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Патент USA US2406622

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Aug. l27, 1946. '
l
J..M. MAvrrY
2,406,622
'f
CONVERSIONv OF _ HYDROCARBONS
' ,
Filed News, 1943
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2,406,622
Patented Aug. 27, 1946
UNITED STATES PATENT OFFICE
n
2,406,622
CONVERSION oF HYDRooARBoNs
Julian M. Mavity, Riverside, Ill., assignor to Uni
versal Oil Products Company, Chicago, Ill., a
corporation of Delaware
'
Application November 8, 1943, Serial No. 509,412
colaims. (Cl. 26m-683.4)
This invention relates to the catalytic conver
sion of hydrocarbons and is more speciñcally con
cerned with an improved catalytic process where
in the catalyst employed comprises an aluminum
halide.
Aluminum halide catalyst such as aluminum
chloride and bromide are well known in the art
as catalysts which accelerate hydrocarbon con
version reactions such as isomerization, alkylation
and cracking. These catalysts have been em
ployed in the solid granular state or have been
deposited upon solid supporting materials and
2
vide an improved process wherein the formation
of the hydrocarbon catalyst complex inthe cata
lyst supply zone is substantially eliminated, there
by eliminating the difficulties discussed above.
In one broad aspect, the present invention com
prises passing at least a portion of a saturated
hydrocarbon charge in substantial liquid phase
through a bed of aluminum halide and a metal
selected from the group consisting of iron, alumi- y
num, magnesium, tin, cadmium, nickel, copper
and zinc under conditions such that at leastI a
portion of the aluminum halide is dissolved in the
disposed in a conñned reaction zone through
hydrocarbon, passing the resulting solution into
which the hydrocarbon reactants are passed.
More recently these catalysts have been employed
version of a substantial portion of the hydro
>in processes- wherein at least-a portion of the '
carbon.
hydrocarbon charging stock is passed through a
bed of granular catalyst disposed within a cata
lyst supply zone, said zone being maintained un
der conditions such that at least a portion of the ‘i
catalyst is dissolved in the hydrocarbon and the
resulting solution introduced into a reaction zone
wherein the desired conversion is obtained. One
of the diñîculties of this latter type of operation
is the fact that under the conditions necessary
in the catalyst supply zone to eiïect the solution
of at least a portion of the catalyst in the hydro
a reaction zone and therein effecting the »con
`
I have found that the presence of a metal such
as iron, aluminum, magnesium, tin, cadmium,
nickel, copper or zinc in the catalyst supply zone
effectively inhibits the formation of hydrocarbon
catalyst complexes in thesupply zone. The exact
reason for the inhibiting action of these metals
is not known'but as shown in the examples in
cluded hereinafter in this specification, this in
hibiting effect is substantial.
The improved process of the present invention
is applicable in general to hydrocarbon conversion
reactions employing aluminum halides as cata
carbon stream, some reaction often occurs be
lysts but is particularly applicable to such reac
tween the catalyst and the hydrocarbons and as
tions
as isomerization of saturated hydrocarbons
30
a result of this action, a high molecular weight
hydrocarbon catalyst complex/is formed.
This
hydrocarbon-catalyst
complex
While
suchras pentane, hexane, heptane, methyl cyclo
hexane, etc., alkylation of alkylatable saturated
hydrocarbons such as isoparañins with alkylating
_possessing some catalytic activity is not as active
agent such as olefins and cracking of higher boil
as the granular aluminum halide. In fact, the
Aactivity of complex appears to be dependent upon 35 ing hydrocarbons to lower boiling saturated hy
drocarbons.
the concentration of aluminum halide in said
It is obvious that the operating conditions em
complex. Therefore, the formation of this com
ployed in the reaction zone willvary depending
plex in the catalyst supply zone increases to a
upon the hydrocarbon charge and the particular
considerable extent the catalyst `consumption per
reaction desired. However, since substantially no
40
unit of hydrocarbon converted.
reaction is effected in the catalyst supply zone,
A further advantage in the operation isy ob
the conditions employed in said zone are de
tained by preventing complex formation in theV
pendent primarily upon the catalyst being em'
catalyst supply Zone. The complex formed is
relatively insoluble in the hydrocarbon stream
and a coating gradually accumulates on the re
sidual granular catalyst. The presence of this
insoluble coating on the catalyst -prevents efli
cient contact between the hydrocarbon catalyst
and retards the solution of aluminum halide in
the hydrocarbon stream. The catalyst concen
tration in the hydrocarbon stream leaving the
catalyst supply zone is gradually decreased neces
sitating various changes in the operating condi
tions to maintain a constant catalyst withdrawal.
It is an object of the present invention to pro
yployed. When employing aluminum chloride as
45 a catalyst, the temperature will fall within the
general broad range of about 100 to 300° F. under
a pressure sufñcient to maintain the hydrocarbon
in a liquid phase in the saturator to effect the
solution of the catalyst in the hydrocarbon.
Somewhat lower temperatures can be employed
when using valuminum bromide as the catalyst
since this catalyst is much more soluble than
aluminum chloride in hydrocarbons. Tempera
tures will ordinarily vary within the range from
about room temperature to about 200° F.
2,406,622
3
In effecting the conversion reaction in the re
action zone, for the best results it is necessary to
have a catalyst activator present such as hydro
gen chloride or hydrogen bromide.
The concen
4
38, This method of operation provides a means
for regulating the amount of catalyst withdrawn
in solution by controlling the amount of hydro
carbon being introduced to the chamber.
tration of the activator present in the reactants
is dependent upon the reaction desired. For
Conversion chamber 6 may comprise a large
cylindrical chamber containing some means of
isomerization, the concentration is ordinarily
retaining a portion of the catalysts introduced
Within the range of about 1 to 40 mol per cent of
into the conversion zone through line 1%.
the hydrocarbon charge and preferably from
about 5 to 20 mol per cent. For alkylation, the
hydrogen halide concentration is somewhat low
er being of the order of 0.5 to about 10 mol per
cent of the charge and preferably within the
range of about l to 3 mol per cent of the charge,
while for cracking the concentration may fall
within the broad range mentioned above for
isomerization.
The conditions of temperature and pressure
employed in the reaction zone are dependent
The re
taining means may comprise solid packing ma
terial such as crushed ñrebrick, Berl saddles,
Raschig rings, broken stoneware, granular alu
mina, granular silica-alumina composites and
’various other packing materials well known to
those skilled in the art, As an alternative, the
retaining material may comprise a liquid such as
a hydrocarbon aluminum halide complex com
monly termed “sludge” or a low-melting mixture
of aluminum halide and other halides such as
antimony, arsenic, zinc, and bismuth. In the
upon the catalyst, type of hydrocarbon charge 20 event that a liquid is employed in conversion
and the hydrogen halide concentrations and the
chamber E as a means for retaining a portion of
particularreaction desired. For isomerization, the
the catalyst being introduced, a more satisfac
temperature will vary within the range of from
tory operation is obtained with the ñow of hy
about room temperature to about 300° F. and
drocarbons upwardly through the body of liq
preferably within the range of about 100 to 250° 25 uid in the conversion chamber instead of down
F. For alkylation of parafñns such as isobutane
wardly as shown in the drawing. A portion of
with oleñns such as butylene and propylene, the
the low melting mixture is withdrawn, and the
temperature will vary from about room temper
metal halide such as antimony halide recovered
ature to about 150° F. Considerably higher tem
and recycled to the reaction Zone.
peratures may be employed for catalytic crack 30 The liquid retaining mediums mentioned all
ing of hydrocarbon mixtures such as gasoline
exert some catalytic effect on the conversion re
fractions, kerosenes and gas oils. These tempera
action. By the retention of a portion of the cat
tures will ordinarily be within the range of about
alyst introduced, the catalyst activity of the liq
150 to about 750° F.
uid present in the Conversion zone is maintained
The reaction in the conversion zone may be 35 at a substantially constant level.
conducted in either the liquid, mixed or vapor
A small amount of cyclic hydrocarbons such as
phase depending upon the pressure employed.
benzene, toluene, xylene or cyclohexane, methyl
Pressures ranging fromV atmospheric to substan
»cyclopentana methyl cyclohexane and the like
tially superatmospheric of the order of 500
may be added to the. reactants entering- conver
pounds or more are applicable.
containing valve 34
L10 sion zone 6 through line
The features of the present invention will be
or into the catalyst supply tower through line
more fully discussed in the accompanying draw
39 containing valve ¿0. The presence of this
ing which illustrates in conventional side eleva
small amount of cyclic hydrocarbons inhibits to
tion one type of apparatus in which the objects
a considerable extent the tendency of the pen
of the invention can be accomplished. For sim
tane to decompose into lower molecular weight
45
pliñcation, the description of the drawing is lim
hydrocarbons.
ited to the isomerization of normal pentane.
_ The. reaction products comprising unconverted
However, it is not intended that this description
normal pentane, isopentane and hydrogen halide
place any undue limitations on the broad appli
and small amounts of decomposition products
cation of the invention, since as' previously point
50 are withdrawn from conversion chamber 6
ed out it is applicable to the conversion of hydro
through line ‘I containing valve 8 and are directed
carbons in general.
into fractionator 9 wherein the unconverted nor
Referring to the drawing', thel charging stock,
in this instance normal pentane is> introduced
through line l containing valve 23 along with re
cycle from line l5 obtained as hereinafter set
mal pentane is separated from the hydrogen
halide and isopentane. The hydrogen halide
substantially free of hydrocarbons is withdrawn
through line 3| containing valve 32 and is cli
forth into the suction of pump 24 which dis
rected into line 29 through which it is again in
troduced into the reaction zone. The isopen
catalyst supply tower 3 wherein it contacts a
tane-normal pentane mixture is withdrawn from
granular bed of analurninum halide and a metal
fractionator 9 into line lil containing valve H
60
selected -from the group consisting of iron, alu
is directed into fractionator I2 wherein a sepa
minum, magnesium, cadmium, copper, nickel, tin
ration is effected between the unconverted nor
and zinc, under conditions such that a portion of
mal pentane and the isopentane. The isopen
the aluminum halide is dissolved in the hydro
tane is withdrawn from fractionator I2 into line
charges through line 28 containing valve 2 into
carbon. The catalyst-containing stream is with
drawn from catalyst supply chamber 3 through
line 4 containing valve 5 'commingled with hy
l~3 containing valve I 4, cooled, condensed and
recovered as the product of the reaction. The
unconverted normal pentane is withdrawn
drogen halide obtained as hereinafter set forth
through line I5 containing valve IE and recycled
and the combined streams directed into conver
to the reaction zone through line l as previously
sion chamber fiv wherein a substantial portion of 70 set forth. The bottomsv of fractionator 9 com»
the normal pentane is isomerized into isopentane.
prising a minor portion of the unconverted nor
As an alternative method of operation, only a
mal pentane and any heavier products of the
portion of the charge is introduced into supply
reaction containing aluminum halide dissolved
chamber 3, the remaining portion by-passing the
therein are withdrawn through line I1 and may
supply chamber through line 3T containing Valvc 75 be removed from the system through valve 20
2,406,622
5
the actual catalyst consumption per barrel of
‘or recycled to the reaction'zone to line I8r con'
isopentane in this operation is about 1.0 pound.
taining valveV I9- which directs the stream into
pump 25 which discharges‘through line 26 con
o
taining valve 21 Ainto line 4. AA small> amount'of ,
VA pentane charging` stock containing about 5.5
'light hydrocarbons formed during the reaction
inf'chamber 6 are withdrawn from fractionator.
`Sth'roug’hï line 35 containingvalve 36and recov
ered as a product of the reaction.
' Example IV
mol per cent isopentane and 94.5 mol per cent.
normal pentane ispassed through a mixture of
80 per cent by weight of aluminum chloride and
2o per cent by weight of powdered aluminum at
f
-During the conversion reaction in chamber 6,
a small portion of the hydrocarbon is converted v10 a temperature of 170° F. and under a pressure
of 500 pounds per square inch gauge. The re
into- a complex by reacting with the catalyst.
sulting solution is commingled with hydrogen
The complex is Withdrawn from the conversion
chloride in an amount equivalent to 12 mol per
chamber into line 2| containing valve 22 and
cent o_f the hydrocarbon charge and the mixture
` >may be discarded or treated in various ways to re
introduced into a packed reaction zone which
cover the metallic halides contained therein. One 15 is maintainedfat va temperature of V350" F. The
particularly suitable way of treating the with~
analysis of the products resulting from the crack
drawn sludge is to contact it with the charging
ing=reaction
is as follows:
'stock' to remove any soluble metal halide by dis-Y
fMol per cent
'solvinglit in the charge. Y This not only permits
ISO, 04H10 ______________________________ __ 18.9
the recovery of a portion of the metal halide but
also Serves to remove impurities such as oleñns
Normal C`4H1o __________________________ __
from the charging stock.
rISOV G51-112 ______________________________ __ 28.0
NOI'l’nal 05H12 __________________________ _... 41.2
06+ ________________________________ __v___ 11.1
The following examples are indicative of the
0.8
improved results obtained inr the isomerization of
normal pentane when operated in accordance 25 The catalyst consumption in the above reaction `
is about 0.94 pound per barrel of pentane charged.
with thev present invention.
'
Example I
Example V
When
the
test
shown
in Example IV is dupli
>A normal pentane charging stock is passed
through the catalyst chamber containing pow 30 cated under substantially the same conditions
with the exception that the powdered aluminum
Ydered aluminum and aluminum chloride. The
is not present in the catalyst supply Zone, a cat
chamber is maintained at a temperature of 170°
alyst consumption of about 1.96 pounds per bar
F. under a pressure of 400 pounds .per square
inch gauge. The eilluent from this chamber con
rel of pentane charge or an increase of about 105
introduced into a packed reaction zone main
tained at a temperature about 210° F. under a
presence of the promoter and an aluminum halide
taining about 1 pound of aluminum chloride per 35 per cent is obtained.
_I claim as my invention:
barrel of pentane is commingled with about 0.2
1. In the catalytic conversion of a saturated
mol per cent of benzene and with hydrogen chlo
hydrocarbon reactant wherein the reactant is
ride in an amount sufficient to produce a stream
of reactants containing about 12 mol percent 40 commingled with a hydrogen halide promoter
and subjected to conversion conditions in the
hydrogen chloride. The stream of reactants is
catalyst, the method which comprises passing at
least a portion of said reactant, in liquid phase
pressure of 400 pounds. The reaction products
and prior to the commingling of the hydrogen
have the following analysis:
'
Mol per cent 45 halide promoter therewith, through a stationary
',Isopentane _____________________________ __ 53
Normal pentane _________________________ __ 42
C4 hydrocarbons ________________________ __ 2.0
C64-___-; _______________________________ __ 3.0
Afterrabout 300 hours of operation, the cat~
bed of solid aluminum halide containing a metal
selected from the group consisting of iron, alu
minum, magnesium, tin,- cadmium, nickel, copper
Y and zinc, whereby to dissolve a portion of the
50 solid aluminum halide in the liquid reactant
while substantially preventing the formation of
hydrocarbon-aluminum halide complex in said
alyst in the supply chamber has substantially
the same physical appearance as it had when
bed.
first placed into the supply chamber.
Example II
55 carbon reactant wherein the reactant is com
Example I was repeated with the exception
that the powdered aluminum was not introduced
into the catalyst- supply Zone. After approxi
mately 491.5 hours of continuous operation, the 60
catalyst supply tower was opened andV it was
found that some of the aluminum chloride had
been converted into a liquid complex. In calcu-V
.
2. In the isomerization of a parailinic hydro
mingled with a hydrogen halide promoter and
subjected to isomerizing conditions in the pres
ence of the promoter and an aluminum halide
catalyst, the method which 'comprises passing
at least aportion of said reactant, in liquid phase
' and prior to the commingling of the hydrogen
halide promoter therewith, through a stationary
bed of solid aluminum halide containing a metal
selected »from the group consisting of iron, alu
lating the actual catalyst consumption per bar
rel of normal pentane charged, it was found that 65 minum, magnesium, tin, cadmium, nickel, cop
per and zinc, whereby to dissolve a portion of
the consumption was of the order of about 1.26
the solid aluminum halide in the liquid reactant
pounds per barrel as contrasted to a catalyst
While substantially preventing the formation of
consumption of about 1 pound per barrel ob
hydrocarbon-aluminum halide complex in said
tained in the operation described in Example I,
or an increase of Yabout 26 weight per cent.
70
bed.
'
3. In the catalytic conversion of a saturated
hydrocarbon reactant wherein the reactant is
commingled with a hydrogen chloride promoter
When the operation of Example I is repeated
and subjected to, conversion conditions in the
but powdered magnesium substituted for the
powdered aluminum in the catalyst supply zone, 75 presence of the promoter and an aluminum chlo
2,406,622
7
ride` catalyst, , the4 method which comprises pass
ing atleast a portionofxsaid reactant, in liquid
phase and prior to the commingling of the hy
drogen chloride promoter therewith, through a
stationary bed of solid aluminum chloride con
taining a metal selected from the group consist
ing of iron, aluminum, magnesium, tin, cadmium,
nickel, Ycopper and zinc, whereby to dissolve Va
8
alkylating agentl in the presence. of- thev promoter
and anyaluminum halide> catalyst,_ the method
which comprises passing at least a portionv of
said reactant, in liquid phase and prior to _the
commingling of the hydrogen halidev promoter
therewith, through a stationary bed of solid alu
minum halide containing a metal selected from
the group consisting of iron, aluminum, mag
portion of the solid aluminum chloride in the
nesium, tin, cadmium, nickel, copper and; Zinc,
liquid reactant while substantially preventing the 10 whereby to dissolve a portion of the solid alumi
formation of hydrocarbon-aluminum chloride
complex in said bed.
4. In the isomerization of' a parañìnic hydro
carbon reactant wherein the reactant is com
num halide in the liquid reactant While. substan
tially preventing the formation of hydrocarbon,
aluminum halide complex in said bed. -
6. In the alkylation of a paraiiinic hydrocarbon
mingled with a hydrogen chloride promoter and 15 reactant wherein the reactant is commingledwith
subjected to isomerizing conditions in the pres
a hydrogen chloride promoter and reacted.v With
ence of the promoter and an aluminum chloride
an alkylatíng agent inthe presencel ofthe pro
catalyst, the method which comprises passing
moter and an aluminum chloride catalyst, the
at least a portion of said reactant, in liquid phase
method which comprises passing at least a; por,
and prior to the commingling of the hydrogen 20 tion of said'reactant; in liquid phase and> prior
chloride promoter therewith, through a station
tol the commingling of the hydrogen chloride
ary-V bed of solid aluminum chloride containing
promoter therewith, through a stationaryy bed-,of
ametal selected from the group consisting of iron,
solid’v aluminum chloride containing a,V metal se
aluminum, magnesium, tin, cadmium, nickel,
lected from the group consisting of iron, alumi
copper and Zinc, whereby to dissolve a portion of
num, magnesium, tin, cadmium, nickel, copper
the solid aluminum chloride in theliquid `re
and zinc, whereby to dissolve- a portion of_ the
actant while substantially preventing the forma
solid aluminum chloride in the liquid reactant
tion of hydrocarbon-aluminum chloride complex
while substantially preventing the formation of
in said bed.
hydrocarbon-aluminum chloride complex in said
5. In the alkylation of a para?ñnic hydrocarbon 30
i‘eactant wherein the reactant is commingled with
ahhydrogen halide promoter and reacted with an
JULIAN M. MAVITY.
bed.
Y
Y
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