1,995,136.
Patented Mar. 19,- 1935
UNITED STATES PATENT OFFlCE
1,095,136 -
PRODUCTION OF HYDBOOARBONS RICH IN
CARBON FROM THOSE POORER 1N CAR
' BON
Fritz Winkler and Paul Feller, Lndwlgshafen-on
the-Rhine, Germany, asignors to I. G. Far-ben
industrie Aktiengesellschaft,
art-on
the-Main, Germany
No
Application July is, 193:, Serial
No. 680,978. In Germany July 26, 1932
4 Claims. (Cl. 260-170)
The present invention relates to improvements ture of from about 400° to about 600° C. suffices.
in the production of hydrocarbons rich in car
bon from those poorer in carbon, in particular to
the production of acetylene from gaseous hydro
_
5 carbons of the methane series.
It has already been proposed to convert gase
When employing pure methane or gases contain- -
ing methane as sole hydrocarbon considerably
‘higher temperatures, namely from 1000° to 1200°
C. or more are necessary for the preheating.
The particular temperature to be selected in each
ous or voporous hydrocarbons in particular those case is dependent on the partial pressure of the
from the methane series, by incomplete com hydrocarbons, such as methane, present in the
bustion with gases comprising free oxygen, such gas and may be easily determined by'a prelimi
10 as pure oxygen or gases containing or supplying nary test. Under the said temperature condi
10
the same into hydrocarbons richer in carbon, by ' tions, considerable amounts of ole?nes are formed
which term we mean hydrocarbons in which the during
the preheating and in the subse
percentage of the carbon in the molecular weight
amounts higher than with the initial hydrocar
bons, as for example into acetylene. The high
temperature necessary for the formation of the
hydrocarbons richer in carbon is produced by
the combustion of a part of the gas. The hy
quent incomplete combustion considerably high
drocarbons or the’ oxygen or both (separately)
tion
er yields of acetylene are obtained than by an
incomplete combustion without preheating or 15
while preheating to lower temperatures. ' More
over, the process according to this invention has
the advantage that inorder to obtain the reac
temperature
only ' a
small
amount 4 of
gas need be burned and, furthermore, it is the
20 may be preheated.
We have now found that considerably greater hydrogen and methane present in the initial
yields of hydrocarbons richer in carbon are ob gases and/or formed during the preheating which
tained from methane or vaporized homologues
of methane by preheating the said methane or
25 homologues thereof and then subjecting the re
sulting gases to incomplete combustion at a tem
20
mainly feed the'combustion. The higher yields
of acetylene are probably due to the facts that
?rstly the materials are already in a preheated
state and thatrtherefore not so much heat is
perature above 1000° C., to such an extent that a needed for bringing the materials to the reac
substantial formation of ole?nes takes place. tion temperature, that secondly hydrogen is
By incomplete combustion we mean a combus present in the gas which is burnt with the evolu
30 tionwith such amounts of free oxygen that hy tion of a great heat and that thirdly the ole?nes 30
drocarbons still remain in the gas. Preferably formed are more readily converted into acetyl-r
‘from 5 to 70 parts of oxygen are employed for ene than are the methane hydrocarbons. The
each 100 parts by volume of hydrogen contained waste heat of the reaction gases may be em
in the free or combined state inthe gases<’to be ployed for the preheating.
The oxygen or the gas containing oxygen is also
subjected to incomplete combustion. The par
ticular amount of oxygen depends on the nature preferably preheated in order to obtain tempera
of the hydrocarbons to be converted and on the tures as high as possible and small combustion
content thereof in the gas. At least 5 per cent zones. The preheating of the gases or vapours
of the methane hydrocarbons should be convert containing hydrocarbons is preferably carried out
40 ed into ole?nes in the preheating step.» The in pipes having walls constructed of materials 40
term “vaporized hydrocarbons” is intended to in which do not give rise to the formation of de
clude not only gaseous or vaporous hydrocarbons posits of carbon at high temperatures, as for ex
but also liquid hydrocarbons in the form of mist. ample carborundum or other silicides orsteels
When starting from coke oven gases or natural coated with chromium or- aluminium, or ceramic
45 gases containing more or less large amounts of materials provided with glazes of- inorganic salts, 45/
homologues of methane, it is necessary to employ and the incomplete combustion is preferably vcar
a temperature of from about 800° to about 900° ried out in pipes or in heat-accumulators (dis
C. during the preheating, when starting from continuously) while producing an inverted ?ame .
crackinggases or mineral oil distillation gases or by surface combustion; it is of advantage to‘
50 containing larger amounts of gaseous methane eifect the preheating or the incomplete com
homologues suchas propane and butane a tem bustion or both operations in the presence of
perature of from about 500°_ to about 800° C. is ' highly refractory materials, as for example in
usually su?icient and when starting from gases chambers which are lined with magnesium oxide
which mainly or exclusively consist-of higher or zirconium bricks. In many cases it is pref
55 - homologues of methane than butane a tempera erable, especially in order to avoid the formation 55
2
1,095,130
of carbon black during the incomplete combus (which term also includes nebulized) cheapv oils
tion, to dilute the methane hydrocarbons to be and oil residues, a much better exploitation of '
converted with inert gases; for this purpose a these materials thus being obtained than by the
part of the reaction gases freed from acetylene processes hitherto known. Furthermore, the
incomplete combustion of the gases formed in
may be employed.
.
g
'
In all cases it is advantageous so to work that the ?rst stage and diluted with hydrogen, may. "
by reason of but slight deposition 5f carbop'black,
the reaction products are cooled rapidly.
The gases richer in carbon, as for example the be carried out more readily industrially and with
acetylene formed, may be recovered'irom the practically the same yields as when working
gas mixtures obtained by the incomplete com with undiluted hydrocarbons.
vThe process may be carried out for example
bustion by washing with organic solvents as for
example with hydrocarbon oils or with liquid by heating the hydrocarbons in the form of gas,
ketones such as cyclohexanone'; the gases-may
also be directly further worked up, as for exam
15 ple into acetaldehyde or benzene.
In the incomplete combustion of gaseous or
liquid hydrocarbons, such as methane and its
vapour or mist at ordinary or increased pressure
either continuously, for example in pipes, or dis
continuously in Cowper apparatus, which are 16
preferably provided with wall material which does
not lead to the deposition of carbon, until con
siderable amounts of liquid hydrocarbons are
taining oxygen for the preparation of hydrocar formed. The reaction products are then cooled,
20 bons richer in carbon, in particular acetylene, the liquid hydrocarbons removed by known
the high temperatures of more than 1000°.C. methods, as for example with washing oil, by
necessary for carrying out the reaction cause compression, with active, carbon or with active
a far-reaching decomposition of the non-oxi silica, and the gas mixture consisting of ole?nes.
dized higher hydrocarbons into hydrogen, me methane and hydrogen subjected to incomplete
25 thane and carbon, 1. e. into less valuable prod combustion with oxygen or gases containing
oxygen. The incomplete combustion is effected,
ucts.'
homologues or olefines, with oxygen or gases con
a
We have further found that in the process preferably with as great a speed of ?ow as pos
hereinbefore described the incomplete combus sible, in pipes or heat-accumulators, with invert
tion is rendered far more economical and more ed ?ame, by surface combustion or, preferably, as
30 advantageous technically by exposing the initial hereinbefore described. In all cases the heat
hydrocarbons as such, before the incomplete com produced by the incomplete combustion may
bustion, to such high temperatures that not only serve for the heating in the ?rst stage of the
ole?nes but also substantial amounts of liquid, process. The gases formed in the ?rst stage may
in particular aromatic hydrocarbons are formed, also be diluted as desired with inert gases.
The following examples will further illustrate
the liquid hydrocarbons being separated and re
covered as such before the further treatment. the nature of this invention but the invention is
Preferably more than 20 com. of liquid hydrocar~ not restricted to these examples.
bons are formed from each cubic metre of initial
Example 1
hydrocarbons, but the advantages gained by this
40
40 manner of working are also remarkable if small
10 litres of oxygen per hour are passed ‘through
er amounts of liquid hydrocarbons are formed.
This modi?cation of the process according to one arm of a forked quartz pipe having an inter
the present invention is also applicable with great nal diameter of 2 millimetres while through the
advantage to gaseous or vaporized olefinic hy other arm are passed 20 litres per hour of a mix
45 drocarbons, such as ethylene, propylene and ture of homologues of methanehaving the fol
butylenes or gases containing the same, such as
cracking gases, oil gas, coke oven ‘gases, and
45
lowing composition:
“
gases obtained by the low temperature carboni
CH4--- __
zation of brown coal. The particular tempera ("one
50 tures employed for bringing about the said for
mation of liquid hydrocarbons depend on the na C3Hs_....-_
ture of the initial hydrocarbons and also on the CsHm
pressure used. At ordinary pressure methane, for can‘
P1“:
Per cent
_
\
8.0
14.2
51.9
_ 11.9
4,5
4.8
example, is converted into liquid hydrocarbons
55 at temperatures between about 900° and l00O° CLHR
0.9 55
3.8
0., ethane, propane°, and butane are converted N9 i
at between about 550° and 900° C., ethylene, Both gases are preheated to about I700° C., the
propylene and butylenes also at between about methane homologues thus being converted for
550° and 900° C. Under pressures between 5 and the greater part (about 36 per cent) into ole?nes.
60 300 atmospheres ethylene, propylene and buty When the hot oxygen strikes the hot gas con
lene are converted, depending on the height of taining ole?nes, a short extremely hot ?ame is
the pressure, at temperatures between 250° and formed. The reaction gases escape at a great
600° C. Dilute gases are converted at higher speed through the attached quartz pipe having an
temperatures than concentrated gases. At high internal diameter of 2 millimetres. With an in
65 er rates of flow higher temperatures are required. crease in volume of about 30 per cent, a gas is 65
The process according to this invention o?ers obtained having the following composition:
various advantages.
Per cent
Not only acetylene, but considerable amounts
2.0
of valuable liquid, in particular aromatic, hydro COz___....
70
70 carbons are obtained from cheap initial mate
Conn__________________________________
__
.._
9.8
rials, such as methane, its homologues, ole?nes C2H4
and gases containing the same, such as natural CO _______ __
gases, cracking gases, distillation gases, waste Hz...
gases from the destructive hydrogenation of CH4--coals, tars and oils, coke oven gases, vaporized
N2
_______ --
10.0
_-_..
-
30.5
33.5
3.2 76
1,995,136
3
The acetylene formed may be recovered by
Example 2
known methods, as for example by washing with
A gas containing mainly homologues of methane organic liquids, or the gas may be further worked
and having the composition:—
up into acetaldehyde or benzene. The heating
Per cent for the ?rst stage of the process may be effected ‘
8.0 by the waste heat from the second stage.
CH4
C2He____ _____________________ __' _________ _ 14.2 ' ~ 'What we claim is:--—
1. A process for the conversion of a hydrocar
bon into a hydrocarbon richer in carbon which
10 C2H4 __________________________________ _._ 4.5 comprises heating a gas essentially comprising a 10
CsHe ________________________ ____ ________ __
4.8
vaporized hydrocarbon of the methane series to
C4112..__
’
0.9
such a temperature that at least 5 per cent of
Na
_
3.8 said vaporized hydrocarbon is converted into
is passed at a speed of ?ow of 20 litres per hour ole?nes, and then subjecting the resulting gas
15 and at a temperature of 850°_ C. through a pipe containing ole?nes to incomplete combustion at a 15
of V2A-stee1 having an internal diameter of 15 temperature above 1000° C., hydrocarbons richer
millimetres which has been coated with molyb in carbon thereby being obtained.
2. A process for the conversion of a hydro
denum by decomposition of a volatile compound
of said metal, as described for example in appli carbon into acetylene which comprises heating a
20 cation Ser. No. 656,630, ?led 13th February 1933. gas essentially comprising a gaseous hydrocarbon 20
Cs'Hs _____________________________ ______..g 51.9
C4H10
___
'
_
11.9
' _While the volume increases by about 50 per of the methane series to such a. temperature
cent, a gas mixture having the following compo that at least 5 per cent of said gaseous hydro
sition is obtained:---
25
' '
-
>
carbon isrconverted into ole?nes, and then sub
jecting the resulting gas containing ole?nes to in
complete combustion at a temperature above
1 0 1000° 0., acetylene thereby being obtained.
Per cent
CaHs and C4HsCol-I4
___34.4
Ha
_._.__.
_.__.....
23-6
CnH2n+2 (n-being on the average equal to
3. A process for the conversion of a hydrocarbon
into a hydrocarbon richer in carbon which com
prises heating a gas essentially‘ comprising a
gaseous hydrocarbon of the methane series to 30
N2
'
2.0
such a temperature that at least 5 per cent of
which contains liquid, in particular aromatic, said gaseous hydrocarbon is converted into ole
?nes, and that in addition normally liquid hy~
hydrocarbons in the form of vapour or mist.
By cooling and electrical deposition in a, high drocarbons are formed, removing these liquid
tension ?eld, 180 grams of liquid condensate con hydrocarbons, and then subjecting the resulting
sisting mainly of benzene are obtained per cubic gas containing ole?nes to incomplete combustion
metre of the original gas. The gas freed from at a temperature above 1000° C., hydrocarbons I
liquid hydrocarbons is preheated to 700° C. and in richer in carbon thereby being obtained.
4. A process for the conversion'of a hydrocar
completely burned with oxygen also pre-heated to
800° C., 1 part by volume of oxygen being employed bon into acetylene which comprises heating a gas 40
for each 2 parts by volume of gas. A gas having essentially comprising a vaporized hydrocarbon
of the methane series to such a temperature that , r
the following composition is obtained:—
at least 5 per cent of said vaporized hydrocarbon
’
Per cent is converted into ole?nes and that in addition
aromatic hydrocarbons are formed, removing
45
30
1.15) ____~_ ___________________________ __ 39.0
CO2
(‘one
C2H4
C0
H:
50 (‘r-‘n
N2-
_____
_ _ _ _ __
____
2.4
____
_____
10,2
these aromatic hydrocarbons, and then ‘subject
15.4 ing the resulting gas containing ole?nes to incomg
12.4 plete combustion at a temperature above 1000° C.,
28.2 acetylene thereby being obtained. '
FRITZ WINKLER.
mm. FEILER.
2.5
28.9
50