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Патент USA US2407817

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Sept 17, 1946.v
A. v. DANNER
_
2,407,17
CONVERTING HYDROCARBONS
Filed March 28, 1945
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INVENTOR
‘
rferwe k?o/mzz ‘
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A
NTOR ATTORNEY
2,407,817‘
Patented Sept. 17, 1946
UNITED/ STATES PATENT 3 OFFICE
2,407,817
CONVERTING HYDROCARBONS ‘
Arthur V. Danner, Villanova, Pa., assignor to
Socony-Vacuum Oil Company, Incorporated,
New York, N. Y., a corporation of New York
Application March 28, 1945, Serial No. 585,349
8 Claims. (Cl. 196-52)
1
This‘ invention has to do with processes for the
conversion of high boiling hydrocarbons of the
nature of gas oil into motor fuel of high anti
knock capability, and is particularly concerned
with processes of ‘that nature which are carried
out in the presence of solid adsorbent materialv
2
gasoline so produced, and treatment for the re-,
moval of such compounds is necessary.
Former
ly, in sweetening, these compounds were changed
to supposedly innocuous compounds, as disul
phides remaining in the oil, but present practise
demands the removal of such compounds, since
the supposedly innocuous disulphides and other
sulfur have been found to have a negative effect.
the production of motor fuels for use in any type
upon the lead susceptibility of the fuel in'which
of internal ‘combustion engine, it is‘ particularly
suitable for the production of fuels for use in high 10 they are present.
This invention is based upon the discovery that;
compression ratio motors.
unusual and unexpected results, bothin terms of
‘This process is particularly concerned with the
operability, of quality and. amount of products,
joint operation of processes for the production of
and in terms of economic operation, can be ob
gasoline together with a relatively high produc
tion of ole?nic gases and the conversion of such 15 tained by a proper setup of operative processes,
as set forth hereinafter.
ole?nic gases to useful motor fue1 components
In order that my process may be understood
of high‘ anti-knock capability, and has for its
readily, reference is now made to the drawing at
principal object the operation of such processes
tached to and made a part of this speci?cation,
in cooperation, one with another, whereby a
greatly enhanced capability in gasoline manu 20 the single ?gure of which shows one operating
setup for the practise of my invention.
facture is obtained.
In the drawing a cracking stock which may be
It has as another object the‘provision of a
While the process here set forth is useful for
unitary process whereby in a two step manner a
a gas oil of normal characteristics, with or with;
lesser storage stability. Additionally, if sulfur
be present in the gas oil originally cracked, sig
ni?cant amounts of lighter mercaptans and other
in furnace 6 where it is heated to a temperature
out admixed heavy naphtha, is introduced
gasoline is produced, and gaseous products of
such reaction are recombined as liquid products 25 through pump l and pipe 2 to pass through heat
ing coils 3, 4 and 5 in furnace 6 and. is then dis
of high anti-knock capability as compounds of
charged through pipe 1 under the control, if de
said gasoline.
sired, of a back pressure valve 8 into vapor.sepa
As another object'it has the effecting of con
rator 9. _A solid particle form adsorbent mate
siderable economies in overall operation by the
concurrent practise and pro-per coordination of 30 rial, as and for a, purpose hereinafter described,
having been added to the charged by pipe Hi, the
certain heretofore independent process steps in
tar separated in vapor separator 9 and leaving
a manner hereinafter disclosed.
through pipe II will contain substantially all of
In the cracking of hydrocarbons, certain proc
that contact mass material. In many cases to
esses frequently give rise when practised at their
optimum conditions for yield of gasoline and 35 'prevent entire vaporization of the furnace efllu
ent in vapor separator 9, it is necessary to intro
anti-knock character of gasoline, to ole?ne prod
duce a quenching oil, later to be described,
ucts, normally gaseous or present mainly in the
through pipe I2. Vapors from vapor separator
lower boiling portion of the gasoline produced.
9 pass through vapor line 13 to fractionator l4,
Among such processes are those wherein a solid
catalyst of [clay-like nature is suspended as a 40 there to be separated into a heavier than gaso-,
line portion leaving the fractionator HI through
slurry in a liquid phase or mixed phase or vapor
pipe l5 and a gasoline and lighter portion pass
phase operation, similar in nature to ordinary
ing overhead through pipe Hi. This gasoline and
thermal processing but conducted at a tempera
lighter portion enters fractionator I‘! and is there
ture sufficiently elevated to take advantage of
separated into a raw gasoline fraction leaving
the suspended, solid adsorbent. A process of this
through pipe l8 and a gasfraction high in ole
general type is described in Jenkins Patent No.
?nic content leaving through pipe [9. In the
2,167,211. The gasoline produced directly from
preferred form of operation, this gaseous frac
such processes, when freed of ole?nic constitu
tion passing through pipes l9 and 20 may be
ents, is of high anti-knock capability, but with
compressed by compressor 2|. and then passes
the ole?nes present, is of lower value, of lower
through pipe 22 and pipe 23 into heating coil 24
susceptibility to anti-knock additives, and has a
appropriate for the following step and passes
through pipe 25 into a catalytic reactor‘ 26. In
low boiling sulfur compounds are present in .the 55 this catalytic reactor 26 the ole?ne containing
3
2,407,817
gases are contacted under reaction conditions of
temperature and pressure with a solid particle
form adsorbent contact mass to bring about their
polymerization into materials largely of gasoline
boiling range. E?‘luent vapors from reactor 26
pass through pipe 27 and may, by means of valve
28 be introduced into fractionator £4 at the same
point as are Vapors from vapor separator 9 or,
4
if desired, as wet re?ux for control of the top
temperature of fractionating tower l1. It will
also be noted that a pump 5| and pipe 52 are
provided so that liquid product from the bottom
of fractionator I‘! may be utilized as wet re?ux
for control of the temperature at the top of frac
tionator Hi.
In case fractionator I1 is utilized to cut sim
valve 28 being closed, they may be introduced
ply between a raw _gasoline and an‘ overhead
through pipe 29 to a higher level in fractionator 10 vapor cut, the raw gasoline emergent from frac
N, there to be fractionated along with the va
tionator I‘! through pipe is is diverted through
pors from the original gas oil cracking.
pipe 53, valve 54 being closed, to enter stabilizer
Frequently, and especially in the case where
55 wherein the gasoline is stabilized to a desired
stocks of relatively high sulfur content are orig
vapor pressure which may be, if desired, a rela
inally cracked, in the gas oil cracking step, it ‘ tively low vapor pressure for more complete re
is desirable to reduce the sulfur content of the
moval of ole?nic materials, to later be raised by
gaseous products prior to their treatment and
addition of light materials from another source.
especially to reduce the amount of hydrogen sul
Stabilized gasoline departing through pipe 55'
phide and similar readily reactive sulfur com
pounds which may be present. In this case,‘ with
valve 3!! closed, the gases from pipe 26 will be
passed through pipe 3| into a scrubber 32 Where
in they may be scrubbed by caustic soda solution
or other appropriate alkaline reagent introduced
is removed from the system as gasoline product
at the lower extremity of pipe it in the flow
sheet shown. Overhead stabilizer gases leaving
the stabilizer through pipe 51 are cooled,‘ con
densed and collected in the‘ customary setup of
cooler 58, condenser 59 andreceivei' 60, there
through pipe 33 and leaving through pipe 34. 25 after to be forwarded by pump 6| through pipe ,
62 to pipe 23 to be treated in the polymerization
scrubber 32 through pipe 35' and reenter pipe
reaction, a portion being diverted through pipe
20 through pipe 36, being disposed of afterward
63 for‘the control of the stabilizer.
'
The scrubbed gases in this case will pass‘ from
in the usual fashion. In many cases, particu
Returning now to the polymerization reactor
larly if a relatively long cut of these gases has 30 26, we find this reactor to be supplied with ‘a
been made, it will be desirable to divert these
gases through valve 3'! to pass through a partial
condenser 33 and into receiver 39 wherein a
liquid/vapor separation occurs, the vapor being
passed through pipe 43 to compressor 2!, and
the liquids being passed by vthe agency of pump
4| into pipe 23 for treatment in the polymeriza
tion reaction.
It is’ also frequently desirable to utilize the
solid particle form catalytic .material' through
pipe 64, hopper 65, and appropriate controlled
feed leg 66. Spent contact masses from this re—
actor removed. through controlled drain leg 6‘!
is collected in a hopperv 68. It is therein pref
erably reduced‘ into a slurry through the agency
of gas oil supplied by pipe 69‘ and passes from
hopper 68 in slurry‘ form through pipe In to be
introducedinto the gas oil cracking reaction.
condenser 38 and receiver 39 to effect a rough 40
Turningvto‘the bottom of fractionator Mjthe
separation between gases to be treated and a
heavier than gasoline or recycle gas oil cut col
liquid fraction which it is not desired to treat,
in which case that liquid may be withdrawn from
the. system through pipe 42. In other cases, liq
uid from receiver 39 maybe passed through pipe
43 to be included with the gasoline withdrawn
from the bottom of iractionator H for stabiliza
tion and disposal in a manner hereinafter dis
closed.
Fractionator ll may also be so operated as to
produce a gas out, which overhead gas out passes
lected therein, is drawn upon by pump 10 and
passed through pipe ‘H from whence a portion or
all may be diverted through pipe 12 to supply
the quenching requirements of the operation
through pipe [2 and/or the slurry producing re
quirements of the operation through pipe 69.
Also material from pipe Tl may pass through
pipe 13 to assist in introduction of the slurry into
the gas oil cracking system as well as to serve
as recycle therein. It wil'l'be noted that, if de
under system pressure through pipe 19 and pipe
sired, all of the recycle stock produced in frac
44 and is introduced directly into pipe 23 to pass
tionator It may thus be recycled to the gas oil
through the polymerizing step under that sys
cracking operation. If it is not desired to recycle
tem pressure.
55 all of this material, a portion may be withdrawn
Fractionator I‘! may also be so operated as to
from the system through. pipe ‘M. It will‘also be
produce a. bottoms cut which comprises the
heavier portions of the desired gasoline, a side
noted that a light gas oil fraction may be with
drawn, if desired, from tower Itv through pipe T5.
out which comprises lighter portions of gasoline
The gas oil cracking operation may be con
containing ole?nic materials emergent from the 60 ducted in vapor phase, in liquid phase or in
fractionator through pipe 45 and a gas cut
mixed phase condition. The process also may
emergent from the fractionator overhead through
be used‘ to crack or vis-break heavier charge
pipe l9. In this case the overhead gas cut may
stocks. Most usually,‘ the process will be con
be handled in any of the Ways hereinbefore set
ducted either in vapor phase or in a mixed phase
forth and‘ it will be usual to take the side out 65 condition bordering upon complete vaporization.
produced through pipe 4:5 and pass it through
The gas oil cracking will’ ordinarily be con
pipes 44 and 48, valve 49 being closed, to con
ducted at temperatures in the range of from
denser 38 and receiver 39, after which through
about 1000° F. to about 1100“ F. and at pressures
the agency of. equipment hereinbefore explained,
of the order of 400 to 500- p. s. i. gauge or more,
both the side cut of light gasoline and the over“ 70 in the presence of from about 2 pounds to about
head out of gases may be combined and passed
101 pounds of contact mass per barrel of total
through pipe 23, heating coil 24 and the poly
charge to furnace. Such‘a process will produce,
merization reactor 26.
from normal gas oiI upon a once through basis,
It will be noted that a. pipe 53 is provided in
from about 20% to about 50% af gasoline of400°
order that liquid from pipe 23 may be utilized,
' F. end‘ point by volume on gas oil‘ consumed in
2,407,817- .
5
carbons of higher boiling point to motor fuel of
high quality the steps which comprise: subject
process, together with from about ?ve to about
twenty percent of gases, (by weight on charge
consumed), which ‘gases are highly ole?nic in
nature and principally composed of C3 and C4
materials. Such gases, when treated in the poly
merization step at temperatures of the order of
500° F. to 1000° F., preferably at about r700" F.
ing a liquid hydrocarbon to cracking conditions
of time, temperature and pressure to convert a
substantial portion thereof to gasoline and other
portions thereof to ole?nes, in the presence of a
solid, particle-form adsorptive contact mass
maintained ‘in suspension in said charge, sepa
rating the products of such cracking into vapors
converted largely into materials‘ of gasoline boil 10 and a liquid fraction containing the suspended
solid, fractionating the vapors into an ole?ne
ing range. Thus the combined process is found
containing fraction, a gasoline, and a heavier
capable of producing from about thirty to about
than-gasoline fraction, contacting the ole?ne
sixty per cent of gasoline of high value from net
fraction at reaction conditions of temperature
gas oil consumed in process.
The polymerization operation is shown herein 15 and pressure with a solid particle form adsorp
tive catalytic contact mass to convert a substan
as an operation wherein the catalyst is employed
tial portion thereof to material of gasoline boil~
as a downwardly moving bed of contact mass
ing range, passing the vaporous products of such
material. The operation at this stage is not re
conversion to common fractionation with the
stricted to such a process and may be conducted
either in this manner or as one wherein the cata 20 vapors of the ?rst‘ cracking operation, removing
750° F. in the presence of an alumina-silica cata
lyst in amounts appropriate for the system, are
contact mass from the ole?ne conversion stage,
lyst is suspended by the reactant vapors in a con
and injecting said contact mass into suspension
dition of hindered settling. It is also within the
in the hydrocarbon in the ?rst cracking opera
contemplation of this invention that a series of
?xed bed catalyst chambers might be used alter
tion.
’
nately, the bed in each chamber being discharged 26 2. In a process for the conversion of hydrocar
bons of higher boiling point to motor fuel of high
to hopper 68 after use and the reactor chamber
quality the steps which comprise: subjecting. a
liquid hydrocarbon to cracking conditions of
time, temperature and pressure to convert a sub:
stantial portion ‘thereof to gasoline and other
being re-?lled.
The solid particle form adsorptive catalytic
contact mass to be used both in the gas-oil crack
ing step and in ‘the ole?ne polymerization step
may be any one of a number of forms of metallic
portions thereof to ole?nes, in ‘the presence of a
solid, particle-form adsorptive contact mass
maintained in suspension in said charge, sepa
complex, of natural or synthetic origin, such’ as
rating the products of such cracking into vapors
fuller’s earth, various other natural clay-like ma 35 and a liquid fraction containing the, suspended
terials, including acid treated clays, and the like,
solid, fractionating the vapors into an ole?ne
various synthetic materials, such as those which
containing fraction, a gasoline, and a‘heavier
may be prepared by the gelation of alumina
than-gasoline fraction, removing sulfur from the
and/or silica, either individually, with mixing, or
ole?ne fraction, contacting the ole?ne fraction
with coprecipitation. Such alumina and/0r sil 40 at reaction conditions of temperature and pres
oxide catalyst. Most usually the catalyst will be
of the nature of an alumina or‘ alumina-silica
ica complexes may also carry oxides of other
metals, as chromia, vanadia, magnesia, manga
nese, etc., added as by mixture, impregnation,
coprecipitation and the like. In normal opera
tion, however, preference is had for the alumina/
silica complexes either natural or synthetic,
without added oxides of other metals, since these
have the type of catalytic effect desired for the
gas-oil cracking, and while they may be neither
as selective nor as highly efficient as certain
sure with a solid-particle form adsorptive cata
lytic contact mass to convert a substantial por
45
tion thereof to material of gasoline boiling range,
passing the vaporous products of such conversion
to common fractionation with the vapors of the
first cracking operation, removing contact mass
from the ole?ne conversion stage, and injecting
said contact mass into suspension in the hydro
carbon in the ?rst cracking operation.
60
3. In a process for the conversion of hydrocar
bons of higher boiling point to motor fuel of high
quality the steps which comprise: subjecting a
liquid hydrocarbon to cracking conditions of
specialized catalytic materials for the ole?ne
polymerization, this process permits their eco
nomic use in such proportions as actually to
achieve an enhanced production against the use
time, temperature and pressure to convert a
of such catalysts. In general, therefore, the 55 substantial portionthereof to gasoline and other
process contemplates the use of any solid, ad
sorbent polymerization catalyst which is stable
portions thereof to ole?nes, in the presence of a
solid, particle-form adsorptive contact mass
under the cracking conditions and hence can
maintained in suspension in said charge, sepa
serve in both operations of the process.
rating the products of such cracking into 'vapors
60
The catalytic contact mass may be utilized
and a liquid fraction containing the suspended
either as relatively small particles, such as those
solid, fractionating the vapors into an ole?ne
used in contact ?ltration, in the form of granules
containing fraction, a‘. gasoline, and a heavier
such as the ordinary particles of fuller’s earth
than-gasoline fraction,‘ contacting the ole?ne
used in percolation ?ltration, or in the form of
prepared pellets, spheres and the like of relative
ly small size, such as many of the synthetically
prepared catalysts.
_
65 fraction at reaction conditions of temperature
and pressure with a solid-particle-form adsorp
tive catalytic contact mass to convert a substan
tial portion thereof to material of gasoline boil
Many variations of the invention herein set
ing
range, passing the vaporous products of such
forth will occur to the man skilled in the art
conversion
to common fractionation with the va
70
when installing and practising this invention.
pors of the ?rst cracking operation, removing
All such I consider as within the scope of my in
contact mass from the ole?ne conversion stage,
vention except as limited by the claims herein
after set forth.
‘
I claim:
1. In a. process ‘for the conversion of hydro
admixing said contact mass with at least a por
tion of the heavier-than-gasoline fraction from
76 said fractionation, and injecting said contact
2,407,817
7
8
mass into _suspension in thehydrocarbon in the
?rst'c'racking operation.
sorptive catalytic contact mass to convert‘ 31251119
stantial portion thereof to. material of gasoline
boiling" range, passing the vaporous products of
_
4. Ina process for the conversion of hydrocar
bons of higher boiling point to motor fuel of high
quality the steps which comprise: subjecting a
liquid hydrocarbon to cracking at temperatures
such conversion to common fractionation with
0
the vapors of the ?rst cracking operation, remov
ing- contact mass from the’ ole?ne conversion
stage, admixing said contact mass with at‘ least
a portion of the heavier-than-gasoline fraction
between about 1000” F. and about 1100° F. to con
vert a substantial portion thereof to gasoline and
other portions thereof to ole?nes, in the presence
from said fractionation, andinject-ing said‘con;
of a solid, particle-form adsorptive contact mass 10 tact mass into suspension in the hydrocarbon ‘in
maintained in suspension in said charge, sepa
the ?rst cracking operation.
’
rating the products of such cracking into vapors
7. In a process for the conversion of hydrocar
and a liquid fraction containing the suspended
bons of higher boiling point to motor fuelof high
solid, - fractionating the vapors into an ole?ne
quality the steps which comprise: subjecting a
containing fraction, a. gasoline, and a heavier
liquid hydrocarbon to cracking conditions of time,
than-gascline fraction, contacting the ole?ne
fraction at reaction conditions of temperature
and pressure with ‘a solid particle-form adsorp
tive catalytic contact mass to convert a substan
temperature and pressure to convert a substan—
tial portion thereof to gasoline and other pore
tions thereof to ole?nes, said cracking being con
ducted at a pressure sufficient to cause retention
tial portion thereof to material of gasoline boil 20 of liquid state by at least a portion of said charge
ing range, passing the vaporous products of such
and in’ the presence of a solid, particle-form
conversion to common fractionation with the
adsorptive contact mass maintained in suspension
vapors of the ?rst cracking operation, removing
in said charge, separating the products of such
contact mass from the ole?ne conversion stage,
cracking into vapors and a liquid fraction con'--‘
and injecting said contact mass into suspension 25 taining the suspended solid, fractionating the va
inthe hydrocarbon in the ?rst cracking opera
pors into an ole?ne containing fraction, acga‘so-e
tion.
.
line, and a heavier-than-gasoline fraction, con
' 5; In a process for the conversion of hydrocar
tacting the ole?ne'fraction at‘ reaction conditions
bons of higher :boiling point to motor fuel of high
of temperature and‘ pressure, with a solid; partie
‘ quality the steps which comprise: subjecting a 30 ole-form adsorptive catalytic contact mass to conliquid hydrocarbon to cracking conditions of time,
vert a swbstantialjportion thereof to material of
temperature and pressure to convert a substantial
gasoliine ‘boiling range, passing the vaporous
portion thereof to gasoline and other portions
products ‘of such conversion to common. fraction=
thereof to ole?nes, in the presence of a solid,
ation with the vapors of the first cracking opera;
pa'rt-icleeform adsorptive alumina-silica contact
35, tion, removing contact mass from the ole?ne con
mass maintained in suspension in said charge,
separating the products of such cracking into a ‘
vapors and a liquid fraction containing the sus
pended solid, fractionating the vapors into an ole
?ne containing fraction,
version stage, and injecting said contact mass into
suspension in, the hydrocarbon in .the ?rst, crack‘
ing
operation.
'
‘
1
-
"
'
8. In a process for the conversion of hydrocar
a gasoline, and a 40 fbons of higher :boiling point to motor fuel of high
heaviepthan-gasoline fraction, contacting the
ole?ne fraction at reaction conditions of tempera
ture and pressure with a solid particle-form ad
quality the steps which comprise: ‘subjecting a
liquid hydrocarbon to cracking at temperatures
between about 1000” F. and about’ 1100° F. to
convert a substantial portion thereof to‘ gasoline
convert a substantial portion thereof to material 45
and other portions thereof to ole?nes, said c'ra'ckfe
of-gasoline boiling range, passing the vaporous
sorptive catalytic alumina-silica contact mass to
ing being conducted at a pressure sufficient‘ to
products of such conversion to common fractiona
cause retention of liquid state by at least a por
tion with'the vapors of the ?rst cracking opera
tion of said charge- and in the presence of a‘ solid,
tion, removing contact mass from the ole?ne
_ particle-form adsorptive‘ contact mass maintained
conversion stage, and injecting said contact mass
in- suspension in said charge‘, separating the prod-"
50
into suspension in the hydrocarbon in the ?rst
ucts of such cracking into vap‘érs and a’ liquid
cracking operation,
fraction containing the suspended solid, frac
6. In‘ a process for‘ the conversion of hydrocar
tionating' the vapors into an ole?ne containing
bons of higher boiling point to motor fuel of high
fraction, av gasoline, and a heavierethan-gasoline
quality the steps‘ which comprise: subjecting a
fraction,v contacting the ole?ne fraction at; reac->
liquid hydrocarbon to cracking at temperatures
tion conditions of temperature and pressure with
[between about 1000° F. and about 1100° F. to
ya solid-particle-form adsorptive catalytic contact
convert a substantial portion thereof to gasoline
mass to convert a substantial portion thereof to
and other portions thereof to ole?nes, in the pres
material of gasoline boiling range, passing the
ence of a solid, particle-form adsorptive contact
vaporous products of such conversion to common
mass maintained in suspension in said charge, 60
fractionation with the vapors of the ?rst crack
separating the products of such cracking into va
ing operation, removing contact mass from the
pors and a liquid fraction containing the sus
ole?ne conversion stage, admixing said contact
pended solid, fractionating the vapors into an
mass
with at least a portion of the heavier-than
ole?ne containing fraction, a gasoline, and a
gasoline fraction from said fractionation, and
heavier-than-‘gasoline fraction, contacting the
injecting- said contact mass into suspension in the
ole?ne fraction at reaction conditions of tempera
ture and pressure with a solid-particle-form ad
hydrocarbon in the ?rst cracking operation.
ARTHUR V. BANNER.‘
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