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Патент USA US2411483

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Patented Nov. 19, 1-946 -' '
2,411,4s3 ’
UNITED, ‘STATES PATENT OFFICE
2,411,483
CORROSION’ INHIBITION IN CATALYTIC
HYDROCARBON CONVERSION
Aaron Wachter, Berkeley, and Richard S‘.
Treseder, San Francisco, Calif., assignors to
Shell Development Company, San Francisco,
_ Caiif., a corporation of Delaware
.
_ -No Drawing. Application August 28, 1943,
-
Serial No. 500,458
'
,
(Cl. 260—.666)
15 Claims.
1
'
2
.
This invention relates to the execution of cata
the product obtained in the preparation of the
lytic reactions with the aid of Friedel-Crafts type
catalyst or added subsequent to the preparation
catalysts and relates more particularly to the
of thecatalyst.
~
'
catalytic conversion of hydrocarbons with the
The organo-metal hahde complex catalysts, for
aid of catalysts comprising an organo-metal 5 examplethose comprising an aluminum halide
halide complex.
.
'
‘
hydrocarbon complex, are utilized with advantage
vIn the execution of catalytic conversions on a
as catalysts in the execution of catalytic hydro
practical scale with the aid of Fridel-Crafts type
carbon conversion processes, such as, for example,
catalysts it is often desirable, and sometimes im
those involving isomerization, alkylation, reform
perative,'that the catalysts employed be of the
ing, cracking, and polymerization reactions.
type‘comprising the metal halide in the form of
Other processes in which they can be applied
an organic complex, because of physical and
comprise the re?ning or treatment‘of hydrocar
chemical characteristics peculiar to these ‘com
bons comprising, for example, normally gaseous
pounds. Catalysts comprising such an organe
hydrocarbons, normally liquid hydrocarbons in
metal halide complex generally consist of a liquid 15 the motor fuel boiling range, recycle stocks,
or sludge obtained by mixing a metalhalide with
an organic compound under suitable conditions,
resulting in the interaction of the .halide with
the organic compound and/or decomposition
lubricating oils, etc.
‘
A di?iculty encountered in the utilization of
the organo-aluminum halide complex catalysts,
often seriously detracting from the advantages
products thereof. I The metal ‘halide constituent 20 otherwise inherent in their use on‘a practical
of the organic complex may comprise a halide
such as the chloride, bromide or?uorlde of such
scale, is their corrosive nature. They are par
ticularly corrosive to steel and iron- or ferrous
metal-containing materials of which the appa
ratus in which the processes are conducted must
metals as, for example, A], B, Ga, In, Te, Be, Mg,
B, Cd, Cu, Co, Zr. Of these metal halides the
halides of- aluminum, particularly aluminum 25 generally be manufactured. Such corrosive
chloride and aluminum bromide, are preferred.
effect, it must be pointed out, not only results in
Suitable organic compounds with which the metal
rapid deterioration of costly apparatus, but in a
halides are combined vunder conditions resulting ,
rapid decline in the useful life of the organo
in the obtaining of the desired organo-metal
metal halide complex catalyst, thereby’further
halide complex comprise, for example, aromatic 30 increasing the cost of. the operation. Though it
hydrocarbons, such as benzene and toluene; hy
is not intended to limit the invention by any
drocarbon fractions such as kerosene extracts;
theories advanced herein to set forth more clearly
cyclic ole?ns such as cyclohexene, cyclopentene
the nature of the invention, it is believed that
and alkyl :derivatives' thereof; parailinic and
such increased rate in the decrease of the catalyst
olef'inic hydrocarbons of straight or branched 35 life is often due, at least in part, to the rapid
chain structure; phenols; organic acids, ethers,
increase of iron in the catalyst as a result of the
etc. In the preparation of the complex catalysts
latter’s corrosive effect upon the ferrous metal
the organic‘compound and metal halide are sub
containing surfaces in contact therewith. The
jected to an elevated temperature, for example,
‘effect of a relatively high concerrtration of» iron
not substantially in excess of about 150° 0., gen 40 on the life of these catalysts is illustratedq'by the
erally in the presence of an added hydrogenv
following example. a
‘ halide, for a su?icient length of time to result in
'
the formation of a liquid, or sludge, consisting '
Example I
A dimethylcyclopentane-containing fraction of
essentially of an organo-metal halide complex.
straight run gasoline having a boiling range of
It is to be pointed out, however, that the present 45 from 85° C. to 98‘? C. was treated with acatalyst
_invention is in no wise limited by the method
. consisting of an AlCla-toluene complex under the
of production of the organo-metal halide cata
lysts.
.
f
‘
,
following conditions:
'
Temperature: 80° C.
The catalyst is generally employed in the pres
ence of an added hydrogen halide promoter, such 50 Contact time: 17 minutes
as, for example, hydrogen chloride, hydrogen
bromide, hydrogen ?uoride, alkyl halides or ma
'
‘
' ' Catalyst to hydrocarbon ratio=1:3
terials capable of producing any of these halide
promoters under the conditions of the execution
Hydrogen chloride in the amount of‘ 0.1% by
weight was added to the charge. The operation
was discontinued when the catalyst activity had
of-the reaction. ‘The complex may, furthermore,
comprise suspended metal halides remaining in
dropped to 50% of the equilibrium conversion of
dimethylcyclopentane
to
methylcyclohexane.
Though ability of the compound to dissolve in
Under these conditions 106 gallons of the hydro
cal operating conditions with a separate portion
the orango-imetal halide complex is not essen
tial to the attainment of the corrosion inhibiting
e?ect, those capable of solution in the catalyst
sludge are nevertheless somewhat preferred.
of the same catalyst in which iron in an amount
Suitable compounds of the inhibitor metals com
carbon charge were treated per pound of AlCla
in the catalyst. In a, second operation a separate
portion of the same feed. was treated under identi- -
of 6% by weight of the catalyst had been dis
solved. ,The amount 'of hydrocarbon charge
prise their halide salts, such as the chlorides, .
treated per pound of AlCls in the catalyst in the -
bromides and ?uorides; their oxides; salts of or
ganic acids, and oxygen-containing mineral
second operation amounted to only '18 gallons.
Certain metals, for example nickel, and alloys
acids; etc. when adding the metal inhibitor in '
the form of its halide salt it is not necessary that
the halide correspond to that of the metal halide
constituent of theorgano-metal halide sludge.
For example, when utilizing a hydrocarbon-alu
containing materials. The cost of these mate-~
rials, however, generally prohibits their use in 15 minum chloride complex catalyst the inhibitor
metal can be added in the'form of the chloride,
practical installations, and even though attacked
bromide, ?uoride, a salt comprising more than
to a lesser degree by the complexes than ferrous
one type of halide atom, or it may be added as a
metals they are nevertheless seriously corroded
mixture of any two or more of such halide salts.
over prolonged periods of contact with these cat
alysts. Resort to expedients such as the coating 20 Compounds of the inhibitor metals, the addition
of which has, proven to be particularly effective
of the metal surfaces in contact with the cat
in suppressing‘ the corrosive activity of the or
alyst is generally found to be impractical and
are availablewhich are not so readily corroded
by the complex catalyst as the ferrous metal
costly. Many of the available coating -materlals,
gano-metal halide complex catalysts, comprise
necessary repairs.
in combined form, a su?lcient amount of the -
compounds containing the metals of group IV in
such as, for example, plastics, are often found
to deteriorate and crack after relatively short 25 their tetravalent ‘form and those of group V in the
trivalent form,v for example SbCla, AszOa, ASCls,
time of use, thereby entailing additional costs, as
TiCh. Whenv the inhibitor metal is thus added
well as a serious loss of time required to'e?ect
compound containing it is added to the catalyst
It has nowbean found that the serious di?i
culties heretofore encountered in the utilization 30 to provide a concentration of the inhibitor metal
therein within the above-‘defined range. The
of organo-metal halide complex‘catalysts can be
presence of SbCla in the complex catalysts in con
substantially completely obviated by maintaining
centrations of from about 0.02% to about 14%, .
in the catalyst small amounts of a corrosion in
and preferably from about 0.1% to about 6%,
hibitor selected from the metals of groups IV and
'
V of the periodic table. By the term "metals” 35 have been found highly satisfactory.
Although it is generally su?icient to effect the
as used throughout the speci?cation and ap
addition of but one of the ‘inhibitor metals to the
pended claims it is intended to include the ele-.
complex, more than one of these metals may be
ments arsenic and antimony.
added to obtain a catalyst devoid of any substan
The inhibitor metal, or
The organo-metal halide complex catalysts
comprising at least one of these metals are sur
40 tial corrosive effect.
compound comprising it, may also be employed‘
prisingly devoid of any substantial corrosive ac
tion upon most metal surfaces, and particularly
in the form of an admixture or even chemical
combination with organic compounds.v Thus, in
hibitor metal-containing sludge recovered‘from
more efficient in their corrosion inhibiting effect 45 one operation wherein the inhibitor metalwas
employed ascorrosion inhibitor and/or catalyst
than others, their comparative e?iciency in this
component, may be added to the charge of ‘the regard being, to some extent, determined by‘ the
same or an entirely separate process. For ex
particular operating conditions used, the com»
ample, an SbClz-containing sludge, obtained in
positionv of the particular catalyst employed, and
the composition of the metal surface in contact 50 the isomerization of para?inic hydrocarbons, in
the alkylation of isopara?ins with olefins, or simi
with the catalyst. The presence of arsenic in
upon ferrous metal-containing surfaces, in con
, tact therewith. Some of the inhibitor metals are
‘even as small an amount as 0.05% by weight of
the catalyst is suflicient to substantially suppress
corrosion of steel in contact therewith. Anti
mony effects substantial suppression of corrosion
of a steel surface in contact with the catalyst
when present in an amount below about 0.1% by
lar operations, with the aid of metal halide-con
taining catalysts may be' introduced into the‘
charge to a naphthene 'isomerization process to
attain
the desired corrosion inhibition.
55. The following
example is given to illustrate the
absence to a surprising degree of any substantial
corrosive action upon metal surfaces by theor
weight of the catalyst.- It is therefore apparent
gano-aluminum halide complex catalysts con
that the exact amount of the particular inhibitor
required to obtain substantially complete inhibi 60 taining a metal of groups IV and V of the periodic
table; it is to be understood,v however, that the
tion of ‘corrosion will vary somewhat with the .
values given are illustrative rather than limiting.
particular metal used. The concentration. of the
inhibitor metal in the organo-metal halide com-v
Example II
. plex catalyst is generally maintained in the range
of from about 0.01% to about 7%, and preferably
In a series of tests, polished metal surfaces of
from about 0.05% to about 3%, by weight of the
low carbon steel and 5% nickel steel were brought
catalyst. Lesser or greater concentrations may
into intimate contact with ‘AlCh-hydrocarbon
however be used within the scope of the inven
complex catalysts at temperatures and for time
tion.
‘
‘ Of the metals of groups IV and V suitable as 70
intervals indicated in the table below. The liquid '
catalyst was agitated by bubbling dry HCl through
corrosion inhibitors, antimony, arsenic and tita
nium are preferred. The inhibitor metals need
not necessarily be introduced into the catalyst
chloride, identi?ed in the'following table by the
in the uncombined or metallic form but may be
letter "A”; an AlCla-toluene complex, prepared ’
it.
The catalysts used were: an AlCla-toluenev
complex prepared with chemically pure aluminum
employed in the form of a‘ suitable compound. 75 with an AlCh of a technical grade of purity, iden-'
2,411,488
5
.
I
ti?ed in the table by the letter “B”; and an AlCla
hydrocarbon complex prepared by the interaction
6
during the course of operation. It is to be pointed
out that it is essential to the attainment of sub
stantial or complete suppression of corrosion that
the presence of the inhibitor in the catalyst, pref
of chemically pure aluminum chloride and a
smokeless kerosene extract, identi?ed in the table
by the letter “C." In a series of separate tests
erably within the prescribed ‘concentration, be
maintained throughout the operation during '
similar metal surfaces were contacted under sub
stantially identical conditions with separate por
' which the catalyst is used. subjection of the
tions of the same catalysts to which the indicated
metal surface to the catalyst containing the in
metals of groups IV and V in the amount and
hibitor or treatment of the metal surface with '
form given in the table below were added. Sepa 10 the inhibitor metal in the form of a suitable com
pound, such as, for example, antimony trichlo
rate runs were also made ‘wherein similar metal
surfaces were subjected under substantially iden
ride, does not render such a ‘surfaceimmune to
subsequent corrosion by the catalyst in the ab
tical conditions to contact with separate portions
of the indicated catalyst to which'Fe and PC]: sence of one of the inhibitor metals. This is'il-_
were added in the amounts shown. The corrosion 15 lustrated by the following examples.
rates ‘of the metal surfaces were carefully deter
Example III
mined and are given‘ in the following table for
_ Three polished specimens of low carbon steel
were immersed for 15 minutes in acatalyst con
- each of theindividual tests in mils per year.
Corrosion rate
.
|
Catalyst
C
Inhibitor per cent of Temp.,
cat. by wt.
‘' C.
t
t
‘2 n 80
tllgls‘f'
20 sisting of an AlCla-toluene complex containing
0.4% SbCls by weight of the catalyst. The speci- .
mens were then contacted for a period of 24
mils per year
Low 7 5%
carbon Ni
steel steel
hours with a portion of the identical catalyst to
425
1
P-196 A..- Nona... .......... --
so’
0-20
a, 530
1.660
P-20l A.-. 0.2% SbCls ........ ..
80
0-24
7
6
80
24-89
’
of 80% C. and agitated by bubbling dry hydrogen
, chloride gas through it. The rate of corrosion in
8
ll
80
0-21
6
.13
80
21-88
9
18
P-l99 A.-. 4% S110]; .......... .,
80
80
0-23
23-41
6
a
5
s
r-zzs B... None .............. ..
so
0-25
5,600
P-233 B... 1% T1014 .......... --
so
0-24
35
were immersed for 1 hour in an AlCla-toluene
80
80
24-89
0-24
25
11
complex to which 0.3% of AszOa had been added.
80
24-87
4
P-m5 A.-- 0.4% SbOl; ........ --
.
- P-247 B... 0.1% A520: ________ ._
.
'
P-251 B... 0.3% A820] ........ _.
P-259
,
which no SbCls had been added. The catalyst in
both instances was maintained at a temperature
80
0-137v
100
0-24
24
.... _.
P-237 B...
1% A501: .......... ..
80
0-24
1
.... ..
so
24-136
3
.... ..
80
0—23
0.3% AS201 ........ _.
100
0—24
2
.... ..
0.3% AS101 ________ ._
100
0-24
2
.... -.
P-260 C...
Example IV
The specimens were then immersed for 24 hours
0. 6
0.3% AS203 ........ --
,
30
Three polished specimens of low carbon steel
_-.
P-198 0... None ............ .."._
mils per year was found to average 2160.
2, 140 .... ..
P-262 A..- 1'7 Fe 288 FcrOz).-.-
80
0-24
2, 250 .... -
P-263 A..-
1 0 Fe ?lings) .... _.
80
0-24
1,500
P-ZM B..- 1% P01; .......... _.
80
0-24
2,630 ......
.... ..
in a separate portion of the identical complex
catalyst containing no AS203. The catalyst in
both instances was maintained at 80° C. and asi
tated by bubbling dry hydrogen chloride through
it. The average rate of corrosion in mils per year
40 was found to be 1870.
I
Often, depending upon the particular material.
being treated. with the organo-metal halide com
plex ‘catalyst containing a metal inhibitor, a cer- '
amount of the inhibitor will be removed from
As shown by the foregoing example, corrosion 45 tain
the catalyst body in the reaction zone by en
trainment and/or solution in the reaction prod
with an organo-metal halide, complex is obviated
uct. This will be the case in processes wherein
of ferrous metal-containing surfaces in contact
substantially completely and considerable saving,
hydrocarbons constitute the material undergoing '
as represented by increase in the life of equipment,
is realized by the inclusion of only relatively small 60 ‘treatment. The inhibitor metals, though added
in metallic or other form, are generally converted
amounts of a metal of group IV or V in the cata
tothe halides in the presence of the catalyst, par
lyst. It is, furthermore, seen from the above ex- .
ticularly when a hydrogen halide promoter is
ample that the ability to effect the suppression of
present. These halides are soluble to a certain
the corrosive effect of the catalyst is not possessed
degree in hydrocarbons and will be extracted
by the purely non-metal phosphorus, or by small 65 from
the catalyst in the reaction zone as the
amounts of iron. That the ability to effect the
process ‘proceeds. The inhibitor metal is, there
suppression of corrosion by sludge-type catalysts
fore preferably initially added to the catalyst in
is not possessed by all metals was further indi
sufficient amount to assure a corrosion inhibiting
cated in tests wherein small amounts of nickel and
concentration therein and additional amounts
copper were added to catalysts of this type with 60 added
continuously or intermittently to the feed
out the attainment of any decrease in corrosive
entering the reaction zone during the course of
nes and resulting deterimental consequences. .‘
execution of the process to assure the main'te- L
The inhibitor metalin uncombined or combined
nance at all‘ times of a corrosion inhibiting con
form may be introduced into the catalyst in any
centration of the metal'in the catalyst. A par
suitable manner. It may be introduced into the 05 ticularly advantageous method of operation com
catalyst in the form of solid pieces; a powder; as
prises the addition of the inhibitor to but a por
a slurry or a suspension in a suitable liquid me
tion of the hydrocarbon charge and thereafter
dium, such as, for example, a suspension in a hy
combining the inhibitor-containing portion of the
drocarbon or a hydrocarbonfraction; as a solu
feed with the rest of the hydrocarbon feed enter
tion in a suitable solvent, for example, an acid, 70 ing the reaction zone. Such method of operation '
such as a hydrogen halide; etc. The inhibitor
wherein but a portion of the charge passes
metal may be introduced into the catalyst before
through a suitable inhibitor-adding zone greatly
contact therewith of the material to be treated;
facilitates maintenance of the inhibiting amount
or it may be introduced in part or in its‘ entirety i
of the inhibitor within the reaction zone. It fur
into the charge or directly into the reaction zone 76 'ther enables separate heating of the main por
'
‘
~ "2,411,488
8
.
tion of the charge to a temperature sumciently
high to maintain the desired reaction conditions
Hydrogen’ chloride in the amount of 0.1% by
and the lesser portion to a temperature most
favorable to solution of the desired quantity of
1 was terminated when the activity of the catalyst
inhibitor therein.
,
weight was added to the feed. The operation
had declined to a point where the conversion of
dimethylcyclopentane to methylcyclohexane had
dropped to 50% of equilibrium conversion. Un
der these conditions 36 gallons of hydrocarbon
‘
Since only relatively low concentrations of the
inhibitor metals are generally required to obtain
the inhibition of corrosion, the concentration of
‘the metal in the reaction product will generally
be so small that its removal therefrom will not
be required. Separation of the inhibitor metal or
a compound containing it from the reaction prod
uct may, however, be effected by any suitable
feed was treated pei'\pound of AlCls in the cata
lyst. The operation was repeated with separate
portions of the same catalyst and feed under
identical conditions with the exception that 0.8%
by weight of AszOa was added to the catalyst.
The amount of hydrocarbon feed treated per
pound of AlCla in the catalyst was increased to
means comprising, for example, one or more of
such steps as water-washing, washing with alkae 15 42 gallons.
line solutions suchas aqueous sodiumhydroxide,
Example ' VI
distillation, fractionation, scrubbing, solvent ex
traction, treatment with solid adsorptive mate
.A portion of the same feedutilized in the op-'
rials, etc. In the processing of hydrocarbons with
eration of Example V was treated under the con-, '
the organo-metal halide complex catalysts in the 20 ditions set forth in. Example V with an AlCla
presence of one of the metal inhibitors, for ex
ample arsenic, antimony or compounds thereof, it
has been found that the-inhibitor or compounds
containing it, such as the halides, can readily be
removed from the reaction product by the addi 25
tion thereto of small amounts of water which
cause the inhibitor to settle out as a hydrolysis
toluene complex catalyst of different origin. 47
gallons of the hydrocarbon feed were treated per
pound of A1013 in the catalyst. Treatment of a
separate portion of the same feed under identical
conditions as the foregoing operation but with
the exception that 1.6% by weight of A5203 was '
added to the catalyst resulted in an increase in
product. The inhibitor thus separated may be
the amount of’ hydrocarbon feed treated to 51
returned to the catalyst in the reaction zone,
gallons.
-
preferably after undergoing a dehydration treat 80
ment and optionally its conversion to a more suit
able form, such as tube metallic form or a. halide
Salt.
‘
.
\l
j
.
I A particular advantage in the utilization of an
Example VII
A dirnethylcyclopentane-containingv hydrocar
bon fraction having a boiling range of from 85° .
C. to 95° C. was treated in continuous operation
inhibitor metal, such as antimony or its com
35 at a temperature of from 80° C. to 100° C. with an ‘
pounds, for example, antimony trichloride, reAlCla-hydrocarbon complex obtained by the in
sides in the ability to separate any antimony tri
chloride in they reaction product by simple frac
a teraction of A1013 and a kerosene extract to con
vert the dimethylcyclopentane content of the feed
The maximum amount
bons the antimony trichloride may be separated 40 .of feed treated per pound of catalyst, in repeated
as a separate Ifraction containing the antimony
operations, amounted to 110 gallons. The op
tionation; Thus, in the treatment of‘hydrocar
' to methylcyclopentane.
trichloride above its melting point. The thus re
erations were repeated with substantially iden
ticalfeed, catalyst and operating conditions with
the reaction 'zone without the need for further
the exception that SbCla in the amount of 0.2%
treatment of the recovered inhibitor prior to re 45 by weight of the catalyst was initially added to
covered antimony trichloride may be returned to
cycling it.
>
the catalyst sludge and additional SbCla was
continuously added to the hydrocarbon feed to
sion inhibitor must be the absence of any sub
maintain a concentration of 0.01% of SbCl: in
stantial adverse effect upon the activity of the
the hydrocarbon feed entering the reactlon'zone.
catalyst. In this respect the metals‘ of groups IV 50 Under these conditions-the treatment of 150 to
and V possess the advantage of having no harm
200 gallons of feed per pound of catalyst as
ful effect upon either the activity or the useful
determined by substantially identical conversions
life of the organo-metal halide complex catalysts.
of dimethylcyclopentane to 'methylcyclohexane
Certain of the metal inhibitors, particularly ar
were obtained.
senic, antimony and titanium and compounds 55 The invention therefore provides a highly e?i
An essential characteristic of a suitablelcorro
containing them, particularly the halides, often
are found to exert not only a promoting effect
cient method for the elimination of the severe
di?iculties heretofore encountered in the use of
metal halide catalysts as a result of the corrosive
depending upon the particular composition of the
catalyst and operating conditions used, but also.
action of these catalysts upon metal surfaces in
to increase the useful life of the catalyst. The 60. contact therewith, thereby enabling the attain
highly advantageous effect upon catalytic activity
and useful catalyst life _by inclusion of these cor
rosion inhibitor metals in the organo-aluminum
halide complex catalysts-is shown in the following
examples.
'
'
Example V
A ‘naphthenic straight‘ run dimethylcyclopen
tane-containing fraction boiling in the range of
_85° C. to 98° C. was treated with a catalyst con
ment not only of a substantial increase in the life
of the equipment and the useful life of the cata
lyst but the substantial savings and reduction in
cost of operation occurring therefrom. '
We claim as our invention:
_ 1. In
the
execution ‘ of
‘
catalytic
reactions
wherein reactants are contacted with a catalyst
, consisting of a preformed organo-metal halide“
complex catalyst in a reaction zone comprising
sisting of an AlCla-toluene complex under the 70 a metal-containing surface in direct contact with
said catalyst, the method of ‘inhibiting corrosion
following conditions:
‘
'
.
of said metal-containing surface and increasing
Temperature: 80° C.
~
the useful life of said catalyst which comprises
Contact time: 17 minutes
' maintaining in said catalyst a corrosion inhibit
Catalyst to hydrocarbon ratio= 1:3
75 ing amount of a member of the group consisting
2,411,483 '
10
of antimony. and antimony halides 'in which all
containing surface and increasing the useful life
halide atoms are the same.v
‘ of said catalyst which comprises maintaining in
2. ‘In a catalytic hydrocarbon conversion proc-,
said catalyst from about 0.05%to about 3% by
ess wherein hydrocarbons are converted in the ' weight of an antimony ‘trihalide in which all
presence of a catalyst consisting of a preformed 5 three halide atoms are the same.
organo-aluminum halide complex in a reaction
9. In a catalytic hydrocarbon conversion proc- ~
zone comprising a metal-containing surface "in
ess wherein hydrocarbons are converted in the
direct contact with said catalyst, the method of
presence of a catalyst consisting of a preformed
inhibiting corrosion of said metal surface and
aluminum chloride-hydrocarbon complex in a
,
increasing the useful life of said catalyst which‘ 10 reaction zone comprising a metal-containing sur
comprises maintaining in said catalyst acorro
face in direct contact withsaid catalyst, the
sion inhibiting amount of antimon .
3. In
,
the
execution - of _ catalytic
method of inhibiting corrosion of said metal sur
face and increasing the useful life of said catalyst
reactions
vwherein reactants are contacted with a catalyst
which comprises maintaining in said catalyst
, consisting of a preformed metal halide-hydro 15 from about 0.1% to about 6% by weight of anti
‘ carbon complex in a reaction zone comprising a
mony trichloride.
metal-containing surface in direct contact with
‘
10. A non-corrosive‘ aluminum halide-hydro
carbon complex catalyst consisting of a pre
said catalyst, the method of inhibiting corrosion >
of said metal-containing surface and increasing
formed aluminum halide-hydrocarbon complex
the useful life. of said catalyst which comprises 20 containing a corrosion inhibiting amount of anti
maintaining in said catalyst a corrosion inhibit
ing amount of an antimony trihalide in which all
three halide atoms are the same.
mony trihalide" in which all three halide atoms
are
the
same.
'
,
‘
11. A non-corrosive aluminum chloride-hydro
carbon complex catalyst consisting of a pre
formed aluminum chloride-hydrocarbon complex
containing a corrosion inhibiting amount of
4. In a catalytic hydrocarbon conversion proc
ess wherein hydrocarbons are converted in the
presence of a catalyst consisting of a ‘preformed
organo-metal halide complexin a reaction zone
comprising a metal-containing surface in direct
contact with said catalyst, the method of inhibit
SbCls.
.
12. A non-corrosive aluminum chloride-hydro
carbon complex catalyst consisting of a pre
ing corrosion of said metal surface and increas 30 formed aluminum chloride-hydrocarbon complex
ing the useful life of said catalyst which com
containing from about 0.1% to ‘about 6% by
prises maintaining in said catalyst a corrosion
weight of SbCla.
'
inhibiting amount of an antimony trihalide in
13. In a catalytic hydrocarbon conversion proc
which all three halide atoms are the same.
ess wherein hydrocarbons are contacted under
5. In a catalytic hydrocarbon conversion proc 35 conversion conditions with a catalystconsisting
ess wherein hydrocarbons are converted ‘in, the
of a preformed organo-metal halide complex
‘presence of a catalyst consisting of a preformed
in a reaction zone comprising a metal-containing
aluminum.halide-hydrocarbon complex in a re
surface in direct contact with said catalyst, the
action zone comprising a metal-containing sur
method of inhibiting corrosion of said metal sur
face in direct ‘contact with said catalyst, the 40 face and increasing the useful life of said catalyst
method of inhibiting corrosion of said metal
- containing surface “and increasing the useful life
of said catalyst which comprises maintaining in
said catalyst a corrosion inhibiting amount of
antimony trichloride._
6.‘ In the execution .of catalytic reactions‘
which comprises adding antimony to said hydro
v carbons prior to contact with said catalyst in
controlled amounts to maintain a concentration
of from about 0.01% to about’! % by weight of
45 said metal in said catalyst.
wherein reactants are contacted with a catalyst
consisting of a preformed aluminum chloride
hydrocarbon complex in a reaction zone com->
. v
14. In a catalytic hydrocarbon conversion proc
ess wherein hydrocarbons are contacted under
conversion conditions with a catalyst consisting
of a preformed organo-metal halide complex in
prising a metal-containing surface in direct con 50 a reaction zone comprising a metal-containing
tact with said catalyst, the method of inhibiting
surface in direct contact with said catalyst, the
corrosion of said metal-containing surface and
method of inhibiting corrosion of said metal
increasing the useful life of said catalyst which
surface and increasing the useful life of said .
‘
comprises maintaining-in said catalyst from about
catalyst which vcomprises adding to said hydro
0.1% to about 6% by weight of antimony tri-' 55 carbons a_ member of the group consisting of an
chloride.
timony and antimony halides in ‘which all halide
7. In a catalytic hydrocarbon conversion proc
atoms are the same prior to contact with said
ess' wherein hydrocarbons are converted in they _ catalyst.
'
presence of a catalyst consisting of a preformed
aluminum halide-hydrocarbon complex in a re
action zone ‘comprising a metal-containing‘sur
face‘in direct contact with said catalyst, the
.method of inhibiting corrosion of said metal- ,
15. In a catalytic hydrocarbon conversion proc- .
ess wherein hydrocarbons are contacted under
conversion conditions with a catalyst consisting
of a preformed organo-metal halide complex in a
reaction zone comprising a metal-containing sur
containing surface and increasing theuseful life
face in direct contact with said catalyst, the
of said catalyst which comprises maintaining in 65 method of inhibiting corrosion of said metal
said catalyst from about 0.01% to about 7% by 1 surface and increasing the useful life of said
weight of antimony.
'
.
8. In a catalytic hydrocarbon conversion proc
ess wherein hydrocarbons are converted in the
presence of a catalyst consisting of a preformed
aluminum chloride-hydrocarbon ‘complex in a.v 70
reaction zone comprising'a metal-containing sur
face in direct contact with said catalyst, the
' method of inhibiting corrosion of said metal
catalyst which comprises continuously adding
SbCh to said hydrocarbons prior to contact with
said catalyst in controlled amounts to maintain
a concentration of from about 0.1% to about 6%
SbCls in said catalyst.
AARON WACHTER.
RICHARD S. 'I'RESEDER.
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