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Патент USA US2112376

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March 29, 1938.
‘2,112,376
J. c. MORRELL
CONVERSION OF HYDROCARBON OILS
Original Filed ‘Oct. 8, 1954
DISTILLING
COLUMN\
HEAT
EXCHANGER
FURNACE l3‘
I
FRACTIONATOR
FURNACE 46
5
4.
,
O
y%
INVENTOR
44
JACQUE Z‘;
BY
TORN
Patented Mar. 29, 1938
,
‘
UNITED STATES PATENT OFFICE
2,112,376
CONVERSION OF HYDROGARBON OILS
Jacque C. Morrell, Chicago, 111., assignor to Uni
versal Oil Products Company, Chicago, 111., a
corporation of Delaware
Application October 8, 1934, Serial No. 747,268
Renewed February 4, 1936
6 Claims.
(Cl. 196-448)
This invention particularly refers to an improved process for the fractional distillation of
As another feature of the invention all or a
portion of the heat required for fractional distil
hydrocarbon oils of relatively wide boiling range,
such as crude petroleum, for example, accompanied by the pyrolytic conversion, under independently controlled conditions, of selected relatively low-boiling and high-boiling fractions of
the charging stock from the fractional distilling
lation of the charging stock may be supplied
thereto by indirect heat exchange between the
charging stock and the highly heated products 5,
from the heating coil to which the low-boiling
fractions resulting from said fractional‘distil
lation of the charging stock are supplied, and/or
operation as well as further conversion Within
10 the same system, of selected relatively low-boil-
the heating coil to which the low-boiling frac
tions of the intermediate conversion products are 10,
ing and high-boiling intermediate conversion
products of the process.
The present invention offers a simple and
uni?ed system for the fractional distillation of
15 hydrocarbon oils of relatively wide boiling range
accompanied by the selective conversion of rela—
supplied. Aside from furnishing heat for the
fractional distillation of the charging stock, this
method of operation serves to cool the highly
heated products from either or both of said heat
ing coils su?iciently to prevent'their excessive 15
further conversion. However, in any case, the
tively low-boiling and relatively high-boiling ‘highly heated products from both heating coils
fractions of the charging stock as Well as, rela-
tively low-boiling and high-boiling fractions of
20 the intermediate conversion products of the
process. Selected relatively low-boiling fractions
of the charging stock and selected relatively lowboiling fractions of the intermediate conversion
products of the process are each subjected to in25 dependently controlled conversion conditions of
elevated temperature and superatmospheric pressure in a separate heating coil succeeded by a
high-pressure reaction‘ chamber, to which reaction Chamber Selected high-boiling fractions of
30 the charging stock and selected high-boiling
fractions of the intermediate conversion products
are directly supplied, whereby said relatively high-
boiling fractions are heated by commingling With
the highly heated relatively low-boiling fractions
35 and subjected, in the reaction chamber, to less
severe conversion conditions than those to which
the relatively low-boiling oils are subjected in
the heating coils.
As a special feature of the present invention,
40 the overhead vaporous products resulting from
the fractional distillation of the charging stock
are preferably Supplied, While still in vaporous
state to the heating coil wherein they are sub.l'ected ‘30 conversion 01' reforming at relatively
45 high temperature, without being ?rst subjected
are cooled sufficiently to prevent their excessive
further conversion in the reaction chamber by
direct contact with the relatively high-boiling 20
fractions of the charging stock and of the inter
mediate conversion products and when desired,
particularly in case a portion or all of the excess
heat from both streams of highly heated prod
ucts from the heating coils is required to effect 10 5
the desired degree of conversion of the higher
boiling oils with which they are commingled in
the reaction chamber, all or a portion of the heat
required for fractional distillation of the charg
ing stock may be derived from any other suitable 30
source.
In one speci?c embodiment the invention com
prises subjecting hydrocarbon oil charging stock
for the process, comprising an oil of relatively
wide boiling range, to fractional distillation at 35
substantial superatmospheric pressure whereby
to separate the same into- relatively low-boiling
fractions, comprising the overhead vaporous
products, and relatively high-boiling fractions,
comprising condensate or bottoms from the dis- 40‘
tilling operation, subjecting said low-boiling va
porous fractions to conversion conditions of ele
vated temperature and superatmospheric pres
sure in a heating coil, introducing the stream of
highly heated products from said heating coil 45
to condensation, which would result in a con-
into an enlarged reaction chamber, also main
siderable loss of heat, and, in order to obviate
the use of a vapor pump to pass the hot vaporous
tained at superatmospheric pressure, and com
mingling therewith said high-boiling fractions of
products from the topping operation through said
5O heating coil, the topping operation is preferably
conducted at a pressure sufficiently higher than
that employed in the heating coil to overcome
the drop in pressure, due to friction, through the
heating coil and succeeding portions of the sys-
the charging stock, withdrawing both vaporous
and liquid conversion products from the reaction 50
chamber, subjecting the latter to further vapor
ization at substantially reduced pressure, sub
jecting the vaporous conversion products, includ
ing those resulting from said further vaporiza
55 tem.
tion, to fractionation in a separate fractionating 55>
‘
‘
2
2,112,376
zone, whereby their insu?iciently converted com
ponents are condensed as reflux condensate and
separated into selected relatively low-boiling and
high-boiling fractions, subjecting fractionated
vapors of the desired end-boiling point from said
separate fractionating zone to condensation, col
lecting and separating the resulting distillate
and gas, returning said relatively high-boiling
fractions at the re?ux condensate to the reac
10 tion chamber for further conversion, subjecting
the relatively low-boiling fractions of the re?ux
condensate to independently controlled conver
sion conditions of elevated temperature and
superatmospheric pressure in a separate heating
15 coil and introducing heated products from said
separate heating coil into the reaction chamber.
The accompanying diagrammatic drawing il
lustrates one speci?c form of apparatus in which
the invention may be practiced. It should be
noted that the optional methods of operation
provided by the present invention are not equiv
alent but may be selected to suit requirements
in order to give the process greater flexibility.
Referring to the drawing, hydrocarbon oil
25 charging stock for the process, preferably com
prising an oil of relatively wide boiling range
containing an appreciable quantity of both rela
tively low-boiling and relatively high-boiling
components, such as crude petroleum, for ex
30 ample, is supplied through line l and valve 2
to pump 3 wherefrom it is fed through line 4,
valve 5, heat exchanger 6, line ‘I and valve 8
into distilling column 9, wherein it is subjected
to appreciable vaporization and fractional dis
35 tillation.
In the particular case here illustrated
the heat required for fractional distillation of
the charging stock may be supplied thereto in
heat exchanger 6 by indirect contact and heat
exchange between the charging stock and highly
40 heated conversion products of the process, which
are supplied to this zone, as well be later more
fully described.
It is however, also within the
scope of the present invention to employ a heat
ing coil of any conventional form for the charg
45 ing stock or to impart thereto all or a portion
of the heat required for its fractional distilla
tion in any other well known manner, not illus
trated.
‘
Distilling column 9 is preferably operated at
a substantially superatmospheric pressure in or
der to eliminate pumping of the overhead vapor
ous products from this zone which are supplied
to cracking coil l2. In the case here illustrated,
the charging stock is separated by fractional
distillation in column 9 into a selected overhead
vaporous product of the desired end-boiling point
and bottoms, which latter comprise components
of the charging stock remaining unvaporized in
column 9 as well as the components which are
condensed in this zone as re?ux condensate. It
is,‘ of course, also within the scope of the inven
tion, particularly in case the charging stock con
tains any desirable low-boiling, intermediate or
high-boiling fractions which it is not desired to
subject to conversion, to separate the charging
stock into more than two selected fractions and
to withdraw said desirable components such as,
for example, straight-run gasoline of good anti
knock value, lubricating oil, asphaltic material,
70 etc., from the system by well known means, not
illustrated in the drawing.
The selected low-boiling components of the
charging stock remaining uncondensed in column
9 are withdrawn, in the case here illustrated,
75 from the upper portion of this zone through line
In to be supplied therefrom through valve II to
conversion or reforming in heating coil l2.
When desired, a regulated portion of the over
head vaporous product from column 9 may be
subjected to condensation, by well known means
not illustrated, for the purpose of forming dis
tillate which may be utilized as a re?uxing me
dium in column 9 by recirculating said distillate
to the upper portion of this zone, by well known
means not illustrated.
This is only one of the
many well known satisfactory methods which
may be employed for assisting fractionation in
column 9 and maintaining the desired vapor out
let temperature from this zone so as to control
the end-boiling point of the materials subjected
to conversion in heating coil l2.
Heating coil I2 is located within a furnace l3
of any suitable form, by means of which the heat
required for accomplishing the desired conver
sion of the low-boiling components of the charg 20
ing stock is supplied thereto. Heating coil i2
is also preferably operated at a substantial super
atmospheric pressure and the highly heated prod
ucts are discharged from this zone through line
84 and may be directed, all or in part, through 25
line l5, valve l6, heat exchanger 6, line I‘! and
valve l8 into reaction chamber 29. The highly
heated products from heating coil l2 passed, as
illustrated, through heat exchanger 6, serve to
supply to the charging stock all or a portion of
the heat required for its fractional distillation.
When desired, all or a regulated portion of the
stream of hot vaporous products from heating
coil l2 may by-pass heat exchanger 6 by di
verting the same from line 15 through valve 19
in line 14 into line I‘! and thence to reaction
chamber 20.
In case only a minor portion or none of the
highly heated products from heating coil l2 are
passed through heat exchanger 6 to be cooled 40
by indirect contact with the charging stock the
heat contained in these products may be utilized
to assist conversion of the relatively high-boiling
oils supplied to reaction chamber 29, as will be
later more fully described, in which case said 45
high-boiling oils serve to cool the highly heated
products from heating coil l2 su?iciently to pre
vent their excessive further conversion in re
action chamber 20.
In the case here illustrated, the high-boiling 50
fractions of the charging stock withdrawn from
the lower portion of column 9 through line 2|
and valve 22 to pump 23 are fed therefrom
through line 24, valve 25 and line 52 into reaction
55
chamber 20.
Reaction chamber 20 is also preferably oper
ated at a substantial superatmospheric pressure
and, although not indicated in the drawing, is
preferably insulated to prevent the excessive loss
of heat therefrom by radiation so that conversion 60
of the various oils. supplied to this zone, and par
ticularly their vaporous components, may con
tinue therein. The heat contained in the products
from heating coil l2 and/ or heating coil 45, which
latter are also supplied to the reaction chamber, 65
as will be later more fully described, serving to
heat the higher boiling oils supplied to this zone
and effect their appreciable conversion therein at
a temperature somewhat lower than the tempera
tures employed in the heating coils. In the par
ticular case here illustrated both vaporous and
liquid conversion products are withdrawn from
the lower portion of chamber 20 through line 56
and valve 57 and are introduced into vaporizing
chamber 26.
It will be understood, however,
2,112,876
that, when desired, all or'a regulated portion of
the vaporous products may be separately with
drawn from chamber 20 at any desired point in
this zone, by well known means not illustrated,
in which case the separately withdrawn vapors
may be supplied, all or in part, direct to fraction
ator 29 or may be introduced, all or in part, into
vaporizing chamber 26 at any desired point in
this zone, by well known means not shown in the
10
drawing.
3.
plied to the oil passing'through heating coil 45
to bring it to the desired conversion temperature,
preferably at a substantial superatmospheric pres
sure, by means of heat supplied from a furnace
46 of any suitable form and the heated products
are discharged from heating coil 45 through line
41 and may pass through line 48 and valve 54
to be introduced, in the case here illustrated,
through line I 1 into reaction chamber'zll, together
with the products from heating coil I2. When 10
desired, a regulated portion or all of the highly
Chamber 26 is preferably operated at a sub
stantially reduced pressure relative to that em I heated products from heating coil 45 may be
ployed in the reaction chamber, by means of utilized to furnish heat for fractional distillation
of ‘the charging stock by passing the same
which further vaporization of the liquid con
through. valve 55 in line 41' and through line l5 15
15 version products supplied to this zone from re
action chamber 20 is accomplished. Residual into heat exchanger 6, from which the resulting
liquid remaining unvaporized in chamber 26 may
be withdrawn from the lower portion of this zone
through line 58 and valve 59 to cooling and storage
20 or to any desired further treatment. The vapor
partially cooled products pass through line I‘!
and valve it! into reaction chamber 29. It will be
understood, of course, that all or any desired por
tion of the heated products from either or both 20
ous products evolved in chamber 26 as well as any
heating coils iii and 45 may be utilized, as de- ,
supplied to this zone from the reaction chamber
may be directed through line 2'! and valve 28 to
scribed, to supply heat to the charging stock
fractionation in fractionator 29, together with
25 any vaporous products which may be supplied,
as previously mentioned, to fractionator 29 di
rect from reaction chamber 20.
The insuiiiciently converted components of the
vaporous products supplied to fractionato-r 29,
including their fractions boiling above the range
of the desired ?nal light distillate product of the
process‘, as well as, when desired, regulated quan
tities of any selected high-boiling components of
the desired light distillate product which are of
35 inferior anti-knock value, are condensed in this
zone as reflux condensate and, in accordance with
the features of the present invention, are sep
arated into selected relatively low-boiling and
high-boiling fractions.
The relatively low-boil
40 ing and high-boiling fractions of the re?ux con
densate are each subjected to further conversion
within the system under different conversion con
ditions, as will be later more fully described.
Fractionated vapors of the desired end boiling
point, preferably comp-rising materials within
the boiling range of motor fuel of good anti-knock
value, are withdrawn, together with uncondensa
ble gas produced by the cracking operation, from
the upper portion of fractionator 29through line
' 30 and valve 3! to be subjected to condensation
and cooling in condenser 32. The resulting dis
tillate and gas passes through line 33 and valve
34 to- collection and separation in receiver 35.
Uncondensable gas may be released from the re
ceiver through line 35 and valve 3'! to absorption,
storage or elsewhere, as desired. The distillate
collected in receiver 35 may be withdrawn there—
from through line 38 and valve 39 to storage or
to any desired further treatment. When desired,
60 a regulated portion of the distillate collected in
receiver 35 may be recirculated by well known
means (not shown) to the upper portion of frac
tionator 29 to ‘serve as. a refluxing and cooling
medium in this zone to assist fractionation of
the vapors and to maintain the desired vapor out
let temperature from the fractionator.
Selected low boiling fractions of the reflux
condensate formed in fractionator 29 may be
withdrawn from any suitable intermediate point
or plurality of points in this zone and supplied,
while any remaining portion of either or both of
these streams or all of either or both may by-pass
heat exchanger 5. It will also be understood that 25
the products. from heating coils l2 and 45 may,
when desired, be separately supplied to reaction
chamber 29 each at any desired point in this zone,
although well known provisions for accomplish
ing this are‘ not shown in the drawing.
In a process of the character illustrated and
above described, the preferred range of operating
conditions may be approximately as follows: The 45
temperature to which the charging stock is sub
jected for the purpose of effecting its fractional
distillation may range, for example, from 500 to
800° F., or thereabouts, depending upon its char
acteristicsthe desired separation to be effect-ed
and upon the pressure employed in the fractional
distilling stage of the process which pressure may
range, for example, from 100 to 500 pounds, or
thereabouts, per square inch. The conversion
temperature employed at the outlet from the
heating coil to which the low boiling fractions of
the charging stock are supplied may range, for
example, from 900 to 1100° F. and preferably a
substantial superatmospheric pressure of the
order of 200 to 500 pounds, or more, per square 60
inch is employed at this point of the system al
though, when desired, lower pressures down to
100 pounds, or less, per square inch may be em
ployed in this zone. The heating coil to which,
the selected relatively low boiling fractions of the 65
intermediate conversion products of the process
are supplied may employ an outlet conversion
temperature ranging, for example, from 950 to
1050° F., preferably with a substantial sup-crat
for example, through line 49 and valve 4|, to
mospheric pressure, measured at the outlet from
the heating coil, of from: 250 to 500 pounds, or
pump 42 by means of which they are fed through
line 43 and valve 44 to further conversion in
more, per square inch. The reaction chamber is
preferably operated at a substantial superatmos
_ heating coil 45 under independently controlled
conversion conditions.
Su?icient heat is sup
30
The high boiling fractions of the re?ux con
densate formed in fractionator 29 may be with
drawn, as illustrated, from the lower portion of
this zone through line 49 and valve 50 to pump
5| by means of which they are returned through 35
line 52 and valve 53 to reaction chamber 29. It
will be understood that the relatively high boil
ing oils from column 9 and fractionator 29 may
be supplied to reaction chamber 29, separately or
in commingled state, at any desired point or plu 40
rality of points in this zone, although only one
point of introduction is shown in the drawing.
pheric pressure of the order of 100 to 500 pounds,
or thereabouts, per square inch, which pressure 75
4
2,112,376,
may be substantially the same or somewhat lower
high-boiling fractions, withdrawing said low
than that employed in the heating coil utilizing
boiling fractions from the fractional distilling
stage in vaporous state and supplying the same,
without intentional condensation thereof, to a
heating coil wherein they are subjected to con
version conditions of elevated temperature and
the lowest pressure, in case different pressures are
UK
employed in the two heating coils. The vaporizing
chamber is preferably operated at a substantially
reduced pressure relative to that employed in the
reaction chamber which may range, for example,
from substantially atmospheric to 100 pounds, or
thereabouts, per square inch superatmospheric'.
10 The pressure employed in the vaporizing chamber
may be substantially equalized or somewhat re
duced in the succeeding, fractionating, condens
ing and collecting portions of the system.
As a speci?c example of one of the many pos
15 sible operations of the process of the present in
vention utilizing as charging stock a Montana
crude‘of about 31.8° A. P. I. gravity containing
approximately 5% of material boiling up to 215°
F. and about 22% boiling up to 400° F. the crude
charging stock is heated to a temperature of ap
superatmospheric pressure, introducing the prod
ucts from said heating coil into an enlarged re—
action chamber also maintained at superatmos
pheric pressure and at a conversion temperature, 10
introducing said selected high-boiling fractions of
the charging stock into said reaction chamber
wherein they are subjected to conversion, with
drawing vaporous and liquid conversion products
from the reaction chamber, subjecting the latter 15
to further vaporization at substantially reduced
pressure,
subjecting the vaporous conversion
products of the process to fractionation, whereby
their insu?iciently converted components are
condensed as re?ux condensate and separated
distilling operation comprising approximately
into selected relatively low-boiling and high-boil
ing fractions, subjecting the fractionated vapors
of the desired end-boiling point to condensation,
collecting the resulting distillate, returning said
high-boiling fractions of the re?ux condensate 25
35% of the charging stock are subjected in a
reforming coil to a conversion temperature of
to the reaction chamber for further conversion,
subjecting said selected low-boiling fractions of
approximately 980° F. at a superatmospheric
pressure substantially equalized with that in the
30 fractional distilling stage. The stream of highly
heated products from the reforming coil is utilized
the re?ux condensate to independently controlled
conversion conditions of elevated temperature
proximately 650° F. and is subjected to fractional
distillation under a. superatmospheric pressure of
approximately 500 pounds per square inch. The
overhead vaporous products from the fractional
25
to furnish heat to the charging stock for its frac
tional distillation and is then introduced into a
reaction chamber maintained at a superatmos
pheric pressure of approximately 350 pounds per
square inch. The high boiling fractions of the
charging stock, comprising bottoms from the frac
tional distilling stage of the process, are also sup
plied to the reaction chamber. Both vaporous
40 and liquid products are withdrawn from the lower
portion of the reaction chamber and introduced
into a reduced pressure vaporizing chamber main
tained at a superatm‘ospheric pressure of approxi
mately 45 pounds per square inch from which re
45 sidual liquid is withdrawn while the vaporous
products from this zone pass to the fractionator
of the cracking system. Selected low-boiling
fractions of the re?ux condensate from the frac
tionator of the cracking system having a boiling
50 range of approximately 320 to 600° F. but con
taining less than 5% of materials boiling below
400° F. are supplied to a separate heating coil
wherein theyare subjected to a conversion tem
perature of approximately 970° F. at a super
atmospheric pressure of about 600 pounds. per
square inch and the heated products from‘ this
zone are discharged into the reaction chamber.
The remaining higher boiling fractions of the
re?ux condensate from the fractionator of the
cracking system are returned to the reaction
chamber without further heating. This operation
may produce, per barrel of charging stock, about
60% of 400° F. end-point motor fuel having an
anti-knock value equivalent to an octane number
65 of approximately 70 and about 26% of good qual
ity residual liquid suitable as premium fuel oil,
the remainder being chargeable, principally, to
uncondensable gas.
I claim as my invention:
1. A process for the fractional distillation and
conversion of hydrocarbon oils, which comprises
subjecting hydrocarbon oil of relatively wide boil
ing range to fractional distillation at substantial
superatmospheric pressure whereby it is sepa
75 rated into selected relatively low-boiling and
and superatmospheric pressure in a separate 30
heating coil and introducing the heated products
from said separate heating coil into the reaction
chamber.
2. A process of the character de?ned in claim
1, wherein regulated quantities of the highly 35
heated products from the ?rst mentioned heating
coil are utilized to supply heat for said fractional
distillation of the charging stock, by indirect
heat exchange therewith, prior to their introduc
tion into the reaction chamber.
3. A process of the character de?ned in claim
1, wherein regulated quantities of the highly
heated products from the last mentioned heating
coil are utilized to'supply heat for said fractional
distillation of the charging stock, by indirect heat 45
exchange therewith, prior to their introduction
into the reaction chamber.
4. A process of the character de?ned in claim
1, wherein regulated quantities of the highly
heated products from both heating coils of the
system are utilized to supply heat for said frac
tional distillation of the charging stock, by indi
rect heat exchange therewith, prior to their in
troduction into the reaction chamber.
5. A hydrocarbon oil conversion process which 55
comprises fractionating the charging oil to form
a relatively light fraction and a heavier fraction,
simultaneously fractionating hydrocarbon vapors
independently of the charging oil and separating
a relatively light re?ux condensate and a heavier 60
re?ux condensate therefrom, passing said light
fraction and said light re?ux condensate through
separate heating coils and subjecting the same
therein to independently controlled cracking
conditions of temperature and pressure, intro 65
ducing the heated products from said coils into
an enlarged reaction zone, introducing said
heavier fraction and said heavier re?ux con
densate, without prior cracking thereof, to the re
action zone, separating the mixture formed in 70
the reaction zone into vapors and residue, frac
tionating the former as said hydrocarbon vapors,
and ?nally condensing the fractionated vapors.
6. A hydrocarbon oil conversion process which
comprises fractionating’the charging oil to form 75
2,112,376
5
a relatively light fraction and a heavier fraction, cracking thereof, with the heated products from
simultaneously fractionating hydrocarbon vapors _ said coils, passing the resultant mixture through
and separating a relatively light re?ux con
densate and a heavier re?ux condensate there
from, passing said light fraction and said light
re?ux condensate through separate heating coils
and subjecting the same therein to independently
controlled cracking conditions of temperature
and pressure, combining said heavier fraction
10 and said heavier re?ux condensate, without prior
an enlarged reaction zone maintained under
cracking conditions of temperature and pressure,
removing the mixture from the reaction zone and 5
reducing the pressure thereon to separate the
same into vapors and residue, fractionating the
former as said hydrocarbon vapors, and ?nally
condensing the fractionated vapors.
JACQUE C. MORRELL.
10
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