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Патент USA US2837583

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2,37,573
Patented June 3, 1958
2
in which R may comprise either an alkyl, aryl, alkaryl,
aralkyl or cycloalkyl radical.
Examples of sulfur-containing compounds which may
be used in this invention include alkyl mercaptans such
as methyl mercaptan, ethyl mercaptan, propyl mercaptan,
2,837,573
ETI-IERS AND ALCGH‘OFLS' VlA SULFUR DEUXIDE
OXIDATION OF SULFIDES AND MERCAPTANS
Julian M. Mavity, Hinsdale, 111., assignor to Universal
Oil Products Company, Des Plaines, lll., a corporation
isopropyl mercaptan, butyl mercaptan, isobutyl mercap
No Drawing. Application January 14, 1955
tan, t-butyl mercaptan, pentyl mercaptan, etc.; aryl mer
cap'tans such as phenyl mercaptan, etc.; alkaryl mercap
of Delaware
tans such as methylphenyl mercaptan, p-ethylphenyl mer
Serial No. 481,973
captan, p-propylphenyl mercaptan, o-methylphenyl mer
7 Claims. (Cl. 260-614)
captan, o-ethylphenyl mercaptan, tolyl mercaptan, etc.;
aralkyl mercaptans such as benzyl mercaptan, p-methyl
This invention relates to a process for preparing oxy
benzyl mercaptan, ethylbenzyl mercaptan, propylbenzyl
gen-containing organic compounds, and more particularly
mercaptan, etc.; cycloalkyl mercaptans such as cyclo
to a process for preparing oxygenated hydrocarbon deriva
pentyl mercaptan,v cyclohexyl mercaptan, cycloheptyl
tives from sulfur-containing organic compounds.
mercaptan, etc.; alkyl sul?des such as dimethyl sul?de,
An object of this invention is to prepare oxygenated
diethyl sul?de, dipropyl sul?de, diisopropyl sul?de, methyl
ethyl sul?de, methyl propyl sul?de, methyl butyl sul?de,
ethyl propyl sul?de, ethyl butyl sul?de, etc.; aryl sul?des
organic compounds.
A further object of this invention is to prepare oxygen
containing compounds such as alcohols and ethers by
such as diphenyl sul?de, dinaphthyl sul?de, etc.; alkaryl
sul?des such as ditolyl sul?de, di(p-methylphenyl)sul?de,
reacting the corresponding sulfur-containing compounds
with sulfur dioxide.
One embodiment of the present invention resides in a
process for preparing an oxygen-containing organic com
di(o-methylphenyl~) sul?de, di(m-methylphenyl) sul?de, di
(o-ethylphenylsul?de, di(p—ethylphenyl)sul?de, di(o-pro
pound by treating an organic compound such as a mer- ‘
captan, sul?de or disul?de with sulfur dioxide, and re
covering the resultant oxygen-containing organic com
pound.
A further embodiment resides‘ in a process for pre
paring an oxygen-containing organic compound by treat
ing a mercaptan, organic sul?de or disul?de with sulfur
dioxide at a temperature in the range of from about 100°
to about 350° C. and at a super-atmospheric pressure in
the range of from about 2 to 500 atmospheres or higher,
pylphenyl)sul?de, etc.; aralkyl sul?des such as dibenzyl
sul?de, di(ethylbenzyl)sul?de, etc.; cycloalkyl sul?des
such as dicyclopentyl sul?de, dicyclohexyl sul?de, dicyclo
heptyl sul?de, etc.; alkyl disul?des such as dimethyl di
sul?de, diethyl disul?de, dipropyl disul?de, diisopropyl
disul?de, methyl ethyl‘ disul?de, methyl propyl disul?de,
methyl butyl disul?de, ethyl propyl disul?de, ethyl butyl
disul?de, etc. ; aryl disul?des such as diphenyl disul?de, di
naphthyl disul?de, etc.; alkaryl disul?des such as ditolyl
disul?de, di(p-methylphenyldisul?de,.di(o-methylphenyl) —
and recovering the resultant oxygen-containing organic 35 disul?de, di(m-methylphenyldisul?de, di(o-ethylphenyl)
compound.
A speci?c embodiment of the invention resides in a
process for preparing ethyl alcohol by treating ethyl mer
disul?de, di(p-ethylphenyl)disul?de, di,(o-propylphenyl)
disul?de, etc.; aralkyl disul?des such as dibenzyl disul?de,
di(ethylbenzyl)disul?de, etc.; cycloalkyl disul?des such as
dicyclopentyl disul?de, dicyclohexyl disul?de, dicyclohep
captan with sulfur dioxide at a temperature in the range
of from about 100° to 350° C. and at a super-atmospheric 4A) tyl disul?de, etc.
The reaction conditions under which thevprocess of
pressure in the range of from about 2 to 500 atmospheres,
this invention proceeds will depend upon the particular
and recovering- the resultant ethyl alcohol.
sulfur-containing organic compound undergoing oxygena
Other embodiments and objects relating to alternative
tion. However, elevated temperatures in the range of
sulfur-containing. organic compounds will be found in the
45 from about 100° to about 350° C. are needed. It is also
following further detailed description of the invention.
desirable that super-atmospheric pressures in the range of
Oxygen-containing organic compounds such as alcohols
from about ZatmoSpheres to about 500 atmospheres be
and ethcrs, the uses of which are well known (e. g., ethyl
used. Generally speaking, temperatures above 350° C.
ether being used as an anesthetic), may be prepared from
are to be avoided. due to the fact that reactions involving
the corresponding sulfur-containing organic compounds
such as mercaptans, sul?des or disul?des by treating the 50 the participation of free sulfur along'with' the ‘formation
of ole?ns and/or other unwanted side products results
latter compounds with sulfur dioxide at an elevated tem
from the use of excessive temperatures.
perature and pressure. It is also contemplated within
It is also contemplated within the scope of this inven
the scope of this invention that the process may be used
tion that appropriate catalysts may be used to speed up
as a step in the conversion of ole?nic compounds to oxy
genated compounds inasmuch as ole?ns readily add hy
drogen sul?de to form mercaptans and/ or sul?des when
reacted in the presence of a proper catalyst such as solid
phosphoric acid, etc. The mercaptan and/ or sul?de may
then be treated with sulfur dioxide to form the corre
sponding oxygenated compounds. In addition, the reac
tion of the present invention may also be utilized in con
junction with supplementary procedures for treating hy
drocarbon mixtures which are contaminated by sulfur
the oxygenation of the sulfur-containing organic com
pounds, said catalysts including, but not limited to, con
tact catalysts such as metal oxides (e. g. aluminum oxide,
silica oxide, etc.) metal sul?des, noble metal catalysts
composited on an appropriate support, etc.
60
The process of this invention may be e?ected in any
suitable manner and may comprise either a batch or con
tinuous type operation. When a batch type operation is
used, a quantity of the starting material comprising either
an organic mercaptan, sul?de, or disul?de is placed in a
compounds to remove the sulfur, thereby “sweetening”
65 suitable reaction vessel along with sulfur dioxide and
said hydrocarbon mixtures.
The reaction of the present invention will proceed ac
cording to the equations hereinafter set forth:
heated to the desired reaction temperature. After a pre—
determined length of time, the reaction vessel and the con
tents thereof are allowed to cool to room temperature,
the unreacted sulfur dioxide bled off and the ether or al
70 cohol separated from the unreacted mercaptan, sul?de or
disul?de by conventional means, for example, fractional
distillation, etc.
‘2,887,673 ,.
.
4
3.
recovering the resultant oxygen-containing organic com
Another method of operation of the present process is
of the continuous type. In this type, the mercaptan, sul
?de or disul?de along with sulfur dioxide is continuously
pound.
v2. A process for the preparation of an oxygen-contain
ing organic compound selected from the group consisting
charged to a reaction vessel maintained at the desired
of alcohols and ethers which comprises treating an or
operating conditions of temperature and pressure. The
ganic compound selected from the, group consisting of
reaction zone may be an unpacked vessel or coil, or it
may contain an adsorbent packing material such as ?re
mercaptans, sul?des and disul?des with sulfur dioxide at
a temperature in the range of from about 100° to 350° C.,
brick, alumina, dehydrated bauxite, and the like. The
and at a super-atmospheric pressure in the range of from
reaction product comprising either an alcohol or other
is continuously withdrawn, separated from the reactor 10 about 2 to about 500 atmospheres, and recovering the re
sultant oxygen-containing organic compound.
effluent and puri?ed by conventional means hereinbefore
3. A process for the preparation of ethyl alcohol which
set forth, while the unreacted starting material is recycled
for use as a portion of the starting material.
If so desired, the catalysts hereinbefore enumerated
may be used in either the batch type or continuous type
' comprises treating ethyl mercaptan with sulfur dioxide
at a temperature in the range of from about 100° to 350°
C., and at a super-atmospheric pressure in the range of
from about 2 to about 500 atmospheres, and recovering
'
the resultant ethyl alcohol.
7
The following examples are given to illustrate the proc
4. A process for the preparation of diethyl ethyl ether
ess of this invention which, however, are not intended
which comprises treating diethyl sul?de with sulfur diox
to limit the generally broad scope of the present inven
20 ide at a temperature in the range of from about 100° to
tion in strict accordance therewith.
350° C. and at a super-atmospheric pressure in the range
Example I
of from about 2 to about 500 atmospheres, and recovering
the resultant diethyl ether.
150 g. of ethyl mercaptan is placed in a reaction vessel
5. A process for the preparation of diethyl ether which
provided with heating and stirring means. The vessel
comprises
treating diethyl disul?de with sulfur dioxide at
is heated to approximately 200° C. while adding sulfur
a temperature in the range of from about 100° to 350° C.
dioxide gas until a'pressure of approximately 100 atmos
and at a super-atmospheric pressure in the range of from
pheres has been reached. The vessel and the contents are
about 2 to about 5 atmospheres, and recovering the re
maintained at this temperature for a period of approxi
mately 4 hours after which said vessel and contents are 30 sultant diethyl ether.
6. A process for the preparation of butyl alcohol
allowed to cool to room temperature. The reaction
which
comprises treating butyl mercaptan with sulfur
mixture is subjected to fractional distillation and the cut
operation.
boiling at approximately 77-80° 0., comprising ethyl
alcohol, is separated out and puri?ed.
Example II
100 g. of propyl sul?de is placed in a reaction vessel
equipped with heating and stirring means. The vessel
is sealed and heated to a temperature of approximately
225° C. while sulfur dioxide is added to the vessel until
a pressure of approximately 30 atmospheres is reached.
After a period of approximately 4 hours, the ?ask and
contents thereof are cooled to room temperature and
the dipropyl ether boiling at approximaely 91° C. is sep
arated from the unreacted propyl sul?de and other reac 45
tion products and puri?ed.
I claim as my invention:
1. A process for the preparation of oxygen-containing
organic compounds selected from the group consisting of
alcohols and ethers which comprises treating an organic 50
compound selected from the group consisting of mercap
tans, sul?des and disul?des, with sulfur dioxide, at a tem
perature in the range of from about 100° to 350° C., and
dioxide at a temperature in the range of from about
100° to 350° C. and at a super-atmospheric pressure in
the range of from about 2 to about 5 atmospheres, and re
covering the resultant butyl alcohol.
7. A process for the preparation of dipropyl ether
which comprises treating propyl sul?de with sulfur diox
ide at a temperature in the range of from about 100°
to 350° C. and at a super-atmospheric pressure in the
range of from about 2 to about 50 atmospheres, and
recovering the resultant dipropyl ether.
References Cited in the ?le'of this patent
UNITED ‘STATES PATENTS
1,855,486
1,955,722
Morrell et a1. ________ __ Apr. 26, 1932
Ahlqvist ____________ __ Apr. 24, 1934
2,553,576
Grosse et al ___________ __ May 22, 1951
OTHER REFERENCES
Wagner et al.; JACS, vol. 53, pp. 3407~13, 1931.
Gilman: “Organic Chemistry,” vol. 1, pp. 851, 888,
889, 2nd ed., 1943.
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