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Патент USA US2112931

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2,112,931
Patented Apr. 5, 1938 ‘I
‘UNITED’ .STATES PATENT orFicE
2,112,931
CATALYTIC MATERIAL‘ AND DIETHOD OF
PRODUCING SAME-
'
Walter A. Schulze, Bartlesville, on... assignorlto
Phillips Petroleum Company, a corporation of
Delaware
' No Drawing.
Application October c, 1936,
Serial No. 104,305
6 Claims.‘ ‘(01. 23-233)
.
An
alkali,
preferably
ammonium
hydroxide,
is
The present invention relates to a catalytic ma
terial adapted more particularly to facilitate the ‘then added and the aluminum hydroxide is pre
decomposition of organic sulfur compounds and cipitated. The aluminum hydroxide gel is thor
to improve the antiknockcharacteristics of those oughly impregnated with the ?nely divided par
, 5 hydrocarbon ?uids utilized as motor fuels.
' {- More speci?cally, the invention relates to an
ticles of carbon black.
In addition to this im- 5.
pregnation I believe there ‘is still another effect,
vextremely porous aluminum oxide and to the namely, the presence of the carbon black particles
process of manufacture of such'catalytic material. causes more rapid precipitation of the aluminum
It has been known heretofore that when sulfur hydroxide when the alkali is added, thus produc
1O
bearing hydrocarbon vapors are passed over
alumina in, certain of its naturally occurring
forms, e. g. bauxite, some of the organic sulfur
compounds are decomposed to hydrogen sulfide.
ing a gel with a structure different from that pro
duced heretofore in the absence of the ?nely
divided carbon black.
_
.
The aluminum hydroxide-carbon black gel is I '
I have found moreover that commercial aluminas filtered'from the aqueous solution and washed
15 when used, for this purpose are frequently much with water to remove the alkali'salt. It is then
less effective catalysts than the naturally occur (dried and ground and screened to a desirable
ring bauxites. I attribute this difference to the sized product, usually 10 to 40 mesh. ‘A stream of
air or oxygen-containing gas is then passed over
physical and chemical structure of'these mate
rials. It is fairly de?nitely established that the said product while at an elevated tempera
'20 among naturally occurring hydrated aluminas ture, so that the carbon blackis oxidized and sub- 20
. ‘gibbsite (or hydrargillite) "and diaspore are re
spectively AlzOaBHaO and A1:O:.H20. The com
position of bauxite is still doubtful. Likewise, the
-crystalline commercial precipitate obtained ‘from
25 solutions of alumina in alkalies is a definite
hydrate, A1203.3H2O, either identical with gibbsite
or isomeric with it. Certain authorities have‘con
cluded also that precipitated .gelatinous alumina
is composed of A1203.3H2O, containing water ad
30 sorbed on its surface and entrained in its inter
stices. None of these forms of alumina appear
1 vto correspond, to the improved alumina which I
. stantially removed.
If desired, the carbon black
may be removed prior togrinding and screen
ing to proper size. The alumina
alyst is,’ of
course,well dehydrated during this burning opera
tion. ‘The product prepared in this manner has
a very low specific gravity, usually ranging from
0.25 to 0.65 but it may be more or less depending
principally on the amount of carbon black used
in the suspension. It hasan extremely high
porosity, yet it is not very friable whereas most 30
catalytic materials of low Specific gravity are
friable.
'
'
A more speci?c example of one preparation of '
lying in the peculiar structure as_well as in the ' ‘this improved alumina catalyst follows: One part
by weight of aluminum chloride was dissolved in
exceptionally high porosity of this new product. '
It is the-object of this invention to provide an twenty parts by weight of water. One part by
weight of carbon black passing a'300 mesh screen
improved alumina catalyst whose physical struc
ture is such that the material has a considerably ' was stirred into the solution of aluminum chlo
have discovered, the improvement'undoubtedly
\
4O
higher catalytic activity than those aluminas pro
0
of dilute ammonium hydroxide was then added .
of the catalyst is so much improved that the rate ‘ to precipitate. aluminum hydroxide, the'carbon
of decomposition‘ of organic sulfur compounds
such as mercaptans and sul?des is so rapid that
complete decomposition can be had at lower
.m. operating temperatures.
4
' ride until a good suspension was had. An excess
duced heretofore, In other words, the activity
black aiding in the formation of a very gelatinous
precipitate. The precipitate was washed several
times to remove the ammonium chloride and ex- 45
Furthermore, certain : cess ammonium hydroxide. The product upon
drying had a black, glossy, vitreous appearance.
' classes of the so-called residual sulfur compounds
are ‘decomposed quite readily-with my improved '- Theparbon black was removed by passing a
catalyst whereas such compounds are normally stream of carbon dioxide’ containing a small
amount (5-10 per cent by volume) of oxygen
50- rather resistant to decomposition.
'
‘ I have discovered that this improved alumina. through the product heated to about‘500° C. The
catalyst of ‘extremely high porosity ‘and low
speci?c gravity can be made, by making a suspen
sion of ?nely divided carbon black in an aqueous
‘ solution of an aluminum salt such as the nitrate.
precipitate after the burning operation was white,
porous and extremely light, tsldenlsity being less
than half that of bauxite or 0 most commercial
\aluminas.
-
-
'
-
'
2,112,931
The ratio of carbon black to aluminum salt
can, ‘of course, be varied over a wide range.
I
have obtained very satisfactory catalysts through
residues may be rezp'enerai a‘ 1i inde?nitely by heat
treatment with air or an. oxygen-bearing gas.
In spite of the‘ very high porosity this alumina
the use of as little as one part of carbon black to
ten or more parts of aluminum salt and likewise
catalyst shows
have secured excellent results from preparations
?nes formed during either the handling of this
gatalyst or during the passage of gasoline stock
wherein the carbon black was equivalent to or
greater than, the aluminum salt.
It is evident
that too high a proportion of carbon black will
10 tend to increase the friability of the resultant
unusually good
mechanical
strength, as is indicated by the low percentage of
apors-at high velocities and/or during regenera
tion;
.
'
alumina and render it un?t as a catalyst for va
desulfurizing hydrocarbon ?uids and of improv
por phase processes but within the limits stated
herein excellent friability _ characteristics are
ing. the antiknock characteristics of motor fuels.
For example, it has speci?c advantages for facil
had.
itating the dehydration decomposition of organic
,
The carbon black referred to herein is that
made from gaseous hydrocarbons but other
>
This catalysthas many uses other than that of
substances and especially the dehydration of al
coholic bodies. Also, due to its highly porous
blacksand similar materials can, of course, be . character and high ‘mechanical strength, it is es
pecially suitable for impregnating with solu—
‘
As an illustration of the activity of my alumina tions of various materials, such as the metallic
20 catalyst, the following examples are given. How
salts. Furthermore, it may be used with or with 20
ever, since the number of examples could bemul - out other substances for ?ltering purposes, or it
used.
tiplied greatly, the ones given here are merely
illustrative and in no sense limit the invention.
> Example 1'
25'
Pentamethylene sul?de
(a member of the thio- -
phane series of sulfur compounds) in a light
naphtha was vaporized and the vapors heated to
a temperature of 705° F. While at this tempera
30 ture the vapors were contacted with alumina cat
alyst prepared originally from sixteen parts of
aluminum chloride to one part of carbon black
at a ?ow rate equivalent to almost three liquid
volumes of the naptha solution per hour per vol
Much hydrogen sul?de was
35 ume' of catalyst.
formed during the treatment; it was removed
prior to further testing. The sulfur content of the
solution prior to treatment was 0.0707 per cent
and after the treatment 0.0025 per cent, indicat
may be used to dehydrate gases and vapors.
Mixed catalysts such as alumina and‘ one or
more of the various oxides may be prepared in a
manner similar to the pure alumina mentioned 25
above merely by starting with a solution contain
ing the proper salts in the correct proportions
and then adding the‘ carbon black thereto.
It is obvious to those skilled in the art that va
rious‘ changes may be made in the composition 30
and procedure as described and in the method of
‘utilizing this improved alumina without depart
ing from the scope of the invention as de?ned in
the appended claims.
-
-
-
I claim as my invention:
1. A process of manufacturing highly porous
35
alumina,v which comprises, adding carbon black
to a solution of an aluminum salt, adding an ex
cess of an alkali whereby the aluminum salt is
40 ing almost complete decomposition of the penta
precipitated as aluminum hydroxide and the 40'
methylene sul?de. Under similar conditions of carbon black is incorporated in the precipitate,
?ow rate and temperature, commercial aluminas Y drying the precipitate of aluminum hydroxide
and even bauxite were considerably less effective. - and carbon black, removing the carbon black
from the precipitate by oxidation, and thereby
Emample 2
obtaining highly porous alumina.
- 45
45
2. A process of manufacturing highly porous
Cracked gasoline produced by pressure crack
ing of Panhandle topped crude was given two alumina‘, which comprises, adding carbon black
successive treatments over highly active bauxite
to a solution of an aluminum salt, adding am
catalyst so as to remove all of the sulfur com
monium hydroxide to the mixture whereby alu
pounds which could possibly be attacked andv minum hydroxide is precipitated as a’gel and the
decomposed by such catalysts. Following this carbon black is incorporated in the gel, drying
the gelatinous precipitate, and substantially re-v
treatment only the so-,called residual sulfur com
pounds were present. The sulfur content was moving the carbon black by oxidation withan‘
oxygen-containing gas at elevated temperature.
0.0946 per cent.
.
'
3. A process of manufacturing an improved 55
This cracked gasoline. stock was contacted in
the vapor form with one of my alumina catalysts catalytic material for decomposing organic sul
fur compounds and for improving the antiknock
with a speci?c gravity of 0.4, prepared as indi
cated above, and at a temperature of ‘750° F. and characteristics of motor fuels, which comprises,
a flow rate of about three liquid volumes per
60 hour per volume of catalyst 16 per cent of the re
sidual sulfur compounds were decomposed to
hydrogenv sul?de. The octane rating of the
cracked gasoline was likewise‘ considerably im
preparing a suspension of carbonv black in a solu
tion of an aluminum salt, adding ammonium hy 60
droxide to the said carbon black suspension in
the aluminum salt solution whereby a black gel
comprising aluminum hydroxide and carbon
black is formed, drying the saidgel, substantial
ly removing the carbon black by oxidation, and
‘thereby obtaining an improved catalytic mate
also at several higher temperatures with the other rial.
conditions remaining constant. At 872° F. the
4. A process of manufacturing highly porous
o
sulfur content was lowered 20.2 per cent, at 905°_ alumina with'a speci?c gravity within the range
it was lowered by ‘24.8 per cent, and at 932° F. of 0.2 to 0.7 and with relatively high mechanical
'70 1".
30.2 per cent of the residual sulfur was removed. strength, which comprises, adding carbon black 70
proved.
65~
‘
'
,
This same cracked gasoline stock was treated
Further improvement in antiknock characteris
tics was noted at these higher temperature lev
els where more of the sulfur was removed.
76
The catalyst when poisoned by carbonaceous
to a solution of an aluminum salt, adding an al
kali to the mixture whereby a black gel comprise“
ing aluminum hydroxide and carbon black; is
formed, ?ltering the gel from the solution, wash
_
_
2,112,981
black} geLcomprising aluminum hydroxide and
ing the gel to remove the various impurities, dry
ing the said puri?ed gel, substantially removing carbon black is formed, washing and drying said
gel, and ?nally substantially removing the car
the carbon black from the gel by oxidation at ele
vated temperature, and thereby obtaining a highs bon black by oxidation.‘
1y porous alumina with a speci?c gravity in the ', f 6. A process of manufacturing a highly porous
catalytic material comprising alumina, which
range of 0.2 to 0.7 and of relatively high mechan
comprises, adding carbon black to asalt solution
ical strength.
'
5. A process of manufacturing a highly porous ' comprising an aluminum compound, adding ant
alumina for. subsequent impregnation .with me
10 tallic salt solutions, which co prises, adding car
alkali hydroxide to the mixture whereby a black
gel is formed, drying said gel, and substantially 10
bon black to an aluminum s/ it solution, adding . removing the carbon black by oxidation.
‘ WALTER A. SCHULZE.
an alkali hydroxide to the mixture whereby a
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