Mamh 1, 1932-
A‘ MITTASCH ET AL
1.847.095
PREVENTION OF THE FORMATION OF CARBON IN OPERATIQNS CARRIED
OUT WITH HYDRQCARBONS AT AN ELEVATED TEMPERATURE
Original Filed March 11. 1927
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INVENTORS
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Rudolf
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BYZLeir ATToRNEYsummd faunaler
Patented Mar. 1, 1932
1,847,095
UNITED STATES PATENT OFFICE
ALWIN MITTASOH, OB‘ MANNHEIM, RUDOLF WIETZEL, OF LUDWIGSHAFEN-ON-THE
BHINE, AND CONRAD PFAUNDLER, OF OPPAU, GERMANY, ASSIGNORS TO I. G.
FARBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANKFORT-ON-THE-MAIN, GER
MANY, A CORPORATION 01' GERMANY
PREVENTION OF THE FORMATION OI‘ CARBON IN OPERATIONS CARRIED OUT WITH
HYDROCARBONS AT AN ELEVATED TEMPERATURE
Original application ?led March 11, 1927, Serial No. 174,694, and in Germany March 13, 1926. Divided and
this application ?led August 2, 1928. Serial No. 287,096.
This is a divisional application relating to ploying, for example, materials, such as iron,
subject-matter which has been divided out copper and the like alloyed with boron or the
from our copending application Serial No. like. For the construction of the apparatus
174,694, ?led March 11, 1927.
_ it is generally su?icient, however, to coat the
This invention relates to improvements in materials with a thin layer of substances to 55
the prevention of the undesirable formation be added by wetting them with solutions of
of carbon and soot in operations conducted boric acid or treating them with gases and the
with gaseous or liquid hydrocarbons or mix
tures containing the same at an elevated tem
10
like containing boron or arsenic or the like.
The addition of the said metalloids may also
perature. As examples of such operations be effected by adding to the hydrocarbons to
conducted with hydrocarbons at an elevated be treated small quantities of the hydrogen
temperature may be mentioned a conversion compounds thereof.
15
of high boiling hydrocarbons into others of
low boiling point, the transformation of gase
ous hydrocarbons into liquid hydrocarbons,
the distillation of hydrocarbons, the dehydro
00
In some cases it may
also be of advantage to mix any non-metallic
substances present in the apparatus, especial
ly insulating masses of ma nesium oxid or 65
the like, and catalysts, with boric acid and
genation of aromatic compounds, the treat the like, or to use for the construction of such
ment of coaly materials by extraction with parts substances containing metalloids as for
solvents with or without the aid of pressure,
20
the hydrogenation of unsaturated com
example boron nitride, diamotaceous earth,
mica and the like. The advantages of this
pounds, for example of ethylene to ethane, method of working are particularly apparent
70
and operations ‘in which hydrocarbons or in operating with liquid hydrocarbons under
mixtures containing the same are formed for pressure. The said method ma also be ap
25
30
35
example by splitting oil water from, ‘or plied,"for example, in the distil ation of hy
hydrogenating organic compounds which drocarbon mixtures, followed by catalytic
contain oxygen, such as lphenols, extraction treatment of the vapors in the presence or
products of coaly materia s and the like. All absence of reactive gases.
such operations are hereinafter referred to
Substances (free iron in particular) lead—
for the sake of brevity as operations carried ing to deposition of soot should be absolutely
out with hydrocarbons at an elevated tem excluded from the hot parts of the of the ap
perature.
paratus. It should however be noted that
We have now found that the formation of iron in the form of alloys such as steels con
coke and soot in these said operations may be taining chromium, manganese, or tungsten,
very considerably diminished or entirely pre and the like does not exhibit any injurious
vented by adding or supplying metalloids to action.
the metallic (and non-metallic, if any ma
According to the present invention, the
terials which come into contact wit
40
45
75
80
85
the substances coming into consideration as ma
liquid or gaseous hydrocarbons at high tem terials for the inner Walls of the reaction
peratures, mere traces of such additions being vessels, for feed and e?iuent pipes, heat ex
often sui‘?cient. Boron, or its compounds, changing devices (if any), and the like, are
are particularly suitable for this purpose, more particularly the noble metals, quartz,
arsenic, antimony, bismuth, phosphorus, ferro-silicon, mica, glazed or fused porcelain,
90
selenium or the compounds thereof and aluminium, molybdenum, tantalum, chromi
silicon being also ap licable. All these ma um, and alloys of chromium free from iron,
terials are capable o furnishing volatile hy manganese, molybdenum, cobalt and the like, 95
drogen compounds. Thus the hydrides of with or without a coating of lustrous carbon
boron, arsenic, antimony, bismuth, phos
and also other materials coated with lustrous
phorus, selenium and silicon are of high carbon, such as coal, or the like. The use of
utiligy in this process. Such additions may catalysts for example in the transformation
50 be e ected in a variety of ways, where em
of gaseous hydrocarbons into liquid hydro
100
i 2
1,847,096
carbons, is not essential, but if they are used, added to the initial gas mixture the tube is
it has been found that all such substances soon clogged by deposition of carbon.
are suitable as do not lead to the production
What we claim is :—
of any appreciable deposition of coke or soot
1. A process for the prevention of an un
(if at all) namely the materials mentioned desirable formation ofcarbon and soot in
above, or silica, pumice, barium carbonate, operations carried out with hydrocarbons at
charcoal impregnated with barium salts, an elevated temperature, which comprises
70
boron, tungsten and the like either alone or supplyin
on suitable carriers or the like, or in con
junction with other compounds.
other than as a catalyst or a
source 0 hydrogen a hydride of a metalloid
selected from the group consistin 1' of boron, 75
In working with carbon monoxid or mix— arsenic, antimony, bismuth, p iosphorus,
tures containing the same, and also in the selenium and silicon to the metallic materials
conversion of hydrocarbons of high boiling which come into contact with the hydrocar
point into others of lower boiling oint, the bons so long as they have a high temperature
15
said method of operating with ad itions of to thereby prevent said undesirable forma
metalloids or metalloid compounds is also tion of carbon and soot.
a matter of considerable practical impor
2. A process for the prevention of an un
tance.
The manner of carrying the process ac
cordin to the resent invention into prac
tice wi be furt er illustrated with reference
80
desirable formation of carbon and soot on
the metallic surfaces and non-metallic sur
faces of the apparatus in operations carried
out with hydrocarbons at elevated tempera
85
to the accompanying drawing, but it should tures, which comprises admixing other than
be understood that the invention is not lim
ited to the modi?cation shown in the draw
in
as a catalyst or a source of hydrogen a small
amount of a hydride of a metalloid selected
from the group consisting of boron, arsenic,
.
90
i hydrocarbon gas to be polymerized is antimony, bismuth, phosphorus, selenium
30
introduced by way of a pipe A into the pres and silicon with said hydrocarbons to thereby
sure vessel C at B. About 0.01 per cent by prevent said undesirable formation of carbon
weight of a hydride of one of the said metal and soot.
loids is admixed with the said hydrocarbon
3. In the conversion of gaseous hydrocar
gas at A. D represents the catalyst. F is bons into liquid hydrocarbons, preventing a
a heat revenerator through which the liquid formation of carbon and soot on the surfaces
hydrocarbons formed and in which they give of the apparatus with which said hydrocar
elf their heat to the hydrocarbon ases en bons come into contact by admixing other
tering at B. The catalyst is heated y means than as a catalyst or a source of hydrogen I00
of the device E. The reaction products are a small amount of a hydride of a metalloid
passed from G into the separating vessel H. selected from the group consisting of arsenic,
Li uid h drocarbon products are drawn off bismuth, phosphorus, selenium and silicon
at
40
The gases pass off at O and through with said hydrocarbons to thereby prevent
the valve K into the separating vessel L from said undesirable formation of carbon and soot. 105
which a further amount of liquid hydrocar
4. In the distillation of hydrocarbons, pre
bons is drawn off at N. The gases pass off venting a formation of carbon and soot on
at P and may either be withdrawn from the the surfaces of the apparatus with which said
45
50
system at Q or may be recycled by way of hydrocarbons come into contact by admix
t e circulating pump R.
ing other than as a catalyst or a source of 110
The following example will further illus hydrogen a small amount of a hydride of a
trate how the said invention may be carried metalloid selected from the cup consisting
into practical effect but the invention is not of arsenic, bismuth, phosp orus, selenium
limited thereto.
and silicon with said hydrocarbons to thereby
Example: A mixture of 80 percent of prevent said undesirable formation of carbon
ethylene, 17 percent of hydrogen and 3 per and soot.
116
cent of carbon dioxide to which from 0.01
5. In the dehydrogenation of h drocar
to 0.05 ercent of hydrides of silicon have bons, preventin a formation of car on and
55
been added, is passed, while under a res
soot on the sur aces of the apparatus with
which said hydrocarbons come into contact 120
nickel tube lined with tin which contains by admixing other than as a catalyst or a
sure of 40 atmospheres, through a chromium
pieces, of the size of peas, of silica gel coated source of hydrogen a small amount of a hy
80
with lustrous carbon by a treatment with dride of a metalloid selected from the cup
vapors of benzene at 850° 0., and which is consisting of arsenic, bismuth, phosp orus
heated to a temperature between 550° and selenium and silicon with said hydrocarbons 125
650° C. By condensing the vapors issuing to thereby present said undesirable formation
from the tube a mixture of low-boiling un
saturated and aromatic hydrocarbons is ob
of carbon and soot.
6. In the conversion of gaseous hydrocar
tained which ma satisfactorily be employed
bons into liguid hydrocarbons, presenting a
as motor fuel.
f no hydrides of silicon are formation 0 carbon and soot on the surfaces 130
Lemons
of the apparatus with which the hydrocar
bons come into contact by admixing other
than as a catalyst or a source of hydrogen
a small amount of a hydride of a metalloid
5 selected from the group consisting of boron
and antimony with said hydrocarbons to
thereby prevent said undesirable formation
of carbon and soot.
7. In the distillation of hydrocarbons, pre
10 venting a formation of ‘carbon and soot on
the surfaces of the apparatus with which said
hydrocarbons come into contact by admixing
other than as a catalyst or a source of hydro
en a small amount of a hydride of a metal
15 oid selected from the
oup consistin
of
boron and antimony wi said hydrocar?ons
to thereby prevent said undesirable forma
tion of carbon and soot.
8. In the dehydrogenation of hydrocar
20 bons, pre'ventin a formation of carbon and
soot on the su aces of the apparatus with
which said hydrocarbons come into contact
by admixing other than as a catalyst or a
source of hydrogen a small amount of a h -
25 dride of a metalloid selected from
e
group consisting of boron and antimony with
said hydrocarbons to thereby prevent said
undesirable formation of carbon and soot.
In testimony whereof, we a?ix our signa
l? tures.
.
ALWIN MITTASCH.
BUDOLF WIETZEL.
CONRAD PFAUNDLEB.
names
3
of the apparatus with which the hydrocar
bons come into contact by admixing other
than as a catalyst or a source of hydrtlilgen
a small amount of a hydride of a meta 01d
6 selected from the group consisting of boron
and antimony with said hydrocarbons to
thereby prevent said undesirable formation
of carbon and soot.
7. In the distillation of hydrocarbons, pre
10 venting a formation of carbon and soot on
the surfaces of the apparatus with which said
hydrocarbons come into contact by admixing
other than as a catalyst or a source of hydro~
fen a small amount of a hydride of a metal
15
oid selected from the
boron and antimony wi
on
consistin?oof
sa' hydrocar ns
to thereby prevent said undesirable forma
tion of carbon and soot.
8. In the dehydrogenation of hydrocar
20 bone, pre'ventin a formation of carbon and
soot on the su aces of the apparatus with
which said hydrocarbons come into contact
by admixing other than as a catalyst or a
source of hydrogen a small amount of a lig
25 dride of a metalloid selected from
a
group consisting of boron and antimony with
said hydrocarbons to thereby prevent said
undesirable formation of carbon and soot.
In testimony whereof, we a?ix our signa
'0 tures.
_
ALWIN MITTASCH.
RUDOLF WIETZEL.
CONRAD PFAUNDLEB.
u
.
CERTIFICATE or CORRECTION.
Patent No. 1,847,095..
March 1, 1932.
nuns nmnscn ET AL.
It is hereby certified that em: appears in the printed specification of the
above numbered patent vrequiring correction as follows: Page 2, line iesmmm
5, for "present" read "prevent"; and line 129, claim 6, for "presenting read
"preventing"; and that the said Letters Patent should he read with these cor
rections therein that the same all!) custom to the record ofuthe case in the
Patent
Otiiee.
_
y
_
’
Signed and sealed this 13th day of December, A. D. 1932.
M. J. Moore.
(Sell) -
-
Acting Commissioner of Patents.
CERTIFICATE OF CORRECTION.
Patent No. 1,847,095.
March I, I932.
ALVIN MITTASCH ET AL.
It is hereby certified that error appears in the printed specification of the
above numbered patent requiring correction as follows: Page 2, line 126, claim
5, for "present" read "prevent"; and line 129, claim 6, for "presenting" read
"preventing"; and that the said Letters Patent should be read with‘ these cor
rections therein that the same may conform to the record of‘ the case in the
Patent 0!! ice.
_
Signed and aealed this 13th day of December, A. D. 1932.
(Seal)
M. J. Moore.
Acting Conmiaeioner of Patents.