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Патент USA US2388937

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Patented Nov. 13,1945
- 2,388,937
V. UNITED STATES PATE
omca
TREATMENT OF HYDROCARBON OILS
I Louis Schmerling and Vladimlr‘N. Ipatiefl', Chi
cago, Ill., assignors to Universal Oil Products
Company, Chicago, Iil., a corporation of Dela
ware _
No Drawing. Application September 9, 1940,
Serial No. 358,040
20 Claims.
(01. lac-5s) '
This invention relates to the treatment of rela
tively heavy hydrocarbons or hydrocarbon mix
tures, of which fractions of petroleum and pri
mary distillates from the distillation of coal,
tion comprises a process for destructively hydro
wood, and shale are typical. It is more specifi
cally concerned with processes forthe so-called
of hydrogen to contact with granular catalysts
comprising essentially composites of zinc chloride
and aluminum oxide.
"destructive” hydrogenation of these oils to-pro
duce lower boiling products therefrom.
genating hydrocarbonaceous materials which
consists in subjecting such materials at elevated I
temperatures and pressure and in the presence
The
An extensive series of experiments which we
have conducted with the above mentioned type
of novel types of catalysts for accomplishing 10 of catalysts indicates that they are of outstand
ing value in promoting destructive hydrogenation
these purposes.
reactions. These catalysts are made by simple
Destructive hydrogenation, as distinguished
methods of mixing in which some formof ?nely
from the simple addition of hydrogen to unsatu
divided or formed alumina is mixed with either
rated bonds between carbon atoms, involves de?
nite changes in structure, and may be designated 15 aqueous solutions of or dry zinc chloride although
as a rule, the use of aqueous solutions is prefer
as cracking under hydrogenating conditions so
invention is particularly characterized by the use
that the lower boiling products of the cracking
reactions are substantially more saturated than
when hydrogen or materials supplying hydrogen
are not present. Destructive hydrogenation 20
may be employed or any of the forms of prepared
processes are most commonly'employed on coals
and heavy residual or distillate oils for the pro
alumina, commonly known as “activated” varie
ties and produced by controlled calcination of the
able.
Bauxite may be used as a source of alu
mina, this mineral having the overall formula
AlzOaZI-IzO.
Precipitated aluminum hydroxide
duction of substantial yields of low boiling satu
hydrated forms. After mixing the materials in
various proportions, they are dried at approxi
rated products and to some extent of intermee
diates utilizable as domestic fuels and still heavier 25 mately 350° C. for a period of about 20 hours.
When formed alumina is impregnated with zinc
cuts suitable as lubricants. These destructive
hydrogenation processes may be operated on a
chloride solution, the particles are then ready for
use in destructive hydrogenation and if powdered
strictly thermal basis or in the presence of cataé
lysts and in this respect an extremely large num
alumina is employed, the material resulting from
ber of materials have been employed, for exam 80 the calcination which will be in the fused condi
tion may be pulverized or granulated to produce
ple, the metals of the iron group, including iron,
particles of the desired size which can be used
nickel, or cobalt and the oxides and sul?des of
chromium, molybdenum, and tungsten, repre
as such or formed by extrusion or pilling methods.
It is not certain whether the composition of
senting the metals in the left-hand column of
group VI of the periodic table. Numerous mixed 35 these catalysts can be designated broadly by the
formula mZnCldnAlzOa or whether zinc oxychlo
metal and metal oxide catalysts have also been
rides are present. When using d-i?erent propor
tried and less commonly metal salts.
- tions of zinc chloride and alumina and different
Destructive hydrogenation operations are com
monly conducted at relatively high hydrogen
amountsof water, catalysts of varying composi
5000 lbs/sq. in. being not uncommon, although
which they may be employed. It has been found
pressures, particularly those which are operated 40 tion are producible» which have varying activities
without the use of catalysts, pressures of 3000
in reactions of destructive hydrogenation in
particularly bene?cial in using the present types
‘reduced. Temperatures are usually those within 45 of catalysts in destructively hydrogenating hy
drocarbons to have minor amounts of hydrogen
or slightly below the oil cracking range, say from
chloride present, the eifect of this addition being
‘700-900" F. Hydrogen is preferably present in
with suitable catalysts, these pressures can be
considerable molal excess and gas mixtures con
shown _in later data in the section devoted to
taining hydrogen and other gases such as meth
ane, carbon monoxide, nitrogen, etc. may be em
examples.
catalysts for use in destructive hydrogenation
1004-500" 0. though as a rule the temperatures
'
'
The present types of catalysts may be used at
ployed. The present process embodies improved 50 temperatures within the approximate range of
most commonly used fall within the limits of
processes, which catalysts permit the attainment
350-450" C. Relatively high pressures of hydro- ,
of the objects of such processes at relatively low
temperatures and pressures.
gen are preferable of the order of 500-2000 lbs/sq.
In one speci?c embodiment, the present inven 55 in. The process may be conducted on a batch
2
2,888,987
-
_
I
,
,_
_
,
more the yield of condensible ga‘s consisting of
or continuous basis although the latterv method
of operation is preferred commercially. In the
batch process, the catalyst is mixed with the oil
to be destructively hydrogenated in a pressure
vessel preferably lined with material such as glass‘
about 40 mol per cent propane, 54 mol per cent
of iso-butane and 6 mol per cent of normal bu
tane was increased from 8 to 26% by weight of the
gas oil charged.‘
Example 11!
which has substantially no catalytic effect in the _
reactions as contrasted with metals, a small
' Using the same catalyst as in'the preceding
examples, the same proportions of oil and catalyst,
and the same temperature and initial. hydrogen
amount of hydrogen chloride is introduced, and
hydrogen is admitted to develop the required
pressure, found by trial to be optimum for the
desired conversions. The pressure vessel is then
pressure, a Trinidad gas oil was treated and
yielded as an average of 3 runs 21% of 300° end
exteriorly heated during mechanical stirring of
point material.
the contents or rotation of the vessel to insure
thorough mixing and contact with the reactants h
and the catalyst. In continuous processes gran
ular catalyst is utilized in stationary beds in ver
tical or horizontal cylindrical chambers and the
,
Example IV
Amyl benzene was destructively hydrogenated
in the presence 'of a zinc chloride on alumina cata
lyst, using av temperature of 400° C. 21% by
weight of pentane was obtained and a 30% yield mixture of hydrocarbons to be hydrogenated,
hydrogen chloride, and hydrogen are forced
of benzene.
Example V
through the granular material ‘after which the 20
products are separated by fractionation and the
A similar run at 400° C. on seo-butylbenzene
unconverted and reusable constituents recycled.
gave a 15% yield of iso-butane and a 31% yield
The present process is applicable to the de
of benzene by weight. These yields were increased
structive hydrogenation of individual compounds
by retreatment of unconverted material after sep
25
such as naphthalene and anthracene to form
aration of the reaction products. It is signi?cant
mono-nuclear aromatics and to the destructive
of the value of the ‘process that the iso-butane
hydrogenation of relatively heavy residua and dis
was obtained from the decomposition of the butyl
tillate fractions of petroleum to produce motor
benzene rather than normal butane.
fuel fractions. The catalyst is also‘e?'ective in
such splitting reactions as the formation of iso-‘ 80
butane and benzene from sec-butylbenzene, and
pentane and benzene from amylbenzene. This is
in contrast with results obtained with more stand
Example VI
To indicate the possibilities of the process in
' continuous operation, a Pennsylvania gas oil was
ard types of hydrogenating catalysts, such as ' destructively hydrogenated in the presence of a
nickel, which, for example. produces very little 35 zinc chloride on alumina catalyst using anhourly
liquid space velocity of one, a pressure of 1000 lbs.
cleavage of the side chain of amyl benzenes and
per square inch, and three moles of hydrogen per
produces rather a mixture of alkyl cyclo-hexanes.
mol of gas oil. Separate runs of approximately
The following examples are introduced to in
18 hours duration were made at temperatures of
dicate the type of results obtainable by using the
present types of catalysts in destructive hydro 40 400 and 450° C. The results in gasoline produced
are given below:
genation reactions, although it is not intended to
limit the scope of the invention in precise corre
spondence with the data thus introduced.
Per cent 300 Per cent 400 Octane No.
Temp" QC‘
Example I
A catalyst was prepared by impregnating %"
by $43" cylindrical activated alumina pills with
400 ___________________ _450 ___________________ __
an aqueous solution of zinc chloride followed by
drying ?rst at 100° C. and then at 350° C. The
catalyst thus prepared contained basic zinc chlo 50
ride
(Zn(OH) C1).
The pressure vessel was
charged with 90 parts by weight of naphthalene
and 10 parts by weight of the above mentioned
sel was heated at 400° C. for a period of 2 hours.
Benzene, toluene, and xylenes were identi?ed in
the product which consisted of 22% of material
boiling up to 175° C., 36% boiling up to 200° C.,
'
Example II
Using a catalyst prepared in substantially the
E. P. gaso.
37.3
40. 0
49. 3
5i. 5
60
300° F. gaso.
76. 5
77. 5
Example VII
Using a gas oil from 9. Trinidad crude, the fol
lowing results were obtained in continuous opera
tion:
catalyst. Hydrogen was admitted to an initial
pressure of 1500 lbs/sq. in. and the pressure ves 65
of 86% recovered liquid.
E. P. gaso.
Temp" 00
'
Per cent 300 Per cent 400 Octane No.
E. P. gaso. E. P. gm. 300° F. gaso.
'400 ___________________ -_
38.0
54
78.0
450 ___________________ -_
37.0
53
............ __
We claim as our invention:
1. A process for the destructive hydrogenation
of hydrocarbonaceous material which comprises
reacting said material mixed with hydrogen in
same manner as in Example I, a charge of 10%
by weight of catalyst and 90% by weight of a 65 the presence of a zinc chloride and aluminum
Pennsylvania gas oil was treated at 400° C. and
an initial hydrogen ‘pressure of 1500 lbs./Sq- in
The average yield of 300 end-point gasoline in a
series of 3 runs was 51.5% by weight of gas oil
oxide.
‘
2. A process for the destructive hydrogenation
of hydrocarbonaceous material which comprises
subjecting said material mixed with hydrogen to
charged. The yield of 400» end-point material 70 contact with a zinc chloride and aluminum oxide
under catalytic destructive hydrogenation con
was 67.5%.
ditions of superatmospheric pressure and elevated
As a variation of the above runs, 2-4% by
temperature.
weight of hydrogen chloride was added to the
3. A process for the destructive hydrogenation
pressure vessel which increased the yield of 300
end-pointmaterial from 51.5 to’ 55%. Further 75 of hydrocarbonaceous material which comprises
2,388,987
3
.
subjecting said material mixed with hydrogen at
duce therefrom substantial yields 01 mono-nu
a temperature of from about 100 to about 500°
C. and under a Pressure of from about 500 to about
clear aromatic compounds which comprises sub
iecting a poly-nuclear aromatic compound mixed
2000 pounds per square inch to contact with '
catalytic material comprising essentially zinc
with hydrogen and a minor amount of hydrogen
chloride at a temperature of from about 350 to
chloride and aluminum oxide.
about 450° C. and under a pressure of from about Q ~
-
1000 to about 2000 pounds per square inch to
contact with catalytic material comprising es
sentially zinc hydroxy chloride and aluminum
4. A process for the destructive hydrogenation
voi’ hydrocarbonaceous material which comprises
subjecting said material mixed with hydrogen
and a minor amount of hydrogen chloride at a 10
temperature of from about 100 to about 500° C.
under a‘pressure' of from about 500 to about 2000
pounds per square inch to contact with catalytic
material comprising essentially zinc chloride and
aluminum oxide.
oxide.
-
12. A process for the destructive hydrogenation
of naphthalene to-produce therefrom substantial
yields of mono-nuclear aromatic compounds
which comprises subjecting said naphthalene
15 mixed with hydrogen at a temperature of from
'
5. A process for the destructive hydrogenation
oi’ hydrocarbonaceous material which comprises
subjecting said material mixed with hydrogen at
about 350 to about 450° C. and under a pressure
of from about 1000 to about 2000 pounds per
square inch to contact with catalytic material
comprising essentially a zinc chloride and alu
a temperature of from about 100 to about 500° C.
under a pressure of from about 500 to about 2000 20 minum oxide.
13. A process for the destructive hydrogenation
pounds per‘ square inch to contact with. catalytic
of naphthalene to produce therefrom substantial
material comprising essentially zinc hydroxy
yields of mono-nuclear aromatic compounds
chloride and aluminum oxide.
which comprises subjecting said naphthalene
' 6. A'process for the destructive hydrogenation
of hydrocarbonaceous material which comprises 25 ‘mixed with hydrogen and a minor amount of
hydrogen chloride at a temperature of from
subjecting said material mixed with hydrogen
about 350 to about 450° C. and under a pressure
and a minor amount of hydrogen chloride at a
of from about 1000 to about 2000 pounds per
temperature of from about 100 to about 500° C.
square inch to contact with catalytic material
under a pressure ofafrom about 500 to about 2000
pounds per square inch to contact with catalytic 30 comprising essentially zinc chloride and alu
minum oxide.
material comprising essentially zinc hydroxy
14.. A process for the destructive hydrogena
chloride and aluminum oxide.
.
tion of naphthalene to produce therefrom sub
7. A process for the destructive hydrogenation
_ stantial yields of mono-nuclear aromatic com
of poly-nuclear aromatic compounds to produce
therefrom substantial yields of mono-nuclear aro~ 35 pounds which‘ comprises subjecting said naphtha
matic compounds which comprises subjecting a
lene mixed with hydrogen and a minor amount
oi hydrogen chloride at a temperature of from
poly-nuclear aromatic compound mixedwith hy
about 350 to about 450° C. and under a pressure
drogen to contact with catalytic material com
of from about 1000 to about 2000. pounds per
prising essentially a zinc chloride and alumi
4.0 square inch to contact with catalytic material
comprising essentially zinc hydroxy chloride and
8. A process for the destructive hydrogenation
num
oxide.
'
I,
V
'
of poly-nuclear aromatic compounds to produce
therefrom substantial yields of mono-nuclear
aromatic compounds which comprises subjecting
said poly-nuclear aromatic compound, mixed
with hydrogen at a temperature of from about
350 to about 450° C. and under a pressure of
from about 1000 to about 2000 pounds per square
inch to contact with catalytic material compris
aluminum oxide.
15. A process for the destructive hydrogenation
of an alkyl benzene to produce therefrom sub
stantial yields of parailins and benzene which
comprises subjecting said alkyl benzene mixed
with hydrogen at a temperature of from about
350 to about 450° C. and under a pressure of from
about 1000 to about 2000 pounds per square inch
lng essentially a zinc chloride and aluminum 50 to contact with catalytic material comprising es
sentially a zinc chloride and aluminnum oxide.
oxide.
.
16. A process for the destructive hydrogenation
9. A process for the destructive hydrogenation
of an alkyl benzene to produce therefrom sub
of poly-nuclear aromatic compounds to produce
stantial yields of paraffins and benzene which
therefrom substantial yields of mono-nuclear
aromatic compounds which comprises subjecting 55 comprises subjecting said alkyl benzene mixed
with hydrogen and a minor amount of hydrogen
a poly-nuclear aromatic compound mixed with
chloride at a temperature of from about 350 to
hydrogen and a minor amount of hydrogen chlo
about 450° C. and under a pressure of from about
ride at a temperature of from about 350 to
1000 to about 2000 pounds per square inch to
about 450° C. and under a pressure of from about
1000 to about 2000 pounds per square inch to 60 contact with catalytic material comprising essen
tially zinc chloride and aluminum oxide.
contact with catalytic material comprising essen
17. A process for the destructive hydrogenation
tially zinc chloride and aluminum oxide.
of an alkyl benzene to produce therefrom sub
10. A process for the destructive hydrogena
stantial yields of .paramns and benzene which
tion of poly-nuclear aromatic compounds to pro
duce therefrom substantial yields of mono-nu 65 comprises subjecting said alkyl benzene mixed
clear aromatic compounds which comprises sub
with hydrogen and a minor amount of hydrogen
jecting a poly-nuclear aromatic compound mixed
chloride at a temperature of from about 350 to
about 450° C. and under a pressure of from about
with hydrogen at a temperatureof from about
1000 to about 2000 pounds per square inch to con
350 to about 450° C. and under a pressure of
from about 1000 to about 2000 pounds per square 70 tact with‘ catalytic material comprising essen
tially zinc hydroxy chloride and aluminum
inch to contact with catalytic material compris
oxide.
ing essentially zinc hydroxy chloride. and alumi
18. A process for the destructive hydrogena
num oxide.
tion of a relatively heavy petroleum fraction to
11. A process for the destructive hydrogena
tion of poly-nuclear aromatic compounds to pro 75 produce substantial amounts of gasoline boiling
4
range material therefrom which comprises sub
jecting said fraction mixed with hydrogen at a
temperature of from about 100 to about 500° C.
' under a pressure of from about 500 to about 2000
terial comprising essentially zinc chloride and
aluminum oxide. .
20. A process for the destructive hydrogenation
of a relatively heavy petroleum fraction to pro
pounds per square inch‘ to contact with catalytic 5 duce substantial amounts " of gasoline boiling
range material therefrom which comprises sub‘
material comprising essentially a zinc chloride
Jecting said traction mixed with‘ hydrogen and a
and aluminum oxide.
19. A process for the destructive hydrogenation
minor amount of hydrogen chloride at a tempera
of a ‘relatively heavy petroleum fraction to pro
ture of from about 100 to about 500° C. and under
duce substantial amounts of gasoline boiling 10 a pressure oi‘ vifrom about 500 to about 2000
pounds per square inch to contact with catalytic range material therefrom which comprises sub
Jecting said fraction mixed with hydrogen and a
material comprising essentially zinc hydroxy
minor .amount of hydrogen chloride at a tem
chloride and aluminum oxide.
perature of from about 100 to about 500° C. under
a pressure 01' from about 500 to about 2000 pounds 15
’
hours scmmanma.
per square inch to contact with catalytic ma
vVLADIMIR. N. IPA'I'IEFF. ‘
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