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Патент USA US2111899

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22, 193s
l 2,111,899 r.
' untreu STATES.. vPA'raN'r-»or (ICE
.moonssron 'nm
a '
Appumßnpeœmber 1s, 1935, serial N9. 55,011 '
,-2 emma
while subjected to suitable pressure -and velocity
method for producing ethylene, a hydrocarbon sc_that upon dashing the preheated oil into a
gas (12H4 of the olefin seriesVfrom liquid hydro-v hotter reaction zone substantially fall of the oil
carbon mixtures of the type round in petroleum.' is almost instantly heated and cracked to ethylene
and hydrocarbons oi.' lessthan’four carbon atoms, 5
»5 „in which _new process the correlation of temper
-' atures, reaction velocities and reaction periods of this hot 'gas being immediately shock chilled be
' The subject matter _of this invention is a new
time produce yields of ethylene far in excess of .
low the polymerization temperature zone toprac- ‘
the ~-yields by the current methods‘of, producing
tically exclude polymerization before a substan
tial amount of ethylene is polymerized.
ethylene from hydrocarbons.
In the oil industry ethylene is a by-product in
converting heavy-oil to >gasoline by pyrolysis and
In the accompanying drawing I have illustrated 10 ’
diagrammatically embodiments of my invention: `
the -yieldvof ethylene, depending upon whether ' Fig. 1 illustrating v_an embodiment of the inven- g
the liquid or the vapor phase method of crack
tion wherein lthe reaction zone is externally s'
ing is employed, varies in amounts up to approx
heated; and
15 imately 6% by weight of the charging stock.
Fig. 2_ illustrating. an embodiment `oi" the inven- 'lo
In the chemical industry, in the operation di- I tion _' wherein the reaction zone is' internally
rected to the production of ethylene from liquid j
“.hydrocarbons,- a` variation of the vapor phase ~
As an example of the practice of my invention ’
method used in the _oil industry is employed.
V Ñfor the production of ethylene from gas oil,` and ^
In the oil industry the yield-of liquids is in the- with reference ilrst of ,all tó Fig. 1:l Tlie oil to be
order of 75% by weight of the charging stock and processed is taken from any suitable source of
the ethylene yield as above indicated is only about ‘supply I and supplied to the pressure preheater
6%; in the chemical industry the yield of liquids 2 at a pressure in the order of, for example, 20
is in the order-oi.’ 40% by weightof the charging ,atmospheres or higher pressure, iiowing continu
stock and the ethylene yield is in the 'order of , ously through the preheater to the reaction zone
10% by weight of 111e chargingstock. _
_3. The _oil -is preheated to a temperature in the
As` distinguished kfrom these prior processes, order of 850° F. In the preheating step of my
the present invention provides a method wherein process temperature and pressure conditionsare
the ~yield of lliquids is reduced` to less than 10% by
s ¿o
weight of the charging stock and the _fyield of .
so controlled that the oil remains in the liquid
phase. The preheated oil iscontinuously in- 30 '
1 ethylene is increased to as high _as 45% by weight - iected into the hotter reaction zone 3, flashing
of the charging stock.
` into vapor, the temperature of the hotter reactlo'n ~
.One of the `objects ofthis invention is the pro- ' zone being so controlled that substantially >all of' .. '
duction of ethylene as'the primary product oi' the ' the oil vapor'is’ converted to ethylene and hydro
operation in converting substantially all of the carbons of less than four carbon atoms at a tem-. 35 .
>charging stock to gases, the yield of >condensible perature of inthe order of 1400° F. _The' hot
gases are immediately shock chilled to below
'~ polymers being inhibited substantially .tol ex‘clu
sion.“ This operation is notof necessity .an ad
'1000°. F. in the cooler- 4 so as to practically- _exfA
junct to .oil reñnery operations but can be con _clude polymerization before a substantial amount
veniently located wherever ethylene isfdesired for
use either directly orfas a process material.V (
" `Another object of this invention is the produc
tion of ethylene from liquid hydrocarbons. where
in I obtain a yield of ethylene as high as 45%
45 by weight of the hydrocarbons charged, my meth# _
’ od providingïor the ñash system cracking of pre,
_heated liquid hydrocarbons, the ethylene thus
-produced beingl prevented from polymerizing to
of ethylene; is polymerized, thereby avoiding yields 40
of a substantial quantity of liquid, i. e., not in
excess of '10% by weight of the charging stockí" '
" The cooled -gas ñows to a fractional distillation
unit 5, which separates the ethylene> from the
products of pyrolysis.
In the embodiment of my inventionlas illus
` trated in Fìg.'2 the procedure is the same as out- ' -
lined above, the reaction zone being internally ’
heavier hydrocarbons'ythereby insuring the maxi- ` heated by hot products of combustion from source
50 mum yield of ethyleneand the
yield of
8. Chilling of the hot gas- is effected by water 5o
injected into the/gas as indicated at 1. The
Mynew process produces these novel results ~ ethylene is separated >from the products of py
from liquid hydrocarbons in a continuous opera
'rolysis by chemical reactionas shown at 8.
In e example given above ‘I have mentioned
tion, the process comprising the operations ofpre
55' 4heating `the oil to a suillcientiy high temperature 'a tem raturein the order oi' 1400° Il'. with refer-' g55l F
ence to the gas in the reaction chamber. This
was in connection with the use of gas oil as' the
charging stock. lIt is to be' understood that with
diiierent charging stocks the temperature at
which the reaction takes place and the time
necessary to obtain the optimum yield oi ethylene
_therefrom vary, but in any case the temperature
should not be less thanv >approximately 1200? F.
and the reaction time should not exceed approxi
mately one and one-half seconds to avoid pro-v
oil are instantly decomposed to ethylene and hy
drocarbons of not more. thanfour carbon atoms,
and immediately upon attaining this temperature
shock cooling the gaseous mixture to below 1000“
F. tov exclude ,polymerizing reactions forming
gasoline hydrocarbons and to retain the hydro
carbons as ethylene and hydrocarbons of not
more than four carbon atoms.
2. The process of producing ethylene from gas
'oil, which process comprises <preheating the oil 10
ducing condensates. Furthermore, the temper-' to a temperature in the order oi' 850° F. while
ature should not exceed 1600° F, because at such ‘ subjected to superatmospheric' pressure, con
temperature ethylene decreases. Preferably the
temperature ranges between ~1300" F. and A1500°
trollingtpressure and time conditions whilelpre
heating so that the oil remains in the liquid
phase, injecting all' of the preheated „oil into a
temperature, preferably ranging from approxi flowing4 gaseous medium which contains sum
mately one and one-halt seconds to less than » cientheat for heat exchange to the preheated
one-half secondA in order to obtain the optimumv oil to ilash heat the preheated oil to within the
yield 'o1 ethylene.
temperature range of 1300° F. to 1600", F., at
What I claim is:
which temperature all of the hydrocarbons' of the
1. The process of producing ethylene from oil, oil are instantly decomposed to ethylene and hy
which process comprises preheating the oil under- drocarbons .of not more than four carbon atoms,
superatmospheric pressure while maintaining the and immediately upon attaining this vtempera
oil slightly below its vaporizing temperature at ture shock cooling to below 1000° F. to exclude 25
25 that pressure, injecting al1 of the preheated liquid polymerizing reactions forming gasoline hydro
15 I". and the time varies in inverse relation to the
oil into a ñowing gaseous medium which contains
suiiicient heat for heat exchange to the preheated - carbons and to retain the - hydrocarbons as
oil to flash heat the preheated oil to within the ethylene and hydrocarbons of not more than four
temperature range of 1300”.F. to 1600” F., at
which temperature all of the hydrocarbons of the _
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