, contain the compounds bu
tane, propane, ethane and the corresponding features of my invention is illustrated in the
bons.
This conversion is generally the result of
unsaturated hydrocarbons as well as the so-called
30 ñxed gases methane, hydrogen, carbon monoxide
and carbon dioxide. It is generally found that
the fixed gases‘are highly stable and generally
that they do not readily undergo conversion un
der the above conditions and thus it is found
35 that through the presence of the ñxed gases the
conversion of the higher boiling compounds be
comes incomplete.
Based on these observations I found it highly
advantageous to remove _the fixed gases from the
40 cracked gases before they are compressed and
heated for admixture and to subject only the
remaining higher boiling incondensable hydro
carbons to higher pressure and temperature
wherethrough they-are very readily and com
' pletely converted and thus they then form the
valuable products as Yrequired for the Aabove indi
cated purpose.
4
‘
-
`
Thus when the highly stable or the ñxed gases
methane, hydrogen etc. are absent, then the
products in the remaining mixture are present at
higher concentrations and `for that reason the
conversion will naturally proceed further giving
a greater yield of liquid products. These conver
sion products may be formed either from the gas
-constituents alone or they may be reaction prod
accompanying drawing and it is to be operated .
as follows:
.
.
_
30
The fresh feed, such as a crude oil or products
obtained from crude oils and similar products,
enters through pipe I and is mixed with the
cracked products at point 2 and from there the
mixture is sent into the flash tower 3. ; Heavy tar 35
and overhead vapors are separated from themixture by condensation in the tower and it is
>continuously withdrawn from the bottom by
means of pipe 4. The overhead vapors are passed
by means of pipe 5 'into the distilling tower 6. 40
A condensate consisting mainly of gas oil is col
lected .in> the cooler 8 and is sent to the sepa
rator 9.‘ The separator contains gasoline as a
solvent for the higher molecular compounds and
is operated at a pressure of ,150 pounds per 45
square inch 'and a gas is. separated from the
liquid. -This gas comprises the ñxed'gases .and
consists of methane, hydrogen, CO and CO2 and _
is withdrawn by means of pipe I3. The liquid is
~sent into the second separator. I0 by means of 50
pipe I4, in which the liquid is heated to around
'300° F. under substantially the samek pressure.
The heating is obtained by the use of steam cir-_
culating through the steam coil 22. A stabilized
gasoline is' withdrawn into the storage tank by 55
2
2,128,960
means of pipe 23 and a gas is taken from the
top of the stabilizer or separator. This gas con
tains the hydrocarbons ethane, propane, butane
and the corresponding unsaturates. The gas is
recycled through pipe I5 and its pressure is in
creased to around 1000 pounds per square inch
drocarbon oil to be cracked, said hydrocarbon
oil being heated to a temperature below its crack
ing temperature and said mixture being in pro
portions suflicient to cause cracking of apart
of said oil, passing said mixture through a crack
ing zone, _and maintaining said pressure on said
mixture in the cracking zone, removing the mix
ture from the cracking zone andadding cold fresh
feed to the cracking mixture.
10 raised to around 1050° F. The heated gas is sent
2. The method of cracking hydrocarbon oils
into the oil cracking zone I9 by means of. the to obtain a high-grade anti-knock motor fuel
pipe I8. The pipe I1 is a bypass and contains. comprising the steps of separating from nor
mally incondensible hydrocarbon gases the fixed
the control valve 20.
,
gases methane, carbon monoxide and dioxide.
The condensate of the distillation tower 6 leav
15 ing by way of pipe 'I is compressed to around ethane, nitrogen, hydrogen etc., subjecting the re 15
maining normally incondensible hydrocarbon
1000 pounds per square inch. Additional distil
before the gas enters the heating zone I6.
In the heating zone consisting of tubes placed
in a furnace the temperature of the recycle gas is
lates can be added to this stream by way of
gases to a pressure between 500 and 3000 pounds
pipe II. _ The stream enters the oil heating zone , per square inch and to a temperature to start
I2 which consists of tubes placed in a furnace.
20 In this zone, the temperature of the oil is raised
to around 800° F.
The heated oil of zone I2 is mixed with the
heated gas of zone I 6 in proportion to obtain a
temperature of between 840 and 880° F. The
25 mixture is passed through the oil cracking zone
I9 consisting of tubes placed in a furnace. The
. furnace is only moderately heated in order to re
polymerization but not exceeding 1200° F., and,
maintaining said temperature to control said
polymerization, mixing said heated gases with a
hydrocarbon oil to be cracked, said hydrocarbon
oil being heated to a temperature below its crack
ing temperature and said mixture being in such
proportion as to result in cracking of a part of
said oil passing said mixture through a cracking
zone, and maintaining said pressure on said mix
place the heat lost during the course of the ture in the cracking zone, removing the cracking
cracking process. Additional amounts of gas mixture from said cracking zone while reduc
30 may also be added into the cracking zone at >vari
ing said pressure and adding fresh feed to the
'
ous intermediate points along zone I9 which are mixture.
' 3. The method of cracking hydrocarbon oil to
not shown. The cracking zone is made sum
ciently long to assure a cracking time of around produce a high-grade anti-knock motor fuel
comprising the steps of freeing normally incon
10 minutes. The temperature of the oil gas mix
35 ture at the beginning and at the end of this zone densible hydrocarbon gases of gases rich in 35
are about the same. 'I'he products> leaving the methane, ethane, hydrogen, carbon monoxide
crackingzone are decreased in pressure by means and dioxide, which are diiilcult to condense and »
of pressure valve 2i and from then on the pressure thereby separating from incondensible gases a
will be around 200 pounds per square inch. The condensible portion, compressing said condensible
portion to between 500 and 3000 pounds per 40
products are mixed with fresh charge oil enter
ing through pipe I whereby the temperature is square inch and heating it to a high temperature
brought to about '700° F. and then the mixture is until polymerization starts but not over 1200° F.
and preventing said temperature from rising in
sent to the flash tower 3.
The conditions of pressure and temperature
45 may vary from those given above according to the
type and kind of oil to be converted and the prod
ucts desired. In general, in the heating and the
cracking zones, the pressure may be between 300
and 3000 pounds per square inch while the pres
50 sures in all other parts of the operation such as
in the distillation vand separation tower should
be below 300 pounds per square inch. The tem
perature of the oil cracking zone is to range be
tween 840 and 960° F. for most of the stocks, while
55 in the gas heating zone it is to be still lower than
these temperatures.
Having thus described one typical example of
my process, I do not bind myself to the exact
details given in the above description, but rather
consider this as one example illustrating the gen
eral broad idea of~ my invention. -
I claim:
1. The method of cracking hydrocarbon oils
comprising the steps of separating normally in
65 condensible hydrocarbon gases into a nrs-t 'frac
tion rich'in methane and into a second fraction
order to control the polymerization products,
mixing said polymerization products with nor
mally liquid hydrocarbon oil heated in a heating
unit to a temperature below its cracking tem
perature and at the same pressure as imposed
on said condensible portion and in proportions
that the temperature of the mixture causes
cracking, passing said mixture through a crack
ing zone, and maintaining said pressure on said
mixture in the cracking zone, removing the mix
ture from said cracking zone, decreasing said
pressure and temperature, adding fresh feed and 55
separating desired compounds from the mixture.
4. 'Í'he method of cracking hydrocarbon oil as
claimed in claim 1, the step of separating the
fraction rich in methane from normally incon
densible hydrocarbon gases being carried out by
compressing the gases at low temperature and in
contact with gasoline as a solvent. removing the
non-condensed gases and reevaporating the dis-_
solved gases.
-
-
5. The method of cracking hydrocarbon oil as
claimed in claim 3; the step of separating the por
substantially free from methane. heating said
tion rich in methane, ethane, hydrogen, nitrogen,
second fraction under a-pressure of between 500
and 3000 pounds per square inch to a tempera
70 ture sufficient to start exothermic polymerization
and not exceeding 1200° F., and keeping said tem
carbon monoxide and dioxide, from normally in
condensible hydrocarbon gases being carried out
by compressing the gases at low temperature
and'in contact with saturated hydrocarbon oils
l perature substantially constant whereby a fully
as a solvent, removing the non-condensed gases
controlled polymerization product is obtained.` and reevaporating the dissolved gases.
mixing said heated second fraction with a hy
HENRY C. PENNRICH.
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