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' Jan. 14, 1947.
`
E. H. LANG
2,414,205
PRQDUCTION oFI MOTOR FUEL
Filed June 4, 1941
@f2l
/
@aw No,
INVENTOR.
2,414,205
Patented Jan. 14, 1947
UNITED STATES PATENT OFFICE
2,414,205
PRODUCTION oF Moron FUEL
Edward H. Lang, Chicago, Ill., assignor to The
Pure Oil Company, Chicago, Ill., a corporation
Application June 4, 1941, Serial No. 396,495
2 Claims. (Cl. 196-12)
' ïThis invention relates to production of motor
fuel.
I
Various methods are known for converting hy
drocarbon oils and gases into motor fuel. The
methods which are in common usage are thermal
2
'I0-90° F. In the absorber substantially all the
C3 and heavier hydrocarbons are absorbed from
the gas together with minor amounts of lower
boiling gases. The unabsorbed gas consisting
primarily of C1 and C2 hydrocarbons together
with a small amount of hydrogen and higher boil
c'racln'ng of oils at high temperatures and thermal
ing hydrocarbons, leaves the top of the absonber
or‘catalytic polymerization of hydrocarbon gases.
through the line 'I controlled by valve 9.
Reforming of low octane naphtha either with or
The fat oil, i. e., charging stock containing
without catalyst is also commonly practiced. In
all these methods the resulting product is highly 10 dissolved therein hydrocarbon gases, leaves the
bottom of the absorber through line ‘I I, passes
unsaturated or oleñnic.
through heat exchanger I3 and is then pumped
Experience has shown that highly oleñnic mo
by means of pump I4 through heating and re
tor fuels have certain disadvantages. First7 their
action coil I5. The fat oil may be heated in its
susceptibility to lead is low as compared with
parañinic hydrocarbons. Moreover, under high 15 passage through coil I5 to a temperature of from
900° to 1150o F., depending upon the nature of the
speed operating conditions oleñnic hydrocarbons
oil. `Where residuum stock is being treated, the
have a tendency to cause knocking in modern
temperature will be in the neighborhood of 900“7
automotive engines of high compression ratio.
F. Where the process is used for conversion of
The object of this invention is to provide a
method for producing a Well-balanced motor fuel 20 naphtha, temperatures approaching l150° F. may
fbe used and where stocks boiling intermediate be
which performs without knocking at all speeds.
tween residuum and naphtha are processed, tem
Another object of this invention is to provide
peratures will be intermediate between 900° and
a method for treating a mixture of hydrocarbons
l150° F.
boiling within the gasoline range and containing
a high percentage of oleñnic hydrocarbons, to 25 rî‘he fat oil is forced through coil I5 at a pres
produce a well-balanced motor fuel.
`
Still another object of this invention is to' pro
vide a method for converting hydrocarbon oil into
motor fuel which gives a high road performance
test.
«
sure which may vary from approximately 500 to
3000 pounds per square inch and the time of
residence in the coil I5 is sufficient to obtain the
desired amount of conversion. The nature of the
30 reaction in the coil I5 is rather complex. Crack
A further object of the invention is to con
vert hydrocarbon gases into motor fuel which
gives a high road performance test.
Still a further object of the invention is to
provide a method for improving performance of
motor fuels by proper treatment of particular
fractions and reblending of the fractions after
ing of the oil and gas takes place concurrently
with alkylation and polymerization. Because of
the high temperatures to which the products are
subjected in the coil I5, the resultant-products
are highly unsaturated. The olefinic content of
the reaction products may be 35 to 50% or more.
The reaction products leave the coil l5 through
valve I1 where the pressure may be reduced to
500 pounds per square inch or less, pass through
Other objects of the invention will become ap
parent from the following description and the ac 40 heat exchanger i3 where the temperature is re
duced to approximately 350° to 550° F. by indirect
companying drawing of which the single figure
heat interchange With the charge to the coil I5
is a diagrammatic elevational view of apparatus
and then pass into the lower portion of the frac
suitable for carrying out the invention.
tionating tower I9. The temperature to which
Referring to the drawing, numeral I indicates
a line through which fresh oil is fed to the unit. 45 the reaction products are reduced prior to enter
ing the fractionating tower will depend largely
The fresh oil may be gas oil, kerosine or naphtha
on the nature of the charging oil. With heavier
or it may be residuum where it is desired to prac
charging stocks the temperature of cooling should
tice vis-breaking. The fresh oil is fed into the
be close to 550° F. in order to avoid partial con
upper portion of the absorber 3 where it passes
in countercurrent contact with hydrocarbon gas 50 densation in the heat exchanger with resultant
coke deposition, With lighter charging stocks
which enters the bottom of the absorber through
the
dew point of the reaction products is consider
the line 5. The absorber is maintained under
ably lower and therefore lower cooling tempera
suitable pressure which may vary from 100 to
tures‘may beused.`
` _
400xpounds per square inch and the temperature
treatment.
I
is maintained in the absorber at approximately 55
In the fractionating tower separation ofthe re
2,414,205
3
¿i
action products into residuum, recycle stock,
heavy gasoline distillate, light gasoline distillate
of through the line 61 and are mixed with air
which enters the line 6l through line 69. The
and gas takes place. The residuum is withdrawn
through line 2l controlled by valve 23 and it may
be discharged from the system and used `as fuel
oil. The recycle stock which is heavier than the
gasoline distillate is withdrawn from the tower
mixture then passes into the chlorine regenerator
'H which may contain a saturated cuprous chlo
ride solution on pumice. In the presence of the
cuprous chloride the air oxidizes the hydrochloric
acid, liberating chlorine. The chlorine regener
through line 2t and may be recycledto the ab
sorber through valve 25, line 2'6,- cooling coil
ator should be heated ‘to a `temperature below
7 50° F. but sufficiently high to cause the reaction
21 and line 29, or may be withdrawn from the
to take place. The reaction products leave the
regenerator 'H through line 'i3 and pass into
washing tower and separator l5. Water vapor
and hydrochloric acid may be washed fromthe
entering gases by means of water fed into the
upper portion of the tower through >the line 11.
[The wash water is withdrawn from the bottom
of the tower through the line 19 controlled by
valve 8l. By maintaining the separator 'l5 under
superatmospheric pressure, the chlorine can be
liquefied in the upper portion of the tower and
,separated from‘the remaining gas such as nitro
gen, oxygen and hydrocarbons which escape from
4the'top of the tower through the line 83 controlled
by valve 85. Chlorine is withdrawn from the sep
arator 'l5 through line 8l controlled byvalve 89
and recycled through line 'I where it is ’mixed
with the vC1 and C2 hydrocarbons from the ab
sorber. The mixture then'passes to the reactor
system through line 3l controlled by valve 33,
or may be charged by means of line 35 and pump
36 either to the reaction coil l5 or through cool
ing coil 3l and line 38 to line 3i! to ’act as quench~
ing liquid for the reaction products, where tem
peratures lower than those resulting from the eX
changer I3 are desired. It will be apparent that
the recycle stock may be divided in any desired
manner. Uncondensed gas is withdrawn from
the top of the fractionating tower through line
4D controlled by valve lli, and cooling coil 42,
and charged to absorber 3.
,
The heavy gasoline distillate is withdrawn from
the fractionating tower through line G3 controlled
by valve fifi. This distillate may have an initial
boiling point of between v200" to 250° F. and- an
‘end boiling point of approximately 400° F. The
boiling range of this vfraction may vary some
what, but in any event it should be within the
upper gasoline boiling range.
The distillate
passes to the reactor or reaction chamber El5 con
iii in which chlorine is combined with the C1 and
i C2 hydrocarbons to -form chlorides of these hydro
,
carbons, Make~up chlorine is added through line
.ed controlled by valve 93. Reactor 9i may be
taining anhydrous aluminum chloride `prefer
ably vdeposited'on a solid comminuted material
maintained under atmospheric pressure or un
‘ such as silicaor fuller’s earth. If the vdistillate is
not sufficiently warm kas it Venters the reaction
chamber 125, the reaction chamber may be heated
to bring .the temperature up to approximately
IOW-250° F. Ordinarily, the distillate will be suf
ficiently warm as it leaves the fractionating tower
so asnot to require additional heating. As the»
heavy gasoline distillate enters the aluminum
chloride reaction chamber it is mixed with methyl
and/or'ethyl chloride >which enter the gasoline
stream through line ät. In the presence of alu
minum chloride these chlorides react with the _
der superatmospheric pressure »somewhat lower
than that maintained in the separator 'l5 and
may be cooled to control the reaction. The re
action products are withdrawn from the reactor
9i through line 9d, compressed by means of com
pressor‘95 and used to alkylate the heavygasoline Y
distillate in the> reaction chamber-45.
Instead »of chlorinatingthe C1 and C2 gases
from absorber 3,»these >gases may be withdrawn
Vfrom the system through'line »d6 controlled by
valve‘ille'and methane and/or other paraiiìnic
gas fronran independent source fed through line
gasoline insuch manner as to alkylate the un
98 controlled by valve‘SQ to chlorinator 5I. More
saturated hydrocarbons contained therein to
>>over, methyl chloride tromV an Vextraneoussource
V:form saturated iso-paraflins. The reaction prod
caribe charged> through line riiii) controlled by
ucts leave the reaction chamber #l5 through line
valve iti to the aluminum‘ chloride reactor'dâ
A1, pass into separator ¿i8 where the liquid hydro- f and the necessity of chlorinating methane and/or
carbons are separated from the gases which may
.ethane as part of the process, dispensed with.
consist of hydrogen chloride,V chlorine and un
It will "oe seen, therefore, that I have devised
oonverted hydrogen and hydrocarbon gases. The
a unitary process for converting hydrocarbon oils
liquid hydrocarbons are mixed with the light gas
and gases into a finished gasoline, the light frac
oline ydistillate which is withdrawn from Yfrac
tionY of which is 'high >in unsaturates and the
-tionating tower ’i9 through line 49 controlled by
heavier `traction of which is high in. saturated
valve 5i and the blend is'passed through line 53
hydrocarbons and 'contains very little unsat
into fractionator 55 Where it is subjected to heat
urated hydrocarbon. The light fractionV will con
ing and fractionation to separate end point gas
sistfpredcminantly ‘of olefinic hydrocarbons with
oline. The gasoline vapors pass overhead, >are
ASonie 'arorr'iatic' hydrocarbons'. Thearomatic hy
withdrawn through line 5l, condensed in cooling
coil 59 and collected in receiver` El. The heavy
vends are withdrawn from the fractionating tower
through line 53 controlled by valve 55 and may be
recycled for further conversion.. [The gasoline
distillate may be given a caustic wash or other
Vsuitable treatmentjif necessary to remove any
traces of chlorine or ’hydrochloric acid which re
main therein.
The alkylation reactionv in the reactor t5 may
’take place --at vatmos'pl’ieric -or superatmospheric
*pressure but itis preferably carried `out at pres
sures ofV the order of 100 vto S50-pounds per square
inch. Higher pressures may -lbe --us'edif desired.
ArEhe gases »from-separator 48 lèaveithe ïtop there
'fdrocarbonsìin therli'ght fraction are ’unobjection
vable 'since-'they appear to 'be 4vbeneii’cial‘for'low
speed operation. AIn the heavy fraction »of the
`‘gasoline will’fbe~¿.present isoparaíiins formed by
the> allai/lation of the aliphatic unsaturated hy- `drocarboneand. some aromatic 'hydrocarbons con
A«taining alkyl side' chains. .The presence of` al
kylated ybenzene and-aiicyclic hydrocarbons in
‘the high 4¿boilinglfrvalction'is not yobjectionable
ï since they-'appear toï'actflilze para?ñnic `hydrocar
bons and? therefore are beneficiall for high-»speed
`perform’ance'.»
-'
»
Although I have >shown Land-disclosed ymym
Vventiovn. in connection V.with aljpolyformlsprocess
‘for producing unsaturated gasolineïîdi'stillates:and
2,414,205
È
6
suffering any decrease in yield of motor fuel.
a -Friedel-Crafts type of process for saturating the
Alkylation or hydrogenaticn of the upper boiling
heavy gasoline fraction, it will be understood that
fraction results in increased octane rating there
the invention is not limited to these specific steps.
of and in an increased amount of liquid product
The invention in its broadest aspects covers the
within the motor fuel range.
saturation of a higher boiling gasoline fraction
I claim:
rich in oleiinic hydrocarbons and the blending
l. The method of preparing motor fuel. which
thereof with a lower boiling highly unsaturated
comprises charging e. mixture of hydrocarbon oil
gasoline fraction, regardless of the manner in
and gas to a conversion Zone, subjecting the mix
which the saturation is effected. For example,
saturation may be eiïected by hydrogenation` with 10 ture in said zone to conditions of time, tempera
ture and pressure to convert a substantial por
hydrogen under pressures of the order of 800
tion thereofinto unsaturated hydrocarbons boil
pounds per square inch at temperatures of the
ing Within the gasoline boiling range, separating
order of 350°-400° F. in the presence of a cat
from the reaction products a fraction boiling
alyst, as, for example, one composed of copper,
magnesium oxide and zinc oxide. The highly 15 within the upper gasoline boiling range, separat
ing the reaction gases into a fraction containing
unsaturated low boiling gasoline fraction may be
predominantly C3 and higher boiling hydrocar
prepared by either thermal or catalytic poly
bons and a fraction containing predominantly
merization of hydrocarbon gases or by thermal
C1 and C2 hydrocarbons, recycling the C3 and
reforming of naphtha at temperatures of the
order of 1000-1050° F., or catalytic dehydrogena 20 higher boiling hydrocarbon fraction to the con
version Zone, converting the C1 and C2 hydrocar
tion of naphtha at temperatures of the order oi
bons to alkyl chlorides, alkylating the fraction
'TSO-950° F. in the presence of a catalyst such as
boiling within the upper gasoline range by means
Activated Alumina impregnated with chromium
of said alkyl chlorides in the presence of alumi
oxide. The method and apparatus describe and
show one way of accomplishing the objects of 25 num chloride and blending with the alkylated
fraction the hydrocarbons rich in unsaturates,
my invention.
boiling within the lower gasoline boiling range.
The invention accomplishes the object of ím
proving road performance of motor fuel with
2. The method of preparing motor fuel which
out the necessity of increasing octane rating as
comprises converting hydrocarbon oil into hy
measured by the A. S. T. M. method. Motor fuels 30 drocarbons rich in oleñnes boiling within the
produced in accordance with my invention will
gasoline boiling range and into hydrocarbon
perform better than motor fuels of equal or even
gases having from 1 to 4 carbon atoms per mole
higher octane number prepared by Well known
cule, chlorinating C1 and C2 gases to alkyl chlo
methods.
rides, alkylating the higher boiling portion of the
It Will be understood, however, that although 35 gasoline boiling range hydrocarbons by means of
the invention relies on modifying the nature of
said alkyl chlorides in the presence of aluminum
the compounds in the upper boiling fraction in
chloride, and blending the resulting alkylate with
order to obtain the desired motor fuel, not on
the lower boiling gasoline boiling range ole?lnic
the necessity of increasing the octane number of
hydrocarbons.
the fuel, in accordance with my invention the 40
EDWARD I-I. LANG.
octane rating of the fuel as measured by the
A. S. T. M. method is in fact increased without
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