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Патент USA US2411236

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Patented Nov. 19, 1946 '
Carlisle M. Thacher, Highland Park, 111., assignm
to The Pure Oil Company, Chicago, 111., a cor
poration of Ohio
No Drawing. Application March 30, 1940,
Serial No. 326,963
7 Claims. (01. 23-206)
This invention relates to a method of convert
sures in?uence the reactions in the desired di
ing hydrocarbons, particularly lowlboiling par
rection. Typical reactions which may take place
a?inic hydrocarbons, .to organic sulfur com
- between a normally gaseous paraflinic hydrocar
pounds, especially carbon-sulfur compounds.
bon such as methane and sulfur are as follows:
This application is a continuation in ,part of
co-pending application Serial No. 177,411, filed
December 1, 1937.
" _
An object of this invention is to convert hydro
carbons into organic sulfur compounds.
Another object of this invention is to convert 10
low boiling para?inic hydrocarbons into carbon
sulfur compounds.
The amount of sulfur charged‘ with the hydro- ’
carbon may be varied between rather wide lim
its depending upon a number of factors among
which are time of residence of the reactants in
A further object of this invention is to cat
alytically convert hydrocarbons into carbon-sul
fur compounds at such temperatures as to afford 15 the reaction zone, particular products desired and .
a minimum of corrosion to the apparatus in : reaction temperature and pressure. Where in
which the process is conducted.
termediate sulfur oxidation products are desired '
the sulfur should not be in excess of that nec
Other objects of the invention will become
essary to react with the'hydrocarbons to form
apparent from the following description.
It has been discovered that hydrocarbons can 20 mercaptans. In general the amount of sulfur
charged with the gas is preferably not in excess
be reacted with sulfur, selenium and sulfur or
selenium yielding compounds at elevated tem‘
of that necessary to stoichiometrically react with
peratures in the‘presence of a suitable catalyst I
the hydrocarbon to form the desired organic sul- -
fur compound. By controlling the proportion of
bon-sulfur compounds and including alkyl sulfur 25 sulfur within this range, maximum yields of de
compounds. As examples of such- compounds
sirable reaction products may be obtained. The
to form organic sulfur compounds such as car
may be mentioned carbon disui?de and methyl,
reactor as well as the remainder of the appara
ethyl, propyl and butyl mercaptans.
In carrying out the invention, substantially
tus may be fabricated from ordinary iron, al
though stainless steel, chromium steel, molyb
30 denum steel, silica, quartz or other materials
which are resistant to sulfur corrosion or non
’ pure hydrocarbons such as methane, ethane, pro
pane or butane or mixtures thereof or other hy
resistant steel lined with a refractory lining
drocarbons may be used as starting materials.
such as silica or quartz are preferred.
For example, when the starting material is a
As shown by the foregoing equations, sulfur
hydrocarbon gas such as'methane, the methane
is heated and mixed with sulfur vapors and the 35 may react with hydrocarbon gas to form mer
captans, thio-ethers and organic disul?des such
mixture fed into a reactor where the mixed gas
and sulfur vapor is contacted with appropriate
as dimethyl disul?de and carbon disul?de. The
catalyst. As catalysts suitable for effecting the
reaction products are cooled and the organic
conversion of hydrocarbons to organic sulfur
sulfur compounds separated therefrom by frac
compounds may-be mentioned oxides or sul?des 40 tionation, absorption in a suitable solvent such
‘as naphtha and subsequently separated therefrom
of vanadium, manganese, copper, iron, cobalt,
nickel, chromium and molybdenum. The sul
by fractionation or by other suitable means. The
. particular method of separation of reaction prod
?des of these metals are generally preferred.
These compounds may be used alone or supported
ucts from unreacted materials will depend large
on materials such as silica gel,~ alumina gel, 45 ly upon the composition of the reaction products.
Any hydrogen sul?de present may be separated
pumice or charcoal, etc., which of themselves may
possess catalytic activity. The reactants are pref
from organic sulfur compounds by conventional
erably contacted at temperatures of approximate- ,
methods such as by scrubbing with water or
ly 400-700° C. and under pressures of approxi
aqueous alkali under appropriate conditions of
mately 1 to 125 atmospheres. While good yields 50 temperature and concentration and prior to sep
, may be obtained under a relatively large number
aration of the organic sulfur compounds from
of satisfactory operating conditions of temper
ature and pressure within the desired range,
those conditions are preferred which maintain
the reactants in the vapor phase. Elevated pres
the remaining gases. Unreacted gases may be re
" cycled for further reaction. Selenium may be
substituted for sulfur when the reaction tempera
55 ture is sufficiently high to vaporize selenium. As
sources of sulfur, compounds thereof which read
ily yield free sulfur. may be used. The appara
tus in which the process is carried out may be
of any conventional type consisting of a heat
ing means and reaction, chamber with cooling
was obtained. In all 0! the foregoing examples
pressures slightly above atmospheric were em
It is not intended that the invention shall be
limited by the foregoing speci?c examples which
‘and fractionating and/or other separating means
are presented for purpose of illustration, but
that the invention shall be limited only by the
connected to the reaction chamber.
In a specific example methane was mixed with
scope of the claims.
What is claimed is:
sulfur in a ratio of 0.58 mol of methane to one
incl oi’ sulfur vapor. calculated as diatomic sul 10
1. The method of preparing carbon-sulfur
compounds which comprises contacting paraf
fur, and the mixture contacted with iron sulfide
at a space velocity of 775 and at a temperature
flnic hydrocarbon gases with sufficient sulfur
, of 594° to 600° C. Space velocity may be de
vapors to stoichiometrically‘ react with the gases
?ned as the ratio of the total volume of vapor
to form mercaptans at a temperature of at least
charged per hour to the total volume of-cata 15 400° 0., at which the sulfur and hydrocarbon
lyst space. A liquid condensate was obtained,
gases chemically react, in the presence of a
the major portion of which was carbon disul?de
catalyst selected from the group of preformed
and which contained minor portions of inter
metal sulfides.
mediate suliur oxidation products. In another
2. Method in accordance with claim 1 in
run using the same catalyst, 0.55 mols of 20 which the ‘temperature is between approximately
methane was mixed with one moi of sulfur vapor,
400° and 700° C.
calculated as diatomic sulfur, and the mixture
3. Method in accordance with claim 1 in
contacted with the catalyst at a space velocity
which the catalyst is supported on a carrier
of ‘794 and a temperature of 594° C. to 598° C.
selected from the group of silica gel, alumina
A liquid condensate was obtained, the major por
gel, pumice and charcoal.
tion of which was carbon disul?de and which
4. Method in accordance with claim 1
contained- minor portions of intermediate sul
which the catalyst is iron sul?de.
fur oxidation products. In another run at a
5. Method in accordance with claim 1
temperature of 594° C. to 599° C. and using a
which the catalyst is cobalt sul?de.
proportion of 5.54 mols of methane to one mol 30
6. Method in accordance with claim 1
of sulfur vapor, calculated as diatomic sulfur,
which the catalyst is nickel sul?de.
the mixture was contacted at a space velocity of
‘7. Method in accordance with claim
806 with a catalyst consisting of manganese sul
which the catalyst is a sul?de selected from the
?de deposited on Activated alumina in a ratio of
group consisting of vanadium, manganese, cop
1 to 20. A liquid product consisting principally 35 per, iron, cobalt, nickel, chromium and molyb
of carbon disul?de and containing minor por
denum sul?des.
tions of intermediate sulfur oxidation products,
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