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Патент USA US2109631

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March 1, 1938.
c. H. ANGELL
2,109,631
CONVERSION OF HYDROCARBON OILS
Original Filed May 16, ‘1955
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av.
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ET
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A
02 0ENGI<U‘
i
INVENTOR
‘CHARLES H. ANGELL
BY
TTORNEY
Patented Ms. 1, 1938
~
2,109,631
fUNlTED STATES "PATENT oFFicE *
2,109,631
CONVERSION OF HYDROCARBON OILS
' Charles H. Angeli, Chicago, ni., assignor to Uni
versal Oil Products Company, Chicago, 111., a
corporation of Delaware
Application May 16, 1935, Serial No. 21,746
Renewed June 5, 1937
7 Claims. ‘(01. 196-48)
This invention refers to an improved process
together with the vaporous products from the
for the conversion of relatively high-boiling hy-
cracking and coking operations with which they
drocarbon oils or oils containing a substantial
are commingled, while high-boiling components
proportion of high-boiling materials wherein the
5 charging stock for the process is subjected to va-porization by being 'commingled with hot vaporous conversion products of the process, the
resulting non-vaporous high-boiling components
oi the charging stock subjected to relatively mild
10 conversion conditions together with intermediate
conversion products of the process previously subjected to more severe conversion conditions and
the resulting residual liquid products subjected to
coking.
15
In one embodiment, the invention comprises
subjecting intermediate conversion products 01'
of the charging stock remaining unvaporized by
contact with the hot vaporous products of the 5
process are returned to the reaction chamber and
thereby subjected to relatively mild conversion,
without passing through a heating coil, by con
tact in this zone with the heated products from
the heating coil to which the re?ux condensate 10
produced by fractionation of the vaporous con
version products and low-boiling fractions of the
charging stock is supplied.
.
_
It is within the scope or the invention to’e?'ect
substantial vaporization of the charging stock 15
in the vaporizing chamber by contacting the same
the process (re?ux condensate) to conversion in this. zone with either the vaporous conversion
conditions of cracking temperature and superat- products from the reaction chamber or the va
mospheric pressure in a heating coil, introduc- porous products from the coking chamber, 01‘
2'0 ing the heated products into an enlarged reac- ‘both, and the invention contemplates regulation 20
tion chamber also maintained at a substantial oi the extent of vaporization to which the charg
superatmospheric pressure, separating vaporous
and liquid conversion products in'the reaction
chamber, withdrawing the vaporous conversion
25 products from the reaction chamber and introducing the same into a reduced pressure vaporizing chamber to which hydrocarbon oil charging
stock for the process is supplied, withdrawing
non-vaporous liquids, including high-boiling
30 components of the charging stock, from the
vaporizing chamber and introducing the same
into said reaction chamber wherein they are sub-
iected to relatively mild conversion together with
the heated products from said heating coil,
3;, separately withdrawing residual liquid conversion
products from the reaction chamber, subjecting
the ‘same to additional heating under non-coking
conditions and introducing the heated materials
into a coking zone wherein they are reduced to
40 substantially dry coke, introducing vaporous
products from the coking zone into said vaporiz_'
ing stock is subjected by regulating the quantity
of such vaporous products from the reaction
chamber and from the coking chamber 00m
mingled‘ with the charging stock in the Vaporlz- 25
ing chamber. Any remaining vaporous products
from the reaction chamber and/or from the cok
ing chamber in excess of those-required fcr~ ef
fecting the desired degree of vaporization oi’ the
charging stock are vsubjected to fractionation 3o
together with the vaporous products from the
vaporizing chnmber- '
The accompanying diagrammatic drawing
illustrates One speci?c 10ml of apparatus in which
the invention may he aeeolnplished- Referring 35
t0 the drawing, heating cell i is located Within
a furnace 2 of any suitable form and the oil sup.
plied to this zone. in the manner to be later more
fully described, is heated therein to the‘ desired
conversion temperature preferably at a substan- 4n
tial superatmospheric pressure- The heated on
ing chamber, subjecting vaporous products from
is discharged from heating 6011 I through line 3
the vaporizing chamber to fractionation for the
and valve I into reaction chamber 5,
_ -
,
_1formation of re?ux condensate, comprising said
4;, intermediate conversion products which are supplied to the ?rst mentioned heating coil, subjecting fractionated vapors'of the desired end-boiiing point to condensation-and recovering the re-
Chamber 5 is also preferably maintained at a
substantial superatmcs'pheric Pressure which may 45
be substantially the same or somewhat lower than
that employed at the Outlet from the Preceding
heating coil. Although 'not indicated in the
suiting distillate.
‘
By this method of operation the excess heat
contained in the vaporous products from the
drawing, chamber 5 is also preferably insulated
in order to prevent the excessive loss or heat 50,
therefrom by radiation so that conversion of the
heated products supplied to this zone is continued
therein. In the case here illustrated, separation
so
cracking and coking operations is utilized to effect substantial vaporization or topping oi’ the
charging stock, the low-boiling vaporous i'rac55 tions of which are subjected to fractions-mien
of vaporous and liquid conversion products is
accomplished in chamber I, the liquid products as
2,109,631
2 .
being withdrawn from the lower portion of the
chamber to further treatment, as will be later
more fully described, while the vaporous products
are removed from any desired higher point in
32 to pump 33 by means of which it is fed through
line 34 and valve 35 into vaporizing chamber 8.
Vaporizing chamber 8 is preferably operated
at a substantially reduced pressure relative to
the chamber, such as, for example, through line "that employed in chamber 5 and the charging
6, and may be directed, all or in part, through stock supplied to this zone is directly commingled
'alve 1 in this line into vaporizing chamber 8, or therein with regulated quantities of the hot va
porous products from reaction chamber 5 and/or
' . regulated portion or all of these vapors may
pass from line 6 through line 9, valve 10 and line coking chamber 22 and is thereby subjected to '
appreciable vaporization. Suitable contacting
I l_ direct to fractionator 30.
Residual-liquid conversion products are with . means such as bubble trays, packing, perforated
drawn from the lower portion of chamber 5 pans, bailles or the like (not illustrated) or any
through line I3 and valve ll to pump 15 by desired combination of such means may be em
means of which they are supplied through line ployed in chamber ‘8, when desired, for effecting
intimate contact between the hot vaporous prod 15
15 l8 and valve I‘! to heating coil l8.
Heating coil I8 is located within a furnace I9 . nets and the charging stock. Contacting of the
charging stock with the vaporous conversion
products from the reaction chamber and coking
to a relatively high temperature sufilcient to chamber in chamber 8, aside from effecting sub
20 e?ect its subsequent reduction to coke in coking , stantial vaporization of the charging stock,
chamber 22, to which the highly heated residual serves the additional purpose of partially cooling
liquid is supplied through line 20 and valve 2|. the vapors and thereby removing therefrom any
The velocity of the residual liquid passing through undesirable high-boiling components such as en
of suitable form capable of quickly heating the
residual liquid passing through the heating coil
heating coil l8 and the rates of heat transfer in
25 this zone are so regulated that the oil is quickly
brought to the desired coking temperature with
out allowing it to remain in the heating coil and
communicating lines for a su?icient length of
trained or dissolved tars and similar heavy liq
uids unsuitable as charging stock for heating coil 25
I.
These undesirable high-boiling components
of the vapors commingle in chamber 8 with the
high-boiling components of the charging stock
time to permit any substantial formation and ‘ which remain unvaporized in this zone and the
commingled materials are removed from the 30
30 deposition of coke therein. '
Coking chamber 22 is preferably maintained
at substantially atmospheric or a relatively low
superatmospheric pressure although pressures up
to 150 pounds, per square inch, or thereabouts, or
35 up to substantially the same pressure as that
lower portion of the vaporizing chamber through
line 35 and valve 81 to pump 38 by means of which
they are supplied through line 39 and valve 40
to 'reaction chamber 5.
In the particular case here illustrated, the rela 35
maintained at the outlet from heating coil l8 tively heavy oil fromvaporizing chamber 8 enters
may be utilized in the coking chamber. It' will the upper vportion of reaction chamber 5 and is
be understood, of course, that although only a sprayed against the inner surface of the walls of
single coking chamber is shown in the drawing the chamber by means of a suitable spray or -
40 any desired number of a plurality of such zones
may be employed, when desired, and may be
either simultaneously operated or, preferably, are
alternately operated, cleaned and prepared for
further operation so that the coking stage, in
46 common with the rest of the system, may be
operated continuously. The heated residual liq
uid supplied to the coking chamber is reduced to
substantially dry coke in this zone and the coke
may be allowed to accumulate therein to be re
50 moved from the chamber, in any well known
manner not illustrated, after- its operation is
completed and after it has been isolated from
the rest of the system. Chamber 22 is provided
with a suitable drain-line 23 controlled by valve
55 Zlwhich may also serve as a means of introducing
steam, water or any other suitable cooling mate
rial into the chamber, after its operation is com
pleted and after it has been isolated from the
rest of the system, in order to hasten cooling
and facilitate the removal of coke from the
chamber. Vaporous products‘ are withdrawn
from the upper portion of chamber 22 through
line 25 and may be directed, all or input,
through line 26 and valve 21 into vaporizing
65 chamber 8, or all or a regulated portion of the
vaporous products, from the reaction chamber
may pass through valve 28 in line 25 into line
H and thence to fractionator 38.
'
~Simultaneous with the operation above de
70 scribed, hydrocarbon oil charging stock for\the
process, preferably comprising an oil of relatively
wide boiling range, such as crude petroleum,
topped crude or the like, or an oil which contains
a substantial proportion at least of high-boiling
75 materials, is supplied through line 3| and valve
spreader device indicated at 56. .In this manner 40
the relatively heavy oil flows downward over the
walls of the reaction chamber to the lower por
tion of this zone and is subjected during its pas
sage through this zone to conversion under the
conditions maintained in the reaction chamber. 45
The residual liquid products resulting‘from con
version of the high-boiling oils from chamber 8
collect in the lower portion of chamber 5 together
with the residual liquids resulting from conver
sion of the heated products from heating coil |
50'
and pass therewith to coking, in the manner pre
viously described. ‘The manner of introducing
the heavy oils from chamber 8 into chamber 5
and causing the same to flow downward'over the
inner surface of the walls of the chamber, aside
from accomplishing relatively mild conversion
thereof, serves to wash the inner surface of the
walls of the reaction chamber and thereby sub
stantially prevent the accumulation of heavy tars
and pitch-like material on the walls of the cham
ber, therebyv substantially‘ preventing the for
mation and accumulation of coke in this zone.
Vaporous products, including the relatively
low-boiling vaporized components ofv the char:
ing stock as well as the components of. the
vaporous conversion products supplied vto cham
ber 8 which tremain uncondensed in this zone,
are withdrawn therefrom through line H and
valve l2 and‘! supplied, together-with any portion
of the vaporous products from reaction chamber 70
5 and/or coking chamber 22 not supplied to
chamber 8, to fractionation in fractionator 38.
The components ‘of the vaporous products sup
plied to fractionator 30 boiling above the range
of the desired ?nal light distillate product of the 75
2,109,631
_
3
process are condensed in this zone as re?ux con
pressure. The temperature to which the residual
densate, which is withdrawn, in the case here il,
lustrated, from the lower portion of the frac
tionator through line 4| and valve 42 to pump
43, by means of which it is returned through line
44 and valve 45 to conversion, in the manner pre
viously described, in heating coil I.
It is, of course, also within the scope of the in
vention to separate the re?ux condensate formed
in fractionator 30 into two or more selected rela
tively low-boiling andhigh-boiling fractions, any
of which may, when desired, be removed from the
system while one or more of said fractions may
be subjected to conversion in heating coil i and,
15 when desired, other selected fractions may be
subjected to independently controlled conversion
conditions in one or more separate heating coils,
not illustrated, heated‘ products from which may
- be supplied, all or in part, to reaction chamber 5
20 or to vaporizing chamber 8 or to coking cham
ber 22.
'
Fractionated vapors of the desired end-boiling
point are withdrawn, together with uncon'den
sable gas produced by the operation, from the up
25 per portion of fractionator 30 through line 46 and
valve 41 and are subjected to condensation and
cooling in condenser 48. The resulting distillate
and gas pass through line 49 and valve 50' to
collection and separation in receiver 5|. Uncon
30 densable gas may be released from the receiver
through line 52 and valve 53. Distillate may be
withdrawn from receiver 5| through line 54 and
valve 55 to storage or elsewhere, as desired.
When desired, a regulated portion of the distillate
liquid from the reaction chamber is subjected in
the heating coil to which it is supplied may range,
for example from 900 to 1050° F., preferably with
‘a relatively low superatmospheric- pressure in this
zone of the order of 20 to 150 pounds, or there
abouts, per square inch, although lower or higher
pressures may be employed in this zone, when de
sired. Any desired pressure ranging from sub
stantially atmospheric to 150 pounds, or there-1 10
abouts, per square inch, which, however, is no
greater than the pressure employed in the pre
ceding heating coil, may be utilized in the coking
zone.
The pressures employed in the fraction
ating, condensing and collecting portions of the 15
system may be substantially equalized or some
what reduced relative to the pressure employed
in the preceding portions of the system commu
nicating therewith.
.
As a speci?c example of an operation of the 20
invention as it may be accomplished in an appa
ratus such as illustrated and above described, the
charging stock, which comprises a California
crude of about 20.5° A. P. I. gravity containing
approximately 12 per cent of gasoline fractions 25
boiling up to 400° F. and about 40 per cent of
materials boiling up to. 572° F., is supplied to the
vaporizing chamber which is operated at a super
atmospheric pressure of approximately 50 pounds
per square inch, the charging stock being therein 30
subjected to appreciable vaporization by contact
with the total vaporous products from the‘ coking
zone as well as a portion of the vaporous prod
ucts from the reaction chamber. The remaining
collected in receiver 5| may be recirculated, by ._portion of the vaporous products from the reac
well known means not illustrated in the draw
tion chamber are subjected, together with the
ing, to the upper portion of ‘fractionator 30, to vaporous products from the vaporizing chamber,
serve as a re?uxing and cooling medium for as—
sisting fractionation of the vapors in this zone
40 and to maintain the desired vapor outlet temper
ature therefrom.
The invention isnot limited to the speci?c
method illustrated and described for reducing the
residual liquid products from the reaction cham-'
45 ber to coke since any other well known method,
including the use of a suitable\heat carrying me
dium for assisting the coking operation as well
as,'when desired, an externally heated coking
chamber or a coking retort of any well known
form, is readily adaptable to the process of the
invention. The invention also contemplates the
omission of the coking step of the process, when
desired, in which case the process may be oper
' ated for the production of liquid residue from the
55 reaction chamber.
The preferred range of operating conditions
which may be employed for accomplishing. the
objects of the present invention in an apparatus
such as illustrated and above described will be
60 approximately as follows: The heating coil to
which the re?ux condensate is supplied may em
ploy an outlet conversion temperature ranging,
for example, from 850 to 950° F., or more, prefer
ably with a superatmospheric pressure at this
in the system of from 100 to 500 pounds, or
6.5 point
more, per square inch. Any desired superatmos
pheric pressure within substantially the same
range but no greater than that employed at the
outlet from the heating coil may be utilized in
70 the succeeding reaction chamber. The vaporiz
ing chamber is preferably operated at a substan
tially reduced pressure relative to that employed
in the reaction chamber which may range, for
example, from 100 pounds, ‘or thereabouts, per
76 square inch down to substantially atmospheric
to fractionation for the formation of re?ux con
densate. The re?ux condensate is subjected in
the heating coil to an outlet conversion tempera 40'
ture of approximately 950° F. at a supe-'atmos—
pheric pressure of about 350 pounds per square
inch and the highly heated products are supplied
to a reaction chamber maintained at substan
tially the same pressure. Non-vaporous liquid 45
products from the vaporizing chamber are also
supplied to the reaction chamber and sprayed
against the inner surface of the walls in the up
per portion of this zone. Residual liquid is with
drawn from the reaction chamber, quickly heated 50
in a separate heating coil to a temperature of
approximately 1000° F. at a superatmospheric
pressure of about 50 lbs. per square inch and in
troduced into a coking chamber operated at sub
stantially the same pressure wherein it is reduced 55
to substantially dry coke. This operation will
produce, per barrel of charging stock, approxi
mately 60 per cent of 400° F. end-‘point motor
fuel of good antiknock value and approximately
100 pounds of low volatile coke of uniform quality 60
and good structural strength,- the remainder be
ing chargeable, principally, to uncondensable gas.
_I claim as my invention:
1. In a process for the conversion of hydrocar
bon oils-wherein intermediate liquid conversion
products, comprising re?ux condensate formed
by fractionation of the vaporous conversion prod
ucts of the process, are subjected to conversion
conditions of cracking temperature and super
atmospheric-_pressure in a heating coil and com 70
municating reaction chamber, vaporous and liq
uid conversion products separated in the reaction
chamber, separately withdrawn therefrom and
the latter subjected to coking in a separate coking
zone, the improvement which comprises with-. 75
4
2,109,681
drawing vaporous products from the coking zone
and introducing a portion thereof into a vapor
izing chamber, supplying hydrocarbon oil charg
ing stock for the process to the vaporizing cham
ber wherein it is subjected to appreciable vapor
ization by contact with said portion of the hot
porizing chamber and introducing the same into
the reaction chamber wherein they are subjected
to relatively mild conversion by contact with the
heated products from said heating coil, with
drawing vaporous products from the vaporizing
chamber, combining the same with the remain
vaporous products from the coking zone, with- . ing portion of the vaporous products from the re- 4
drawing nonvaporous liquid products from the
vaporizing chamber and returning the same to
the reaction chamber wherein they are subjected
to relatively mild conversion by contact with the
heated products from‘ said heating coil, supply
ing vaporous products from the vaporizing cham
ber, together with vaporous products from the
15 reaction chamber and, the remaining portion of
the vaporous products from the coking zone, to
action chamber and subjecting the resultant mix
ture to fractionation for the formation of said
re?ux condensate which is returned to the heating 10
coil for further conversion, subjecting fraction
ated vapors of the desired end-boiling point to
condensation and recovering the resulting dis- .
tillate.
4. A process for the conversion of hydrocarbon 15
oils which comprises subjecting intermediate liq
fractionation for the formation of said re?ux _ uid conversion products, comprising re?ux con
condensate which is returned to the heating coil
for further conversion, subjecting fractionated
20 vapors of the desired end-boiling point to con
densation and recovering the resulting distillate.
2. In a process for the conversion of hydrocar
bon oils wherein intermediate liquid conversion
products, comprising re?ux condensate formed
.25 by fractionation of the vaporous conversion products of the process, are subjected to conversion
conditions of cracking temperature and superat
mospheric pressure in a heating coil and com
municating reaction chamber, vaporous and liq
30 uid conversion products separated in the reac
tion chamber, separately withdrawn therefrom
conditions of cracking temperature and superat 20
mospheric pressure in a heating coil and commu
nicating ‘reaction chamber, separating vaporous
and liquid conversion products in the reaction
chambenseparately withdrawing the same there
from, heating the residual liquid conversion prod 25
ucts withdrawn from the reaction chamber to a
high temperature under non-coking conditions,
introducing the heated materials into a coking
chamber, reducing the same therein to substan
tially dry coke, introducing regulated portions of 30
the vaporous products withdrawn from the coking
and the latter subjected to coking in a separate
chamber and from the reaction chamber into a
coking zone, the improvement which comprises
supplying a portion of the _‘vaporous products
charging stock for the process into the vaporizing
35 withdrawn from the coking zone and a portion
of the vaporous products withdrawn from the
reaction chamber to a vaporizing chamber, sup
plying hydrocarbon oil charging stock for the
process to said vaporizing chamber wherein it is
40
densate formed by fractionation of the vaporous
conversion products of the process, to conversion
subjected to appreciable vaporization by contact
vaporizing chamber, introducing hydrocarbon oil
chamber whereby it is subjected to appreciable 35
vaporization by contact with said portions of the
hot vaporous products supplied to this zone, with
drawing non-vaporous liquid from the vaporiz
ing chamber and introducing the same into the
reaction chamber wherein they are subjected to 40
with said portions of the hot vaporous‘products ‘ relatively mild conversion ‘by contact with the
from the coking zone and reaction chamber, heated products from said heating coil, with
drawing vaporous products from the vaporizing
withdrawing non-vaporous liquids from the va
porizing chamber and introducing the same into chamber and subjecting the same, together with
y the remaining vaporous products from the reac 45
45 said reaction chamber wherein they are subjected
to relatively mild conversion by contact with the tion chamber and the coking chamber, to frac
heated products from said heating coil, combining tionation for the formation of said re?ux con
vaporous products from the vaporizing chamber densate which is returned to the heating coil for
further conversion, subjecting fractionated vapors
with the remaining portions of the vaporous prod
of the desired end-boiling point to condensatio 50
ucts
from
the
reaction
chamber
and
coking
zone
50
and recovering the resulting distillate.
'
'
and subjecting the resultant mixture to fractiona
5. A conversion process which comprises frac
tionating hydrocarbon vapors formed as herein
conversion, subjecting fractionated vapors of the ' after set forth, heating resultant re?ux conden
to cracking temperature under pressure in a 55
55 desired end-boiling point to condensation .and sate
heating coil and separating the same into vapors
recovering the resulting distillate. .
and unvaporized oil in a reaction chamber, re
3. In a process for the conversion of hydro
moving
the unvaporized oil and further distilling
carbon oils wherein intermediate liquid conver
tion for the formation of said re?ux condensate
which is returned to the heating coil for further
sion products, comprising re?ux condensate
formed by fractionation of the vaporous conver
sion products of the process. are subjected to con
a version conditions of cracking temperature and
superatmospheric pressure in a heating coil and
communicating reaction chamber, vaporous and
liquid conversion products separated in the re
action chamber and separately withdrawn there
from, the improvement which comprises intro
ducing a portion of the vaporous products with
drawn from the reaction chamber into a vaporiz
70 ing chamber, introducing hydrocarbon oil charg
ing stock for the process into the vaporizing
chamber wherein it is subjected to appreciable
vaporization by contact with said portion of the
hot vaporous products from the reaction chamber,
withdrawing non-vaporous liquids from the va
the same in a second chamber, contacting a por
tion of the vapors from the second chamber with 60
charging oil for the process to vaporize a portion
of the charging oil, introducing the unvaporized
portion of the charging oil to the reaction cham
ber, supplying vapors from the reaction chamber,
the vapors from said contacting step and the re 65
maining portion of the vapors from the second
chamber to said fractionating step, and finally
condensing the fractionated vapors.
6. A conversion process which comprises frac
tionating hydrocarbon vapors formed as herein 70
after set forth, heating resultant re?ux conden
sate to cracking temperature under pressure in
a heating coil'and separating the same into vapors
and unvaporized oil in a reaction chamber, re
moving the unvaporized oil and further distilling 75
5
9,109,081
the same in a second chamber, contacting a por
tionof the vapors from the reaction chamber
with charging oil for the process to vaporize a
portion or the charging oil, introducing the un—
vaporized portion of the charging oil to the res:
action chamber, supplying vapors from the sec
ond chamber, the vapors from said'contacting
step and the remaining portion of vapors from the
and unvaporized oil in a reaction chamber, re
moving the unvaporized oil and further distilling
the same in a second chamber, contacting a por
tion of the vapors from the second chamber and
a portion of the vapors from the reaction cham
her ‘with charging oil for the process to vaporize
a‘ portion of the latter, introducing the unvapor
ized portion 01' the charging voil to the reaction
reaction chamber to said rractionating step, and > chamber, supplying- the vapors from said con
?nally condensing the fractionated vapors. :
tacing step and the remaining portions 0! the
- 7. A conversion process which comprises trac
tionating hydrocarbon vapors formed as herein
after set forth, heating resultant re?ux conden- -
sate to cracking temperature under pressure in a
15 heating coil and separating the same into vapors
vapors from said chambers to the fractionating 10
step, and ?nally condensing the fractionated
vapors.
'
>
'
'
CHARLES H. ANGEIL.
15
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