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Патент USA US2107269

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' Feb. 8,‘ 1938.-
2,107,269
J. B. BARNES
HYDROCARBON OIL CONVERSION
Original Filed Ma‘rch 16, 1951
FURNACE 25
' FRACTIONATOR
FURNACE 56
INVENTOR
>
JOHN B. BARNES
BY F ozf?ééy!
ATTORNE
Patented Feb. 8, 1938
' 2,107,269'
UNITED STATES PATENT" OFFICE
2,107,269
HYDROCARBON OIL CONVERSION
John B. Barnes, Chicago, Ill., assignor, by mesne
assignments, to Universal Oil Products Com‘
pany, Chicago, 111., a corporation of Delaware
Application March 16, 1931, Serial No. 522,865
Renewed March 4, 1936
2 Claims.
This invention relates to the treatment of
hydrocarbon oils andrefers more particularly
to the conversion of relatively heavy hydrocar
bon mixtures into mixtures containing material
5 amounts of hydrocarbons boiling within the
range of motor fuels.
'
More speci?cally the invention contemplates
the treatment under elevated temperatures and
pressures of relatively heavy hydrocarbon frac
10 tions from petroleum and other naturally occur
ring hydrocarbons to produce therefrom sub
stantial yields of motor fuel fractions of superior
quality as regards their tendency to burn with
out “knocking” in the cylinders of internal com
15
bustion engines.
In one speci?c embodiment the invention com,
prises passing heavy hydrocarbon oils through'a
heated zone, discharging the heated material into
an enlarged reaction zone in which separation
20
(Cl. 196-60)
to the primary heating zoneand the line leading
the products from the primary heating zone to
the primary reaction zone.
To assist-in more clearly de?ning the inven"
tion and describing any operation comprised 5
within its scope, the attached drawing is pro~
vided which shows diagrammatically a side'ele
vational view of an arrangement of equipment
which may be used in e?ecting some of its aims
and objects.v
1O
Raw oil charging stocks typi?ed by heavy
hydrocarbon oil mixtures such as, for example,
those obtained as residues when crude oils are
stripped of their lighter fractions or relatively
heavy distillates produced from similar crudes
may be taken from line I by pump 3 through
valve 2 and discharged into line 4 containing
valve 5 or line 6 containing valve 1. Line 4 leads
to secondary fractionator $6,v hereinafter to be
of vapors and nonvaporized liquids is effected, 7 described more in detail, and such portions of _
discharging the nonvaporized liquids into a va
porizing chamber under reduced pressure where
in further separation of vapors and nonvaporized
liquids is e?ected, ‘discharging the nonvaporized
liquids from the process, passing the vapors from
thesecondary vaporizing zone to a primary frac
tionating zone to produce liquid re?uxes to be
returned to the primary heating zone and vapors
which are combined with the vapors from the
30 primary reaction zone to form a mixture which
is further heated in a secondary heating zone,
discharging the products of the second heating
into a second reaction zone, again separating
vapors and nonvaporized liquids which may be
35 returned in part to the primary heating zone
for further conversion and in part to a succeed
ing. secondary fractionating zone, passing the
vapors from the secondary reaction zone into the
secondary fractionating zone designed to pro
duce vapors of desired boiling point range which
may be cooled, condensed and collected and a
plurality‘ of higher boiling intermediate frac—
tions to be utilized as material for blending with
the liquid products discharged from the vaporiz
ing zone or returned in part to the primary heat
ing zone for further conversion. The invention
further comprises the injection of relatively cold
raw oil at suitable points in the line of flow to
reduce temperatures, such points of injection
including the lower portions of the secondary
fractionating zone, the line discharging re?uxes
from this equipment to the primary heating zone,
the primary fractionating equipment, the liquid
discharge line between the primary reaction. zone
and the vaporizing zone, the combined feed line
the raw oil as- are admitted fromHthisline-may
assist in fractionating the cracked-vapors from
the secondary reaction zone of the process and
be themselvespreheatedv and discharged through
line ‘l0 ‘containing valve "in admixture with 25
re?ux condensates from the cracked vapors.
Line 6 constitutes a raw oil header having
branch line 8 ‘containing valve 9, line l0 contain~
ing valve II and line 12 containing valve I3. Line
8 containing valve 9 leads to line 10' containing
valve ‘H’ on the suction side of pump l6 which
pump is preferably employed to return heavy
liquid re?uxes from secondary reaction chamber
59 and fractionator ??vto primary heating zone
24. Line 60 containing valve 6| may provide a
means of discharging nonvaporize'cl liquids from
reaction chamber 59 into suction line 10' and
line 10 containing valve ‘H enables the admis
sion of liquid r'e?uxes from. secondary frac
tionator 66. Line 68 containing valve 69 may i
lead from collecting pan 6‘! (typifying one of. any
number of such devices that may be used at dif
ferent levels in fractionator 66) to line 10 and 7B’
and thus to the suction side of pump l6. Line 62
containing valve 63 may branch from line 60
containing valve BI and enable the transfer- of
liquid residuals either in whole or in part vfrom
reaction chamber 59 to the bottom of fraction‘
ator G6 to assist in reboiling. Pump I6 which
may be designated as the reflux pump for the
secondary cracking stage of the process dis
charges through line ll containingvalve [8 into
line 26 on'the discharge side of. combined feed
pump
I9.
.
Line l0 containingevalve H may permit the
2
2,107,269
introduction of relatively cold charging oil into
primary fractionator 40, the raw oil being pre
heated and stripped of its lighter portions and
the effectiveness of fractionator 40 being in
creased. Line l2 containing valve l3 may join
with line 38 containing valve 3| conveying the
liquid products from primary reaction chamber
28 to vaporizer 32, the introduction of raw oil in
some instances serving to cool the discharge liq
10 uids to a degree sufficient to prevent continued
reactions resulting in the deposition of coke in
the line and evaporator. Line 14 containing
valve l5- may branch from line [3 and convey
cool raw oil to line 26 through which the prod
15 ucts from the primary heating element 24 are
passing, thus effecting a control of temperature
at this point and providing a means of inhibiting
undesirable side reactions which otherwise might
occur in reaction zone 28.
Combined feed pump
I9 preferably takes suction on primary fraction
ator 40v through line 4| containing valve 42,
heavy nonvaporized portions of the products en
tering this fractionator being thereby returned
to the heating element for further conversion
though a portion of this material may be di
verted into reaction zone 28 through line 22 con
taining valve 23 to control coking reactions and
insure the ejection of substantially liquid resi
dues from reaction zone 28. Pump l9 discharges
30 preferably into line 29 containing valve 2| so that
a mixture of raw oil from line 6, reflux conden
sates from secondary reaction zone 59 and sec
ondary fractionator 66 and re?ux from primary
fractionator 40 may pass in varying proportions
35 into heating element 24 disposed in furnace 25,
Heating element 24 may be composed of tubu
lar elements connected to produce a continuous
coil and furnace 25 may be of any type found
suitable for the transmission of heat thereto.
it) During passage through the primary heating ele
ment temperatures necessary for cracking are
12 containing valve 14 as will also be described
later. The vapors from vaporizer 32 may pass
through line 38 containing valve 39 and enter
primary fractionator 40 which preferably sep
arates intermediate re?uxes for further heat
treatment which may be discharged through line
4| containing valve 42 topump l9 as already in
dicated, Vapors from this fractionator may pass
through line 43 containing valves 44 and 49 un
der slightly superatmospheric pressure and pass 10
either through line 41 containing valve 48 to join
with the vapors coming from reaction zone 28
through line 45 or pass through valve 49 to pump
59 which may discharge into line 53 containing
valve 54 leading to secondary heating element 55
disposed to receive heat from furnace 56. Pump
58 is preferably provided for raising the pressure
on the vapors from fractionator 40 to any point.
desired for the secondary conversion stage but
not above that pressure on the vapors in line 20
45 which pass into- line 5| containing valve 52
and join line 53 prior to its junction with the
heating element.
In heating element 55 pressures v‘maintained
may be substantially lower than those main
tained on primary element'24 being, for example,
of the order of 100 pounds per square inch more
or less. and temperatures employed may be sub
stantially higher, being, for example, of the or
der of from 900° to 1200° R, such changed con 30
ditions being in general conducive to the forma
tion of relatively large amounts of hydrocarbon
compounds of a cyclic or closed ring character,
which compounds have notably high anti-knock
ratings when used as motor fuel.
'
The heated materials from element 55 pass
preferably through line 51 containing valve 58
to secondary reaction zone 59 in which time for
reconversions and reformations may be given,
liquid portions being withdrawn. through line 60 40
as already indicated and vapors leaving through
line 64 containing valve 65 to secondary frac
tionator 66. This fractionator may be of a con
struction known as “bubble tray” construction
1000° F. more or less, at the exit of the heating
element, the heated products passing preferably and be designed to effect an ef?cient separation 45
through line 26 containing valve 21 to primary‘ of low boiling hydrocarbon fractions. Raw oil
may be admitted from line 4, refluxes withdrawn
reaction zone 28 which may be any arrangement
through line 18 and intermediate or side cuts
of enlarged equipment in- series or parallel en
abling the employment of prolonged reaction taken off through line 68 as previously described.
Vapors of desired boiling point range may pass 50
time in the conversion process. Pressures de
veloped during the conversion period may be of through line 15 containing valve 16 to condenser
the order of approximately 100 to‘ 500 pounds ‘H which may cool and partially liquefy the
entering products, these passing through line 18
per square inch in reaction zone28, suitable dif
ferentials being maintained at the entrance to containing valve 19 to receiver 80 in which liquids
and gases may be segregated, the former being
the heating element to cause ?ow.
withdrawn to storage through line 83 containing
The reaction chambers of zone 28 may be pro
valve 84 and the latter released through line 8|
vided with removable manheads 29 and 29’ to
permit cleaning at intervals andare preferably containing valve 82. The gas release may fur;
preferably acquired by the oil mixtures, such
temperatures being, for example, from 800 to
well insulated to conserve heat necessary for con
60 version reactions. The elements of reaction zone
28 are preferably provided with bottom outlet
lines 30 cotaining valves 3| which release pres
sure so that vaporization may be effected in va
porizer 32 under substantially atmospheric pres
sure conditions.
The vapors from reaction zone
28 mayv pass through line 45 containing valve 46
with or without pressure reduction to a second
ary heating zone to be described more fully later.
Vaporizer 32 preferably effects the separation
of relatively heavy portions of the cracked prod
ucts, these being released throughyline 33 con
taining valve 34 and passed through cooler 35,
the cooled residue passing through line 36 con
taining valve 31 and passing to storage not shown
after mixing with second stage re?uxes from line
nish a convenient method of controlling pressure
on preceding portions of the equipment.
60
To assist in controlling the boiling point range
of the vapors issuing from fractionator 66, a
pump 81 may be provided to take suction on a
suitable portion of the end product liquids
through line 85 containing valve 86 and discharge
the same into the top of fractionator 66 through
line 88 containing valve 89. A portion of the
intermediate fractions produced as side cuts and
bottom Vrefluxes in fractionator 66 may pass
through line 10 to blending pump ‘I2 as permitted
by the opening of valve 10", pump ‘I2 discharg 70
ing through line 13 containing valve "to the
residuum run-down line 36.
'
The foregoing detailed description will serve to
indicate the general operations characteristic of 75
2,107,269
Ch
3,
the process of the invention but since many other
that their benzol equivalent as determined in test
types and arrangements of equipment may be
employed the speci?c description is not to be con
motors may be as high as 65 to. 70% or higher
depending on the inherent character of the
sidered in a limiting manner.
As an example of an operation that may be
process.
conducted according to the process of the inven
tion and results obtainable therefrom, the case
of a 24 A. P. I. gravity Mid-Continent topped
crude may be taken. The feed of this charging
10 stock may be split so that approximately 20% of
the same is admitted to the secondary fractiona
tor, 75% to the primary fractionator and the
remaining 5% to the line leading from the
primary heating element to the primary reaction
zone. The temperature maintained at this last
named point may be approximately 945° F. which
is immediately cooled to approximately 900° F.
before the products enter the primary reaction
zone.
Pressures maintained on the primary re
20 action zone may be 250 pounds. per square inch,
the nonvaporized liquids being reduced to sub
stantially atmospheric pressures for vaporization
and the vapors reduced in pressure to‘ approxi
mately 100 pounds per square inch before ad
mission to the secondary or substantially vapor
phase conversion zone, in which case the vapors
from the primary fractionator may be compressed
to an equivalent degree. Temperatures employed
in the secondary conversion zone may be of the
30 order of 1050 to 1100° F. more or less and there
may be produced as an overall yield a fraction
of gasoline boiling point range equal to 60% of
the raw oil charged.
At the same time there
charging oil and the details of operation of the
The above example is given merely for purposes
of illustration and is not intended as a limitation
of my invention.
I claim as my invention:
1. A hydrocarbon oil cracking process which 10
comprises subjecting the oil to cracking condi~
tions of temperature and pressure and separat
ing the same into vapors and unvaporized oil,
?ash distilling the unvaporized oil by pressure
reduction, dephlegmating the flashed. vapors and
returning resultant re?ux to the cracking step,
combining the ?ashed vapors uncondensed by
the
dephlegmation
with the first — mentioned
vapors, heating the commingled vapors to- vapor
phase cracking temperature,Vdephlegmating the thus heated vapors to condense heavier fractions
thereof, blending such condensed fractions with
the residue of the ?ash distillation and recover
ing the resultant blend as a product of the
process, and ?nally condensing the deplhlegmated
vapors.
2. A process for cracking hydrocarbon oil to
product low boiling products comprising passing
the oil through an initial heating coil wherein it
is raised to a cracking temperature, thence pass- -
ing the oil in succession through a series of vapor
releasing chambers, uniting vaporous fractions
taken off from said chambers, subjecting the
may be produced a yield of low viscosity fuel oil
residuum equal to 20% of the charging oil, the
same to vapor phase cracking in an independent
heating zone, separating the products of the ..
remaining 20% being represented by losses in gas
vapor phase cracking step into vapors and residue,
and directly returning the residue thus obtained
and coke, the latter being formed in minimum
or negligible amounts. The gasoline fractions
produced may be of a highly aromatic nature so
to the initial heating zone.
JOHN B. BARNES.
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