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Патент USA US2133070

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Oct. 11, 1938.
Original Filed Feb. 12, 1932
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Oct. 11, 1938.
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BY a”? Q,»
Patented Oct. 11, 1938
, A
Malcolm P. Youlrer, Bartlesville, Okla, assignor
-to Phillips Petroleum Company, Bartlesville,
0kla., a corporation of Delaware I
Original application February 12, 1932, Serial No.
592,614. Divided and this application Febru
ary 25,vv 1936, Serial No. 65,689
2’ Claims. (01. 196-9)
This invention relates to improvements in proc
9 through the vent pipe ll. Liquid will be with
esses for converting hydrocarbon liquids or gases,
and the present application is a division of-my
drawn from the salt settler 2 through a pipe l2
by a pump l3 and will be deliveredby pump I3
through pipe l4 and thence through a heating
tube I5 which passes through furnace 5 and de
application Serial No. 592,614, ?led February 12,
An object of the invention is to provide a proc
ess by which gasoline having a high. antiknock
rating and other desirable qualities may be man
ufactured directly'from crude oil.
Another object is to minimize the losses due to
conversion of liquids t9 gases which normally
results from the conversion of heavy hydrocarbon
liquids to lighter hydrocarbon liquids.
These desirable ends, as well as others, are at
tained by the process.'
With the foregoing objects outlined and with
other objects in view, which will appear as the
description proceeds, the invention consists in the
novel features hereinafter described in detail,
illustrated in the accompanying drawings and
more particularly pointed out in the appended
The form of apparatus by which my new proc
ess is carriedout is illustrated on the accompany
Figure 1 illustrates in elevation the complete
_ Figure 2 is an elevation of the furnace 5 shown
in Figure l, the side wall of the furnace being
shown removed and the arrangement of the heat
ing tubes and ba?ie wallsin the furnace thereby
being revealed.
. f
heating tube l5. Liquid which is passedthrough
the heating tube 15 will be heated therein and
will, upon entry into the fractionating tower 16,
to a large extent, vaporize, and the vapors thus
generated will-flow upward through the frac
tionating tower I6 and bubble traysv l8, and 15
thence through pipe 19 and condenser 29 and
pipe 2 I‘ into the gas-liquid separator 22.
Gas which will accumulate in the separator 22
in gaseous. condition will -be vented therefrom
through the pipe 23 in which is mounted a valve 20
24. A part of the gas which will accumulate in
liquid state in the separator 22 will be pumped
25 ‘ing' drawings.
livers into the lower ‘portion of fractionating .
tower 16. A valve I‘! which is mounted in heat
ing tube 15 between furnace 5 and fractionating
tower It will be utilized to maintain pressure in
, -'
‘Figure 3 is a plan view of the furnace 5, the
top of which is shown removed thus revealing
therefrom-through the pipe 25 by means of the
pump 26 into and through heating tube I 5. A
part of the lique?ed gas which will accumulate 25
in the separator 22 will be delivered thence by
pump 21 through pipe 28 in which is mounted
valve 29 into the top of fractionating tower l3.
As a result of delivering said liquid through pipe
23 into the top ‘of fractionating tower l6, liquid
re?ux will flow downward through fractionating
tower 16 over bubble trays l8 and will contact
and condense a portion of the vapors which will
rise through fractionating tower > l6, and as a
I. .the arrangement of- the ba?ie walls and heating result of said condensation, liquid, consisting‘ of 35
- gasoline and heavier ?uid, will accumulate in the
tubes in theinterior of the furnace.
fractionating tower l6. Liquid which will collect
Crude oil will be delivered through they pipe I
into the salt settler 2 which is a horizontal cylin
- drical tank.
A liquid level normally} above the
40 center of the salt settler 2 ,will be maintained.
Liquid will be delivered from the tank 2 through
the pipe 3 by means of the ‘pump 4 through a
. furnace 5 and into the pipe I. The liquid thus
delivered through pipe 3 will-1 be heated'in pass
in the bottom of fractionating tower 16 will flow
thence through pipe 28' in which is mounted a
valve 29’ into a fractionating tower 30 at a point 40
below‘thebubble trays 3| which aremo'imted. in
fractionating tower 30.
Pressure will be maintained in fractionating
tower, IS in excess of the pressure which will be
ing through the furnace 5 and being delivered
maintainedin the fractionating tower 30, and, 45
into the pipe I will mix with’j and heat the crude.
oil fl'o‘wing through the pip'en into the salt set-'
tler 2. As a‘result‘of heating the crude oil enter
tower l6 through . pipe 28' into fractionating
ing-the salt settler/2, vapors will be'generated
therein, and these vapors will ?ow through the
pipe 6 into condenser ‘l. ,éondensate will ?ow
from the condenserl] through‘ the pipe 8 into the
accumulator 9. The temperature maintained in
the salt settler 2 will be‘ insu?ivcient to crackthe
as a result, liquid flowing from fractionating‘
tower 30, will partially vaporize upon entry into
fractionating tower 30, and vapors thus gener
ated will ?ow upward through bubble plates 3| 50
in fractionating tower 39, and thence through
pipe 32, clay treater 33, pipe 34, and condenser.
35. Condensate, will ?ow from condenser 35
through pipe 36 into accumulator 31. M
oil and only suchthat gasoline ,vapors distilled _ A su?icient quantity of the liquid which will 55
therefrom will flow into the condenser 1,‘ and gather in the accumulator 3] will be pumped
therefore, gasoline only will. be accumulated‘ in therefrom through pipe 38 by means of pump 39
the accumulator 9. Gasoline may be withdrawn - into the top of fractionating tower. 30 to main
from the accumulator 9 through the valved pipe ' tain a. temperatureat the top of'fractionating
l0.‘ Gases will be vented ‘from the accumulator
tower 30 such that only gasoline vapors will pass
therefrom to the condenser 35. Thus gasoline
tained at lower pressures, I=wi1l preferably main
onlywill be delivered into the accumulator 31.
Gasoline will be withdrawn from accumulator
tain a pressure of approximately 3000 pounds per
square inch in the heating tube l5. Normally the
pressure set up at the discharge of the pumps {3
and 26' will be 3000 pounds per square inch,
and pressure taken at intermediate points along
I 31 through the pipe 40 in which is mounted valve
4|. Gas will be vented from accumulator 31
through vent pipe 42. As a result of introducing
cold gasoline into'the topv of fractionating tower
30, re?ux liquid will'?ow downward over bubble
the heating tube I5 will be less than 3000 pounds
per square inchby the amount of friction heat
between .the point of which such pressure is taken
‘and said pumps. A pressure ‘of between 200
pounds per square. inch and 1000 pounds per
square inch, preferably about 500 pounds per
square inch, will be maintained inv'the fractionat
plates 3| and will condense that part of the vvapors
10 rising through fractionating tower 30 which is
heavier than gasoline. Distillate which is heav
ier than gasoline may be withdrawn from one of
the bubble trays 3| which is intermediate between
the point 'of entry of pipe 28’ in fractionatmg ' ing tower IS, the separator 22, the condenser 20,
and inter-connecting pipes.
15 tower 30 and the top of fractionating tower 30
. through a pipe 43 in which is mounted a valve 44. ‘
' The pressure maintained in_ the fractionating
Distillate will be delivered‘by a pumpv45 from one column 30,.the clay treater 33, condenser 35 and
of the bubble plates 3| through a pipe 46 which, inter-connecting lines. will be only in excess of
will ‘pass through furnace 5 and lead into the pipe , atmospheric pressure, to the extent'that pressure
They liquid which will be passed throughpipe
' 46 will be heated in passage through furnace 5
and will, upon entry into the pipe 28',‘heatvthe
liquids which will ?ow from the fractionating
25 tower l6 through the pipe 28'.
Fuel oil will be withdrawn from the bottom of
fractionating tower‘30 through pipe 41 in which
‘is set up by reason of the resistance to ?ow of 20
vapors and condensate through this system, as
the accumulator 31 will be operated at approxi
mately atmospheric pressure.‘ -
Thev length of that part of .the pipe 3 which
will be exposed to heatin the furnace 5 will be 25
so proportioned that the liquid which will enter
the salt settler 2 will be heated toabout 250° F.
is mounted valve 48. A pipe 1 49 in which is
mounted a valve 50 will serve to conduct liquid
from an-intermediate one of the bubble trays l8
Therefore,‘ nothing heavier thanfgasoline will be
into fractionating tower 30.,
vary between 800° F. and 900° F._, andthis tem
vaporized in the salt settler 2.
By regulation of the quantity of fuel ?red in 30
in fractionating tower l6 into fractionating tower the‘ furnace 5, the temperature to which the liquid
‘30 at a point above the entry point of pipe 28' . passed through heating tube l5 will be heated will
_ _
. ‘
A conventional caustic washer 5| is mounted in‘
35 the pipe 25 and serves to remove hydrogen sul?de
and other impurities from the lique?ed gas which
?ows through the pipe 25. ~
perature will preferably bebe
117345’ F. and
865° F. The temperature nia
‘ ved at the top 35
of the fractionating tower' is ‘by‘ih‘éans of regulat
ing the delivery of re?ux liquid into the top of
A‘ pump 56 is mounted ‘in a pipe 51 in which is
mounted a valve 58 and which leads into heating
tube l5 by means of which straight run gasoline,
hydrocarbon gas, either in liquid or gaseous form,
this towerwill be such that the vapor pressure of
the liquid leaving the bottom ‘of this fractionating
tower will be in accord with the current speci?ca
tions for motor fuel, which at this‘ time vary be
fuel oil, hydrogen,>or any other hydrocarbon ma-.' tween 8 pounds per square inch and 13 pounds
terial or treating agent ‘may be introduced into
per square inch when taken by the Reid method
and passed through the heating tube I5. I may
45 elect to deliver gasoline collected in the accumu
lator 9 and into and through the heating tube
l5 by means of the pump 56 and the valved pipe
at 100° F. That part of the pipe 46 which will be
Water or water containing treating agents,
50 either in suspension or in solution, or treating
agents alone,v may be introduced through valved
pipe tli‘into the heated hydrocarbon which will
flow from the furnace through heating tulbe I5
into fractionating tower l6.
exposed to heat in the furnace 5rwill be so propor 45
tioned that the bottom of thefractionating tower
30 will be heated to the extent necessary to re
move from the liquidswhich will‘ collect in the
bottom of fractionating tower‘ .30 practically all
, gasoline fractions.
The heating tube l5
a heating
portion and a conversion portion after the man
ner which has already been disclosed in applica
- tions for patent ?led by the present applicant
Crude oil being vpreheated and delivered into
salt settler 2 will ?ow slowly through this salt
under the following listedpatentv applications:
settler and any salt contained in the crude, as
well as ‘other debris,ywill be settled from the crude
U. S. Serial No. 545,309, ?ledjJii'n'e:ll8, 1931; U. S.
Serial No. 579,044, ?led December‘4', 1931; and
therein and will be periodically removed.~ '
U. S. Serial No.'579,538,'?led' December 7, 1931.
A body of fuller’s earth will be so disposed in
the clay treater 33 that vapors~may readily flow
' through this body of clay and intimately contact
the particles thereof. Polymerized hydrocarbon
. U. S. Serial No. 399, ?ledjJanuary' 4, 1935;
As outlined in the above mentioned applica 60
tions for patents, inv order to' avoid'rapid deposi
tion of coke in the apparatus and to at the same
time‘ obtain satisfactory conversion in the heating
liquids which will be formed in the clay treater tube l5 of the materials passed therethrough, it
65 33 as a‘ result of the contact between vapors and is desirable to ?rst rapidly heat these materials‘ 65
fuller’s earth therein, will be withdrawn there 'to conversion temperatures in the ?rst part‘of
from through a pipe 52 in which is mounted a the heating tube l5 and then pass' the thus heated
valve 53. These polymerized hydrocarbons may material through a latter portion of the heating
either be withdrawn to storage or theymay be, tube I5’which is so arranged in the furnace as to
V70 delivered by means of a pump 54 which is mount be only mildly heated.
ed in ‘a pipe 55 into fractionating column 30.
Referring to Figures 2*and'3 of the drawings, it
The pressure maintained in the salt settler 2 ' "will be noted that the interior of the furnace 5
will be only that which is set up therein by resist
is so partitioned off by abridge wall GI and
ance to ?ow of vapors through the pipe 6 and the a ba?le wall 62 that a combustion chamber is
76 condenser 1. Although good results may be ob'- , formed between bridge wall gland the end wall 75
69-0f the furnace and that gases of combustion
portion of the heating tube l6 to any desired
developed in this combustion chamber are re-_
stricted to ?ow upward over the top of bridge
wall 6| thence downward through a passageway
between bridge wall 6|Z and- ba?ie wall 62 thence
under ba?le wall 62 and thence upward through
a passageway between bridge wall 62 and the ad
jacent end wall 10 of the furnace and thence
through a breeching 63 in which is mounted a
temperature and in this way heat- transfer from
the gases of combustion to the conversion portion
of the heating tube I 6 may be caused to take place
at a low rate and the quantity of heat so trans
ferred may be regulated. It is apparent that some
other stream of liquid might be passed through
the pipe ‘46 to accomplish this purpose and that
my reasons for using the particular stream of liq
10 damper 64 and thence upward through a smoke ' uid designated are economic.
stack 65. A breeching 66 in which is mounted a
fan 61 and a damper 66 is_inter-connectedn_be
The manner in which the breeching 66, to
gether with the fan 61 and the damper 66, may
tween the bottom of said last-mentioned passage- ' be advantageously used to abstract gases of com
way between said ba?le wall and said adjacent
15 end wall and the bottomof said smoke stack 66.
bustion from the furnace before the same have ,'
passed over the conversion portion of the heat 15
The fan 61 may be operated to force gases of com- - .ing tube II or to force recirculation of gases from
bustion from the smoke stack into the furnace, the smoke stack back into the furnace and over
thus recirculating gases of combustion through said conversion portion of said tube is already dis
'said last-mentioned passageway, or said fan may closed in the above-mentioned patent applica
be allowed to remain stationary in which‘case tion Serial No. 579,044, previously filed by the 20
gases of combustion-will flow from the furnace present applicant. ‘
I into the smoke stack through the breeching 66,
and in either case the damper 68 may be used to
regulate the ?ow of gases. of combustion through
25 the breeching. 66. Temperature recording devices
not shown on the drawings are of course in
stalled'at the junction of the heating portion and
the conversion portion and at the outlet of the
heating tube l5 to indicate and record the tem
80 perature of material passing through the heating
tube at these points. The heating tube I5 is made'
up of a plurality‘ of horizontal tubes intercon
nected by means of return bends in a convention
al manner and is supported in the furnaceby
35 conventional tube sheets which are not shown“
That portion of the heating tube l5 which is uti
lized for the rapid heating of the materials passed
therethrough to conversion temperature is so dis
posed over the combustion chamber and in the
Circulating gases of combustion from the bot- ‘ I
tom of the smoke stack 66 by means of the fan‘
61 through the breeching‘ 66. into the furnace
and thence upward through the passageway be 25
tween ba?ie wall 62 and end wall ‘I. and thence
through breeching 66 into smoke stack 66 in regu
lated quantities will result in regulated cooling of
the gases of combustion prior to their passage over
the conversion portion of heating tube l6, thus 30
permitting regulated moderate heating of the ma
‘terials passing through the conversion portion
~ of heating tube l6. - Withdrawing gases of com
bustion in 'regulated quantities from the furnace
6'into smoke stack 66 through the breeching 66 35
will ‘result in regulating the quantity of gases of ,
‘combustion which will flow over the conversion
portion of the heating tube l6 and will thus result
in the regulated moderate heating of the mate
passageway between bridge wall 6.] and bailie wall . rials passing through the conversion portion of
62 that gases of combustion developed in the com
the heating tube l6.
bustion chamber immediately and before con-J
It should be noted that while ?nally contacting
tacting any other heat absorbing surface are gases of combustion with the preheating pipe 6 is
contacted therewith. The conversion portion of
an economic‘ arrangement the principally ad- '
45 the heatingjtube IS in which conversion of the‘
vantageous feature of the furnace and heating 45'
materials passed therethrough takes place is dis
arrangement shown is. that the gases ‘of combus
posed in the passageway between the ba?ie wall tion after being contacted with the heating por
62 and the adjacent end ,wall ‘III of the furnace. tion of the heating tube II are cooled by being
' That portion of thepipe 46 which passes through‘ contacted with the heating pipe 46 before being
50 the furnace 5 is disposed in the passageway be-' contacted with the conversion portion of the 50
tween bridge wall-6| and ba?le wall 62 and. in 'a heating tube‘ I6k thus permitting mild'heating
- positionbelow
tuberl5. That the
of the
pipe 3ofwhich
the heating
passes, = of'said conversion 'portion of said tube.
The materials passed through the heatingtube
through furnace 5 is disposed in‘ the passageway [6 should be heated in passingitherethrough to a .
55 between the bai?e wall 62 and the‘ adjacent end‘ maximum temperature in‘ the heating portion of
wall 10,0f the furnace in a position above the
conversion portion of the heating tube [5.‘
this tube and the temperature of these materials 55
should‘ not thereafter be increased in passing
It will beseen that the flow of gases of combus- ~ through the conversion portion of the tube. In
; tion through the furnace 5 is such that these ‘other words, a portion ofv the h€ating tube l6
adiace‘nt'to'the exit end“ of said tube should be 60
60 gases ?rst contact the heating portion of the
heating tube l5;- second, contact that portion of
theipipe 46 which passes through the furnace 6;
third, contact the conversion portion of the .heat
ing tube l5: and, fourth, contact that part of the"
65 pipe'3 which passes through the furnace 5.1 The
quantity of liquid which will be pumped through
the pipe 46 will be so regulated and the length
and size of that portion 'of the‘pipe 46 which is
disposed in the furnace 5 will be so proportioned’
as to reduce the temperature of the gases of com
bustion passing around the pipe 46 to any desired
temperature before these gases contact the con
version portion of the heating tube i5. Increas
ing the ?ow of oil through pipe 46 wilL cool the
gasesv of combustion passing over the conversion
heated in a manner such that only heat absorbed
by the conversion reaction is supplied‘ to the ma
terials ?owing therethrou'gh'and such that the
. temperature of suchv materials is not increased in
passing through thislatter portion 'of said heat
' ing ~tube. - The conversion‘ portion of the heating.
tube is should be of substantial‘ length. / While
some results may be obtained by using a three
inch ‘inside diameter tube as short as 500 feet,‘it
is desirable ‘to use a three inch‘ inside diameter 70'
tube at,least 2000 feet 1038, and preferably 3000 '
or M00v feet long, for conversion j purposes,
through which the material to be converted is
flawed after such material has been b‘roughtj'to
conversion temperature. While I ‘have described is '1
- 2, 183,070
tained in the conversion portion of the heating
returning some of said condensate in lique?ed
condition into the upper portion of said recti-,
tube I5, I would say that in order‘ to obtain re
?cation zone for re?uxing said zone, dividing said
the desirablev conditions which should boob
sults su?iciently practical to permit commercial
operation it is absolutely necessary that not less
ihan the latter 500 linear feet or" the heating tube
- I5 be supplied with heat in quantity such that
the temperature of the materials passing there-'
through be raised not more than two degrees
Fahrenheit per 100 feet of travel through said
latter portion of heating tube ,l5 and as stated
above heat should preferably be supplied to the
materials passing through the latter portion of
said hea‘ing tube in considerably less than this
normally liquid hydrocarbons into a plurality of
streams and after releasing the pressure on the
same introducing these streams at different ele
vations into a second recti?cation zone main
tained under substantially atmospheric pressure,
heating the lower portion of the second recti
?cation zone by withdrawing a portion of the
normally liquid hydrocarbons, heating the with
drawn portion and returning the same to the
lower portion of the second recti?cation zone,
rectifying the normally liquid hydrocarbons in
the second rectifying zone and thereby separat 15
The maximum advantageous tempera‘ ure to be ing hydrocarbons in the gasoline range from
used will be found to ‘vary with the type of - heavier hydrocarbons,- discharging the hydrocar
bons in the gasoline range from the upper por
material undergoing conversion. I have con
structed and have in operation two heating tubes tion of the second recti?cation zone and con
similar to the heating tube I5 herein described, densing the ‘same, returning'a portion or‘ the
one of which, is used for the conversion of heavy resulting condensate into the upper portion of
fuel oil to gasoline and gas oil and one of which
is used for converting gas‘oil to gasoiine. I-?nd
that maintaining temperatures of approximately
850° _F. and 840° F., respectively, at the inlet
and the outlet of the conversion portion of the
heating tube obtains very good results in the
conversion or‘ the fuel oil when operated under a
pressure of about 350v pounds per square inch,
30 while for the advantageous conversion of gas oil
temperatures of approximately 885° F. and 375°
K, respectively, maintained at the iniet and out
_let of the conversion portion of the heating tube
appear to be the best temperatures when operat
ing under about 350 pounds per square inch pres
the ‘second recti?cation zone as a re?ux, and
withdrawing hydrocarbons heavier than gasoline
from the second recti?cation zone.
2. In a process for converting hydrocarbon
fluids in which the fluid is subjected to pressure
conversion in a conversion zone from which the
resulting mixture is removed, the improvement
which comprises rectifying said. mixture in a
?rst recti?cation zone under a pressure su?icient 30
to maintain some of the normally gaseous com
ponents of the mixture in lique?ed condition,
discharging normally gaseous components from
the top of said recti?cation zone and cooling the.
sure. It should be noted that while the present
same to condense a heavier portion of said nor-'
mally gaseous components, then passing said
- process is speci?cally outline-:1, for and appears'to
gaseous components into a separating zone and .
be particularly advantageous for the conversion
of crude oiis the process may also be advanta
40 geously utilized for the conversion of other oils
such as fuei oil or gas oil.
It appears that the conversion of oils, which
already con‘ain gasoline, to gasoline may be ac
separating the condensate from the uncondensed
portion, discharging the uncondensed portion
from said separatinguzone, passing a portion of i
said condensate from the separating zone into
the upper portion of said recti?cation zone and
using it as a re?ux to prevent normally liquid
by the combination ‘ hydrocarbons from leaving the upper portion of
complished particularly
said recti?cation zone, passing another portion 45
of said condensate in liquid condition to the
inlet of the conversion zone, passing a light liq
pounds per square inch particularly in that the , uid fraction from the medial portion of said
45 of steps outlined herein; that is, by passing the‘
same through the heating tube iii in the manner
described under a pressure upwards of 1500
' an'iknock rating of the gasoline as a whole thus
produced from crude oil is‘ high.
In the present application I am claiming the
fractionating method disclosed in my prior ap
plication Serial No. 579,538 dated Dec. 7, 1931.
While I ‘have described in detail a method by
recti?cation zone into the medial portion of a
second recti?cation zone maintained under lower
pressure, passing a heavier liquid fraction from
the lower portion of the ?rst recti?cation zone ,
into the lower portion of the second recti?cation
zone, withdrawing a‘ distillate stream- from the .‘
second recti?cation zone at a point between the 65
55 which'my ‘newprocess?may be carried out, it
is to be understood that I do not intend to limit ' points where the liquid fractions are'introduced
my [claims to these detailsbut intend to claim into‘ the same, reheating said distillate stream
broadly aii of the advantages which are-inherent
in this process.
‘What I claim and desire-to, secure by Letters
Patent isi
and mixing it with said heavier liquid fraction
before the latter enters the second recti?cation
zone, vwhereby the lower portion of ,the second 60
‘recti?cation zone is heated sufiiciently to cause
in vapor phase to be discharged from
Lin a process of the character described, in“ gasoline
producing thermally conrerted hydrocarbons in the upper portion of the second recti?cation
heated condition into the lower portioniof a ?rst zone; condensing the gasoline vapors discharged
65 recti?cation zone main‘ain'ed under relatively from the upper portion of the second recti?cation
‘high sup-eratmospheric pressure, rectifying said zone, withdrawing a part of the gasoline conden
hydrocarbons in said zone and thereby effecting V sate as a product of‘the, process, and returning
a relatively sharp separation between normally
“' gaseous,hydrocarbonsé and normally liquid hy
70 drocarbons, discharging said normally gaseous
‘hydrocarbons from the upper portion of ‘said zone
and cooling and condensing some of ,thesame,
a part of the gasoline condensate ,to the upper
portion of theysecond recti?cation zone as a
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