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Патент USA US2404498

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Patented July 23, 1946 '
2,404,498 ,
UNITED STATE s
rATENTJ omceff
2,404,498
PRODUCTION OF TOLUENE
I ' VladimirN. Ipatieff and George S. Monroe, River-7
side, 111., assignors to Universal Oil Products ‘
Company, Chicago, 111., a corporation ofvDela
I
' ware
No Drawing. Application Mai-011' 27, 1944, .
Serial No. 528,345 ,
7 Claims. (01. 2604-671)
1
2.. '
refractory carriers such as natural-‘occurring’s'ili
This invention relates to the production of tolu
ene from benzene and methane in therpresence of
a catalyst and is more speci?cally concerned with
ceous or aluminiferous materials or synthetically '
prepared'supportsn
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clude kieselguhr, acid-treated‘ clays, bauxite and
stantial yields of toluene in the presence of a par
similar substances. Synthetic carriers may-com‘
prise silica, alumina, thoria and similar refractory .4
ticular catalyst and under speci?c conditions'of
temperature and pressure.
'
Natural-occurring supporting materials will in
the conversion of benzene and methane into- sub- -
‘
materials. ‘The various catalysts ‘produced by
compositing the above refractory carriers and the
conversion processes such as cracking, reforming; 10 active metals or metal 'oxides'are not necessarily
equivalent in their ability to accelerate the de-v
etc. 'Heretofore, because in ordinary operation
sired reaction. The activity of each catalyst will
it is chemically inert, the primary uses of meth
be dependent to a certain extent ‘upon the vpar
ane in industry has been for fuel, for the manu
/ Methane’ is obtained in abundancefrom natural
gases or as a by-product of various hydrocarbon
facture of carbon black or as an inert diluent in
ticular metal or metal oxide and carrier chosen.
reactants.
guhr, 'A-detailed method‘of preparing this cata:
various hydrocarbon conversion ‘processes to ef 15 A particularly active catalyst comprises a com
posite of metallic nickel, nickel oxide and kiesel
fect a ‘lowering of the partial pressure of the
'
'
lyst is given hereinafter in this speci?cationl. 5
, The'carrier materials maybe‘ obtained by a
number of methods, some‘ of ‘which are herein
It_ is recognized that methane has been con
verted to methyl chloride and the methyl'chlo
ride employed as an alkylating agent to alkylate
benzene in the presence of aluminum chloride to
produce toluene and more highly alkylated ben
zenes.‘ However, the preparation of the methyl
chloride is expensive and, for this reason, the
process has not assumed any commercial impor
tance.
'
after set forth:
In' one broad embodiment, the‘present inven
tion comprises a process for producing toluene by
subjecting a mixture‘ of benzene and methane to
contact with a catalyst'comprising at least one
substance selected from the group consisting of
the metals having an ‘atomic number of 26 to 29 .
inclusive and the oxides thereof.
vention comprises a process for producing toluene
by subjecting a mixture of benzene and methane
to contact with a catalyst comprising at least one‘
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occurinnature, to Wit, hydrargillite or gibbsite,
and dihydrated minerals are suitable for the man-.
ufacture of the present types of catalysts‘and
these materials have furnished types of activated
alumina which are entirely satisfactory; Precipi
tated trihydrates can also be‘ dehydrated at mod
erately- elevated temperatures-to form satisfac
tory types of alumina; crystallographically and
X-ray -spectroscopically,,"this; most satisfactory
type of alumina is referred to as gamma-alumina,
crystallizing in the cubic system; the length of
edge of the unit cube being about 7.9 "Angstrom
units.
In a more speci?c" embodiment, the present in
'
25 bauxite, and diaspore. Of these three minerals
the corresponding oxides from the trihydrated
It is an object of the present invention to pro
vide a method for producing toluene from ben
zene and methane directly thereby obviating the
necessity of ‘forming expensive intermediate al 30
kylating agents such as'methyl chloride. ‘
‘
In regard to the production of alumina, it may
be stated that three hydrated oxides of aluminum
,,
,
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t,
.
It is best practice in the ?nal steps of prepara
tion of aluminum oxides for use in the'catalyst
composites to ignite them for- some time at tem
peratures within the approximate range of 500°
to 600°, C; jThisdoes not correspond-‘to ‘complete.
substance selected from the group consisting of
dehydration of ‘the hydrated oxides but gives
the metals having an atomic number of 26' to 29
inclusive and the oxides thereof at a temperature 45 catalytic materials of goodstrength and porosity,
so that they are able to resistior along time the
within the range of about 275° C. to about 450° C.
deterioration effects of the service and there
and under‘ superatmospheric pressure within the
range _ of about 10 atmospheres to about 450
atmospheres.
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As previously set forth,’the catalysts useful in
the process of the present invention comprise‘
metals having an atomic number of 26 to 29 and
include nickel, cobalt, iron, copper and the oxides
thereof. JThesecataly'sts can‘beused alone or in
activation periods to which they aresubjected.
Aluminasv having ;the physical characteristics of
“activated alumina” of commerce arewelladapt
editor use as a supportjfor these ‘catalysts. -
'
» Silica suitable-for compositing with activating
oxides to produce catalysts maybev obtained con-1
veniently by‘ precipitating silica gel “from a-solu
admixture-with one another oncomposited with 5.5. tion of a water-soluble‘ silicate bythe addition‘ of "
2,404,498
an aqueous solution of a mineral acid followed
by washing to remove water soluble salts and dry:v
of this invention, consists in passing a mixture
' of benzene and methane over a fixed bed of cata- .
lyst maintained at a ' temperature from about "
ing to produce a granular material comprising essentially silica.
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275 to 450° C. under a pressure of from about
‘
Thoria utilized in the production of- dehydro
10 to about 450 atmospheres. The reaction mix-'
genating catalysts may be obtained by. known_ _ tureundergoing treatment preferably contains
methods from a number ‘of minerals including,
between about 21 and about 20 molecular pro
thorite, orangite, and thorianite.
The catalyst may be prepared employing varié.
portions of methane per one molecular propor
"tion of benzene in order to favor production of '
ous procedures; for example, the prepared re 10. toluene and to diminish the reactions which re
fractory material such as calcined silica,- alumina ' ‘ sultin'the formation of diphenyl and alkylated
or thoria or natural-occurring siliceous material
diphenyl which are valuable products although
such as kieselguhr may be suspended in aqueous, ,
not preferred products of the present process.
solutions of soluble salts of the various metals
> The reaction may also be conducted in a ?uid- Y
and the entire solution evaporated .to dryness. 15 ized or moving-bed, type of operation wherein
the reactants are introduced into a bed of ?nely
The residue may then be dried and calcinedto
divided catalyst at suf?cient velocity such that
decompose the salt deposited thereon to form the ‘
the catalyst particles are motionalized to form
oxide of the metal. This composite may be’fur;
a catalyst bed resembling a liquid in appearance.
'ther treated with a reducing gas such as hydrogen
or carbon monoxide to convert the oxide into the 20 The reaction products are withdrawn from the
catalyst zone, entrained catalyst separatedwthere
metal," said reduction forming a very active cataT v
from’ recycled tothelreaction zone. The’ reac- v
lyst. ' The extent. of reduction can be variedso
that the i?nal catalyst is a composite" of ref-rac
tory carrier, metal and metal oxide.
‘
tion products are then passed through suitable
fractionating systems wherein the desiredprod
Another procedure which may be employed for
manufacturingnthe catalyst consists of ‘suspend
ing the 'hydrogel of the refractory carrier such
rial and the latter recycled to. the ‘reaction-zone.‘
In the compact moving-bed type ofoperation,‘
as silica orralumina hydrogel in an aqueous solu
a compact bed of ?nely divided'catalysts may be
ucts are separated from’ the unconverted .mate
passed through the reactiorrzonev eitheri courier
tion of thevmetal salt followed by drying and cal- V
cining and the reduction as set forth above.
30; current or concurrent with the hydrocarbon re-‘_
Still another. method may comprise impregnats
actants, the reaction productswithdrawn from.
the reaction zone into a'suitable'separation sys
ing the prepared refractory carriers by immersing
tem and the spent catalyst passedinto' a're‘geni
eration’ zone in which it is reactivated andlreé
the carrier for a short time in a solution of a
‘ soluble salt again followed by the calcination and
reduction operations. Although all the catalysts,
. I
cycled to the reaction zone.
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The catalyst after continued use accumulates:
a deposit of carbonaceous materials which’ impair
the catalyst activity. The regeneration‘ofl the‘
catalyst may be accomplished by comb'ustion‘in
mentioned herein ‘possess activityvfor the dis
closed reaction, it, is not intended to infer that
they are‘ the equivalent in their. ability to ac
celerate the interaction of benzene and methane. '
. the presence "of regulated quantities‘ofoxy'gen,
The general method of preparationof a nickel
" or oxyge‘n-c'zontainir'igr gases;
kieselguhr catalyst involves the following steps:
Kieselguhr is suspended. ina relatively dilute
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Another method of regeneration consistslof
subjecting ‘the carbonaceous deposit to‘ contact‘
aqueous solution of nickel sulfate and a saturated
hot solution of sodium carbonate is added grad.
with high pressure hydrogen which hydrogenates,
ually with constant agitation. ‘The proportions.
the deposit to form hydrocarbons which are the'r'e- '‘
of kieselguhr, nickel sulfate and sodium carbonate.‘
beingchosen so that after washing, drying the
precipitate and reduction with hydrogen, the de
sired composition is obtained. The primary pre-v
the‘ catalyst, this hydrogenation treatment‘will.
after easily removed from the catalyst surface. i
In case there is considerable sulfur present on
convert the sulfur tohydrogen sul?de which is
cipitate consists of kieselguhr, nickel carbonate,v 50 subsequently separated‘ along with thel'eii‘luent“
from the regeneration zone. In general, the prod
and nickelous hydroxide. This precipitate is then
ucts
formed during treatment of mixturesofben- ‘
dried and mixed with about 4% of its Weight
zene and methane witha dehydrogenating cata-.
of powdered graphite and pelleted into small
lyst are separated from theunreac'ted' benzene‘.
cylindrical forms in any standard type operating.
machine.
The formed pellets that still contain 55 and methane‘ by suitable means as by distillation. I
and the unreacted portions‘- of the‘_ benzene. and’.
a mixture of carbonate and hydroxide are then
heated in a stream ofair or nitrogen to eliminate
carbon dioxide. After the requisite amount of
carbonaterdecomposion has been effected, reduc
tion of the nickel oxide is conducted at increase 60
ing temperatures in, a stream of hydrogen until
a temperature of approximately 425° C. is reached.
The weight per cent of nickel which maybe in;
vcorporated in the composite catalyst will vary
from about 20 to about 95% and preferably with; 65'
in the range of about 60 to about 90 Weight per
cent.
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As previously stated, methane is ordinarily considered'chemically inert. - However, we havevdis
covered that'in the presence of the-catalyst pre 70
viously described and under selected conditions
of operation, toluene can be produced from a
mixture of benzene and methane. '
The procedure preferably utilized for’ effecting";
methylation of benzene, according to the process’
methane recycled andlcommingled with .addi-.
tional quantities of‘ these ‘hydrocarbons being’
charged to the‘catalyst zone- ‘Hydrogen or hy
drogen-containing gasesproduced in the'process
may alsobe recycled. ‘with the. recovered benzene ~
and methane. The reaction product boiling
higher thanlbenzene‘ is'"separated in'to' desired"
fractions or individual compounds including'tol-f.
uene and diphenyl by distillation at;v ordinary; or
reducedpressure or by other “suitable means.’ ‘The.’
following examples. are given to‘ illustrate! the}
character of results obtained’by’the useof-the?
present process although the data presentedjar'le'
not introduced with theintention .of‘unduly lim-v
itmg the generally broad scope of (they invention-.7
~J EXAMPLE liif
About" 72.8 grams ,of benzene
‘(grams
_ of- methane were charged jalQng" With'j72" gramsf
75‘
of" reduced nickelkieselguhr catalystv into‘ a roe"e
2,404,49Q
2. A process for producing toluene which com
tating autoclave of about 330 cc. capacity. The.
prises subjecting a mixture of benzene and meth
ane to contact with a catalyst comprising a re
fractory carrier and at least one substance se
lected from the group consisting of the metals
having an atomic number of 26 to 29 inclusive
and the oxides thereof at a temperature within
products removed therefrom. The hydrocarbons
the range of about 275° C. to about 450° C. and
were separated from the catalyst and subjected
under superatmospheric pressure within the
to fractional distillation. The hydrocarbon prod
ucts had the following analysis:
10 range of about 10 atmospheres to about 450
atmospheres.
Per cent
3. A process for producing toluene which com
Unreacted benzene ____________________ ..
74.5
prises subjecting a mixture of benzene and a
Alkylate (chie?y toluene) ______________ __ 20.9
autoclave was heated to 400° C. and held at this
temperature for 4 hours. The maximum pres
sure reached in the autoclave was 7500 pounds
per square inch. The autoclave was allowed to
cool to approximately room temperature and the
Naphthenes __________________________ __
0.6
. molar excess of methane to the action of a cata
4.0 15 lyst comprising at least one substance selected ~
from the group consisting of the metals having
an atomic number of 26 to 29 inclusive and the
Total ___________________________ __ 100.0
oxides thereof at a temperature within the range
The following table presents the results ob
of about 275° C. to about 450° C. and under a
Residue, no tar-naphthalene derivative---
tained in Examples 2 to 6 inclusive. These results
pressure within the range of about 10 atmos
were obtained in a continuous operation in which 20 pheres to about 450 atmospheres.
a pelleted nickel-kieselguhr catalyst was disposed
4. A process for producing toluene which com
in ?xed bed relationship to the incoming react
prises subjecting a. mixture of benzene and meth
ants.
ane to the action of a catalyst comprising nickel
Table
and kieselguhr at a temperature within the
25
range of about 275° C. to about 450° C..and under
Example No.
a pressure within the range of about 10 atmos
pheres to about 450 atmospheres.
2
3
‘ 4
5
6
Operating conditions:
emp., °
5. A process for producing toluene which com- 1
30
372
348
370
351
366
Pres. #lsq. ” _____________ __ 8, 000
_____________ _.
6, 000
6, 000
4, 000
1, 000
0.6
0.5
0.5
0.6
41. 0
30. 7
36. 2
31. 7
28. 1
8. 6
1. 5
5. 3
1. 4
5. 6
1. 6
5. 7
1. 5
4. 5
l. 4
Benzene (recov.) ________ _.
48. 0
62.0
55.8
60.0
63. 7
Carbon ................. __
0.9
0.6
0.8
1. 0
2. 3
100. 0
100. 0
100. 0
100. 0
100. 0
Mols 05H; per mol of CH4_
Products wt. per cent of total
0. 4
. _____ _.
__
charge:
Methane__
Toluene..Higher HC__‘_____
We claim as our invention;
1. A process for producing toluene which com
35
prises subjecting a mixture of benzene and meth
ane to the action of a catalyst comprising nickel
at a temperature within the range of about 275° C.
to about 450° C. and under a pressure within the
range of about 10 atmospheres to about 450 at
mospheres.
6. A process for producing toluene which com
prises subjecting a mixture of benzene and meth;
ane to the action of a catalyst comprising iron.
at a temperature within the range of about 275° C.
40 to about 450° C. and under a pressure within the.
range of about 10 atmospheres to about 450 at
mospheres.
prises subjecting a mixture of benzene and methe
7. A process for producing toluene which com
ane to contact with a catalyst comprising at least
prises subjecting a mixture of benzene and meth
one substance selected from the group consisting
45 ane to the action of a catalyst comprising cobalt
of the metals having an atomic number of 26 to
at a temperature within the range of about 275° C.
29 inclusive and the oxides thereof at a tempera
ture within the range of about 275° C. to about
to about 450° C. and under a pressure within the ,
450° C. and under superatmospheric pressure
mospheres.
Within the range of about 10 atmospheres to about
450 atmospheres.
range of about 10 atmospheres to about 450 at
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VLADIMIR N. IPATIEFF. .
GEORGE S. MONROE.
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