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Patented Oct. 29, 1946
2,410,044.
UNITED STATES PATENT OFFICE‘
2,410,044
HYDROCARBON OATALYZING PROCESS
Robert E. Burk and Everett 0. Hughes, Cleve
land Heights, Ohio, assignors to The Standard
Oil Company, Cleveland, Ohio, a corporation of
Ohio
No Drawing. Application May 29, 1941,
1
Serial No. 395,827
5 Claims. (Cl. 260——668)
This invention relates to catalysis, and more
particularly catalysis involving operation on hy
drocarbons; and it is among the objects of the
invention to provide improved operating e?‘i
2
onally adjacent atomic numbers 4 and 13 in the
periodic table and chromium may be combined.
Thus, antimony chloride and aluminum nitrate
and chromium nitrate at the rate of 34.2, 2512
ciency, and without undue complication. Other 5 and 713 g. respectively per 18.8 liters of distilled
objects and advantages will appear as the de
water, being brought into solution, the solution is
scription proceeds.
warmed and with vigorous agitation ammonium
To the accomplishment of the foregoing and
hydroxide is introduced at the rate of 2310 g. of
related ends, the invention, then, comprises the
concentrated ammonium hydroxide with 1500 g.
features hereinafter fully described, and particu 10 of ammonium acetate per 11.2 liters of distilled
larly pointed out in the claims, the following de
water. Again similarly, SnCh and Be(NO3) z and
scription setting forth in detail certain illustra
C‘r(NOa)s may be dissolved at the rate of 78.2,
tive embodiments of the invention, these being
1550 and 713 g. respectively per 18.8 liters of dis
indicative, however, of but a few of the various ,
tilled water, and the solution being warmed and
Ways in which the principle of the invention may 15 agitated ammonium hydroxide is introduced at
be employed.
the rate of 1820 g. of concentrated (28%) ammo
The raw material for reaction may be non
nium hydroxide and ammonium acetate 1,500 g,
benzenoid hydrocarbons, or fractions containing
in 11.2 liters of distilled water.
them, etc., as more particularly detailed herein
Where a part of the tin or aluminum is replaced
after, and it is subjected to the action of a com 20 by antimony or beryllium respectively, the cata
pound catalyst of peculiar character, and heat.
lyst involves tin and antimony and aluminum and
This catalyst may be prepared preferably from
chromium, or beryllium and aluminum and tin
soluble salts of tin, aluminum and chromium for
and chromium, or beryllium and aluminum and
example by dissolving the salts in water at the
tin and antimony and chromium, etc., on the lines
rate of one mol percent of tin, seventy-nine mol 25 as indicated and within the proportions stated for
per cent of aluminum and twenty mol per cent of
the permissible ranges of the tin and aluminum
chromium, and the solution is treated with am
components, the generic properties of the catalyst
monia to neutralization. Thus, tin chloride and
being maintained.
aluminum nitrate and chromium nitrate at the
The compound catalyst is suitably granulated
rate of 39.1, 2512, and ‘71.3 g, respectively, based 30 to provide interstitial spaces for passage of the
on anhydrous salts, per 18.8 liters of distilled
material to be treated, in adequate contact, and
water, being brought into solution, the solution is
is arranged in a reaction zone with adeguate
warmed to about 55° 0., and being introduced into
heating means, such that the temperature of the
a container provided with an agitator, concen
mass may be maintained at 800-l200° F., the
trated ammonium hydroxide 2310 g. and 1500 g. . raw material being passed into contact with the
ammonium acetate per 112 liters of distilled wa
catalyst. The raw material generally involves
ter is supplied. A blue-green precipitate is
non-benzenoid hydrocarbons, as aliphatic hydro
formed which is allowed to settle for about two
carbons or paraf?ns and ole?ns and naphthenic
hours, and the cake‘ resulting is washed three
hydrocarbons or their mixtures, naphthas, dis
times by dispersion into four liters of water, and is
tillates, as naphthas or distillates from stocks
?ltered. The precipitate is dried at about 140°
which are predominantly non-benzenoid, as for
15"., and then under vacuum‘ at about 400° F. A
instance derived from Pennsylvania, Michigan,
vitreous gel results. The proportions of tin and
Kentucky, Ohio, Mid-Continent and the like pe
aluminum and chromium are most desirably
troleum, and therewith a gas providing hydrogen.
those as above-indicated, but in general the tin " Hydrogen as occurrent in the off-gas may be em
need not advisably be less than one or more than
ployed, or relatively pure hydrogen. The hydro
thirty mol per cent and the aluminum not less
gen in the catalyst zone may be from 40-400
than ?fty nor more than ninety mol per cent, the
pounds per square inch, Desirably also, butanes
remainder being chromium. In some instances
or four carbon atom gaseous hydrocarbons may
antimony may replace all or part of the tin. 50 also be supplied, Such may be provided by the
Again in some instances beryllium may replace
oil-gas, or from special sources, as convenient.
all or part of the aluminum. That is, an element
When butanes are also included in the material
from the group of laterally adjacent atomic num
fed to the catalyst zone in excess of the mols of
bers 50 and 51 in the periodic table and an
amphoteric oxide forming element from the diag
normally liquid hydrocarbon charged, the pres
55 sure may be as high as 800 pounds per square
2,410,044
3
inch. Conveniently, the gases formed may be re
cycled, by adding such gas or any portion thereof
to the naphtha vapors for passage over the cata
lyst. Or, these gases may be added in successive
portions to different, but not necessarily consecu
tive, bodies in‘apparatus where arrangement of
4
We therefore particularly point out and dis
tinctly claim as our invention:
1. In a process of aromatizing, subjecting hy
drogen and a hydrocarbon of four carbon atoms
and a naphtha containing non-benzenoid hydro
carbons," at elevated pressure and la'ltemperature
of 800-1200" "F., to the ‘action of an oxide con
the catalyst is in a series of bodies. With this
tact-mass formed from co-precipitation from dis
combination of normally gaseous and normally
solved salts of tin and aluminum and chromium,
liquid hydrocarbons, an advantageous feature is
that the catalyst does not tend to accumulate .10 the tin in the contact-mass being 1-30 mol per
coke quickly, and at the same time a component
cent.
_2. In a process of aromatizing, subjecting
of heat is generated in situ in the catalyst bed by
hydrogen and a hydrocarbon of four carbon atoms
the combining of hydrogen in ‘a reaction. ‘Flow
and a naphtha containing non-benzenoid hydro
rates of naphtha may be 0.1-10 liquid volumes
carbons, at elevated pressure and a temperature
per volume of catalyst per hour. ‘At the higher
of»800-l200°'TF., to the action of an oxide con
temperatures correspondingly shorter contact
' time may be used.
Hydrogen is fed at the rate
of 0.1-10 mols of H2 per mol of naphtha. And
where hydrocarbons such as butane or isobutane
are Provided, their feed rate may be l-lO mols
thereof per mol of naphtha.
tact-mass formed from col-precipitation from
dissolved salts of antimony, aluminum and
chromium, the antimony in the contact-mass be
ing 1-30 mol per cent.
3. In a process of "aromatizing, subjecting ‘hy
drogen and a hydrocarbon of four carbon atoms
"After contacting with ‘the catalyst, aromatic
and a naphtha containing non-benzenoid hydro
and unsaturated hydrocarbons may be extracted
carbons, at elevated pressure and a temperature
orpartially extracted from the products, for ex
ample by mixing with a solvent having‘ the se 25 of 800—1200° F., to the action of an oxide contact
mass formed from co-precipitation from dissolved
lective character of ‘sulphur dioxide, or a high
salts of tin and beryllium and chromium, the tin
boiling amine, or hydroxy compound, or other
in the contact-mass being 1-30 mol per cent.
solvents 'or combinations of such solvents ‘and
4. In a process of ‘aromatizing, subjecting hy
the undissolved or non-benzenoid portion may be
drogen' and a hydrocarbon of four carbon atoms
re-passed into contact with the catalyst. The
and a naphtha containing non-benzenoid hydro
gases formed may be recycled in whole or in part.
carbons, at elevated pressure and a temperature
v'I‘he catalyst may be regenerated in situ by sup
of 809-l200° R, to the action of an oxide contact
plying to it, the temperature being 800-1200° II,
oxygen-containing gas suchas air, or air diluted » mass formed from co-precipitation from "dis
solved salts of chromiumand an amphoteric oxide
‘with forv instance ?ue gas.
forming element from the group consisting of
Operating with a naphtha for instance, at 980°
beryllium and aluminum, and another oxide
‘F. and '100 pounds pressure, in a run for ?ve
forming element from thegroup consisting of tin
hours, and the flow rate of'naphtha 1.4 v. v. h.
and antimony, such amphoteric oxide forming
and gas providing hydrogen at a 3:1 ratio of hy
drogento the hydrocarbon, the catalyst being a 40 element and other oxide forming element in the
contact-mass being "50-90 mol per cent and 1-30
co-precipitated catalyst of 1 per cent of tin oxide,
mol per cent respectively.
'79 per cent of ‘aluminum oxide and 20 per cent of
5. In a process of aromatizing, subjecting hy
chromium oxide, a yield of 81.5 per cent con
drogen’and a hydrocarbon of four carbon atoms
densate having a Kattwinkel test corresponding
: 'anda normally liquid no'n-benzenoid hydrocar
to61 per cent-aromatics and unsaturated hydro
bonpatelevated pressure and a temperature of
carbons is obtained. In an analogous run with a
800-1200°
to the action of an oxide contact
catalyst of co-precipitated character involving 1
mass formed from co-precipitation from ’ dis
per cent of antimony oxide, '79 per cent of alu
solved salts of chromium and an amphoteric oxide
minum oxide and 20 per cent of chromium oxide,
‘a liquid yield of 80 per cent having a Kattwinkel 50 forming‘element from the group consisting of
beryllium and aluminum, and another oxide
test ‘of '60 per cent was obtained.
forming element from the group consisting of tin
This application is a continuation, in part, and
and antimony, such amphoteric' oxide forming
as to common subject matter, of our application
element and other oxide forming'element in the
"Serial'No. 228,005, ?led Sept. 1.1938.
Other modes of applying the principle of the 55 contact-‘mass being 50-90'mol per cent and 1-30
invention ‘may be employed, change being made
as regards the details described, provided the
‘features stated in any of the following‘claims, or
the equivalent of such, be employed.
mol-per cent respectively.
‘ROBERT E.'BURK.
EVERETT C.’ HUGHES.
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