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Патент USA US2128909

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Sept. 6, 1938.
2,128,909
J. E. BLUDWORTH
PREPARATION OF OXYGENATED COMPOUNDS
Filed Nov. 19, 1935
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N VENTOR
n.JOSEPH
m
E. BLUDWURTH
Q; W ATTORNEYS
Patented Sept. s, 1938
2,128,909
UNITED STATES PATENT OFFICE
2,128,909
PREPARATION OF OXYGENATED COM
POUNDS
Joseph Elliott Bludworth, Arlington, Tern, as
signor to Ceianese Corporation of America, a
corporation of Delaware
Application November 19, 1935, Serial No. 50,519
16 Claims. (Cl. 260451)
This invention relates to the preparation of
oxygenated compounds by processes involving
the oxidation of hydrocarbons and relates more
particularly to the formation of lower aliphatic
5 oxygenated compounds in relatively large yields.
An object of my invention is to prepare oxygenated compounds by the oxidation of hydro-
for the oxidation of hydrocarbons wherein the
number of oxygenated compounds formed is relatively small and whereby such compounds may
reactions take place. While nitrogen or low boil
ing hydrocarbons may be used as a diluent,
steam is preferred as it presents a protective in
?uence not enjoyed by other diluents.
Conveniently. the DI‘OCESS may be Carried out 5
by separately heating a relatively large amount
of steam or other diluent to the high tempera
tulle required for the Tea?tion and then mixing
therewith the hydrocarbon to be oxygenated and
the required amount of air or other oxygen-con- 10
mining eras under conditions whereby rapid and
thorough mixing is attained. Prior to admixture
with the heated steam, the hydrocarbon and air
be separated in relatively pure form from the
15 products of reaction. Other objects of this in-
may 01’ may not be preheated, but if it is pre
heati‘fi it Should be at a temp?rature below the 15
carbons in such a manner that the nature of the
products formed may be controlled.
A further
10 object of my invention is to provide a, process
[6 G
vention will appear from the following detailed
description.
It has been proposed to form oxygenated oompounds by the oxidation of hydrocarbons. How-
decomposition point thereof. Upon this mixing
of the hydrocarbon with the heated steam, the
entire mass is brought to the reaction tempera
tulle and Oxygenation of the hydrocarbon takes
ever, in such prior processes, the number of oxygenated compounds formed in the reaction is
very large with the result that it is practically
lJlace- After the Oxygenation reaction is initi- 29
ated, the sham Serves the purpose of maintain
ing dilution and by absorbing heat acts as a heat
impossible to separate them into commercially
pure components. Moreover, the yields of desired
lower aliphatic compounds, such as acetaldehyde,
acetone, methyl alcohol, etc., have been relative1y smalL I have found that if the oxidation of
the hydrocarbons is permitted to proceed over a
relatively large range of temperatures and for a
dampenel' to Prevent rise of temperature to an
undesired eXteht- The Steam is employed as a
diluent. & dampeher to prevent excessive heat 25
generated by the reaction and also a substance
used as a protective element for the products of
Oxygenation. Also, the steam is used as a heat
transfer agent.
30 relatively extended period of time, secondary re-
_ The time during which the Oxidation reaction 3“
actions causing the formation of the large number of oxygenated compounds take place,
on the other hand, I have found that if the
oxygenatation process is allowed to proceed for
a'relatively short time under conditions whereby
the hydrocarbon is raised to the desired reaction
temperature, large yields of lower aliphatic oxygenated compounds are produced, the number of
which compounds is relatively small whereby the
.10 compounds may be separated into relatively pure
state quite readily. Whereas, heretofore, oxidation reactions have produced a large number of
18 Permitted t0 066111‘ Should be sufficiently Short
SO as to inhibit the setting in Of decomposition
reactions that tend to form undesirable prod
llcts- Ordinarily the Watt-10h is permitted to
proceed for a Period of 0-1 t0 3 Seconds, prefer
ably 9-3 to 0-5 Second. The time at which ,he
mass is permitted to remain at the temperature
of reaction is conveniently controlled by spray
ins 0!’ Otherwise injecting Water 01' other Cooling
liquid into the reaction mass in su?icient quanti- ~10
ties to quench the gases and vapors so as to re
duce the temperature thereof to below the dc:
compounds in small amounts, I have found that
by varying the conditions of oxidation so that
4:, the reaction time is short the lower molecular
composition temperature and preferably below
350° F. The resulting vapors and gases are then'
conducted to a suitable system for the recovery 45
Weight more desirable compounds are produced
in larger quantities.
and separation of the oxygenated products
formed.
Moreover, I have found that if a large amount
of diluent, such as steam, nitrogen or other inert
50 gas or vapor is present during the oxidation process, such diluent prevents or diminishes undesir~
able reactions and formation of undesired products by absorbing the heat generated during the
oxidation process and thus preventing the rise of
While I prefer to employ butane as the hydro
carbon to be oxygenated, other hydrocarbons such
as propane, pentane, light petroleum distillate-s,
gas oil, etc., either alone or in admixture with
each other, may be oxygenated by this process.
The amount of steam, nitrogen or other gas
used as heat transfer agent, diluent and heat
as temperature to the point where such undesired
dampener is large in order to control the reaction 55
0
2
2,128,909
properly, and is from 30 to 200 or more, pref—
erably 50 to 100, parts by gas volume per one part
by gas volume of the hydrocarbon gas or vapor
to be oxygenated.
The amount of oxygen employed in the reac
tion is also of importance in determining the
nature and yields of the oxygenated product
formed. For the best results, the amount of oxy
gen employed is that equivalent to that present
10 in 7 to 14, preferably '1 to 10, parts by gas volume
of air per one part by gas volume of the hydro
carbon gas or vapor to be oxygenated. By ln~
creasing the amount of diluent gas present the
amount or oxygen employed may be increased.
15 The amount of oxygen may vary between the ex
plosive limits by a corresponding variance in
amount of diluent employed.
The heating medium whether steam, air or a
mixture of steam and air or other diluent should
20 be raised to suitable temperatures, say 1,000°
F. or more immediately prior to admixture with
the hydrocarbon, such that when mixed with the
hydrocarbon the temperature will be from 550°
to 850° F. and preferably 750° to 800° F.
The hydrocarbon may be preheated prior to
admixture with the air and steam, but should
be preheated to a temperature below that at
which decomposition tends to take place.
In order to obtain rapid heating of the hydro
30 carbon and consequently rapid reaction, the air
and steam and the hydrocarbon are caused to
approach at a high velocity to a suitable mix
ing device that causes mixing at high turbulence.
The reaction is preferably conducted under
35 super-atmospheric pressures, say on the order
of 25 to 500 pounds per square inch. Generally,
50 to 200 pounds per square inch pressure are
su?‘icient to produce the desired results.
By my process, there are formed products of
great commercial value and which can be sepa
rated into pure or substantially pure chemical
introducing recycle gas to the compressor It.
The course of the recycle gas will be hereinafter
set forth.
At the mixer I‘! the air, hydrocarbon, recycle
gas and steam may be admixed.
The use of
superheated steam produced in the superheater
l2 not only aids in the heating of the mixture
but also acts to maintain the same at a constant
temperature. The mixture of reacting gases is
led from the mixer IT to a reaction chamber It. 10
The conduit leading from the mixer H to cham
ber l9 may be provided with a temperature regis
tering device It. The reaction chamber l8 com
prises a reaction zone 20 for the reacting gases.
The reaction chamber l9 may be enclosed in a 15~
heater jacket. The point of initiation of reac
tion may be determined by the readings of ther
mometers 2i, a number of which are inserted at
regular intervals throughout the length of the
reaction zone 20. The heated and reacted gases 20
pass from the reaction zone 20 to the quench
chamber 23 where the latent heat is removed
from the gases and the temperature thereof is
reduced from the temperature of reaction to
about 320° F. or less. In place of the furnace, 25
shown as the reaction chamber l9, any suitable
means may be employed to maintain the reac
tion zone 20 at a constant temperature. An al
ternative means may be the mere insulation of
the reaction zone 20.
30
A pipe or conduit 24 may be provided for car
rying the products of reaction from the quench
chamber 23 to a ‘cooler 25. The .temperature of
the quenched reaction gases may be indicated by
a temperature indicator placed in the line 24. 35
The cooler 25 acts to control the temperature of
the reaction products and to remove su?icient spe
ci?c heat to follow the mixture of gases, water and
other products of reaction to pass to an accumu
lator and absorber 28 at the proper temperature
for purposes of crude distillation. A pipe or con 40
compounds, such a acetaldehyde, formaldehyde,
acetone, methyl alcohol, acetic and other organic
duit 32 may be provided leaving from the ab
acids as well as small proportions of methyl,
cording devices 26 and 30 may be inserted into
the feed and discharge lines of the absorber 28.
For the purpose of regulating the level of the 45
liquids in the system a valve 3i is placed in pipe 32.
propyl and butyl alcohol.
The accompanying drawing shows diagram
matically a form of apparatus that may be used
in carrying out the invention.
There is provided a pipe I for introducing wa
50 ter into the system. Pipe I leads to a meter
9 and then to a pump 69. A pipe line 22 is pro
vided to carry the water from the pump 69 to a
quench chamber 23. The quench chamber 23 is
so constructed that the products of the reaction
may be cooled from the elevated temperature of
reaction to about 320° F. or less.
There is a pipe 2 through which steam may
be introduced into the system, which pipe may
pass through a metering device 8 and into a
60 superheater-furnace l2. The superheater fur
nace I2 may be provided with a coil l3 for car
rying the steam therethrough. The heating coil
l3 may be connected by a pipe to a mixer I3.
The pipe for carrying the steam from the heat
65 ing coil l3 to a mixer ll may be provided with a
temperature recorder H.
A pipe or other conduit 3 may be provided
for introducing air or other oxygen-containing
gas into the system. Pipe 3 may pass through a
70 meter 1 and compressor l6 into the mixer IT.
A pipe 4 may be provided for introducing
butane or other hydrocarbon into the system.
The pipe 4 may pass through a vaporizer 5, a
metering device 6 and then to the inlet of the
75 compressor ii. A pipe l5 may be provided for
sorber 28 to a still 35. Suitable temperature re
In the absorber 23 the liquid and gaseous re
action products and also the uncombined elemen
tary gases of the mixture are separated. The
liquid portion passes through the line 32 to the 50
still 35. The gases pass out of the still by way
of a pipe line 29. The liquids leaving the ab
sorber 28 through the pipe 32 may be mixed at
33 with a very small amount 01' water previously
used to absorb the product contained in the "tail" 55
gases from the distillation system. The liquids,
leaving the absorber 28 through the pipe 32, and
the water injected into the system at 33 are led
through a conduit or pipe 34 to the still 35, where
such products of the reaction as acetaldehyde.
acetone and alcohols together with some water
are ?ashed oil.’ overhead. By means of suitable
pipes the remainder of the liquid fraction of the
reaction products, which liquid fraction comprises
organic acids, formaldehyde and water, pass to a
re-boller 36. The re-boiler 36 may be provided
with a pipe 31 through which said boiler may
be drained to waste or the liquids contained there
in may be passed to further treatment. Gases
liberated in the re-boiler may be returned through 70
a suitable pipe to the bottom of the still 28.
The still 35 may be connected in any suitable
manner with a dephlegmator 38 which is pro
vided with a pipe 33 connecting it with a con
76
3
amaooo
denser 88. The products of the still or ?ash
column 38 pass through the dephlegmator 88 to
the final condenser 48. The condensed product
from the condenser 88 may be passed by means
5 of a pipe 4| to the crude distillate storage tank
42. The distillate in the storage tank 42 may be
led to stills, not shown, for ?nal re?ning.
The crude distillate storage tank 42 is con
nected by a pipe 43 to an absorber 44. Any vapors
10 vented during ?ash distillation are led by pipe 43
to absorber N, which absorber uses an absorbent,
such as water, which may be injected into the
absorber by means of a pipe. .8 connecting the
connect the boster pump or the pipe ‘ll to the
mixer II. In this modi?cation. the gases from
trap 84 do not enter the gasometer 81 but instead
pass through pipe line ‘H and meter 18 to the
booster compressor 12. Regulation of ?uctuating
gas ?ows is eilected by means or by-pass ‘II and
valve 14. The “boosted" gases leave the com
pressor 12 by means of pipe 18 and are injected
back into the system at H instead of at I! as
when using the low pressure gasometer system. 10
In order further to illustrate my invention but
without being limited thereto, the following spe
ci?c example is given.
absorber with the supply of water I‘. The absorber
15 44 maybe connected by a pipe 81 to a recycle
system into which the stripped vapors vented rrom
the absorber 4! are passed. The reference nu
merals l8 and II indicate metering devices for
measuring the quantity of water passed into ab
V
20 sorbers 28 and N.
The gases vented from absorber 28 are led by
a pipe 29 from the absorber 28 to an oil-absorber
58 on the top of which is mounted a pipe 45
adapted to carry the stripped gases from the oil
25 absorber out of the system. Pipe 45 may be
equipped with suitable control valves and measur
ing devices. To the absorber 58 is also attached
a pipe 5| and pipe 54, which connects the ab
sorber 58, through an oil heater 52 and pipe 54,
30 to a ?ash chamber 55. A suitable temperature
indicating device 53 may be provided in this line
to enable a constant temperature of oil to be
maintained. The enriched absorber oil leaves
absorber 58 by means of the pipe 5| and then
35 passes to oil heater 52 where, by means of tem
perature indicator 53, sufficient heat is main
tained to ?ash off in the ?ash chamber 55 the
absorbed hydrocarbon without the need of boil
' ing the absorber oil. A cooler 55A may be provided
40 in the ?ash chamber 55 to cool the gases in the
heat thereof. The gases removed from 55, after
being cooled by means oi the cooler 55A, are
passed through pipe 58 to a trap 84. A pipe 68,
provided with a metering device 55, is adapted to
connect the trap 64 with a gasometer 81. A
suitable pipe I5 may be provided for connecting
the gasometer 51 to the compressor IS. A suit
able valve is provided to regulate the flow of re
cycle gases to the compressor. Metering devices
are also included in this line. The gasometer 61
5 is employed to maintain a constant ?ow of gases
to the intake of compressor It.
A ?ash chamber 55 is connected through pipe
51 with an oil cooler 58. surge tank 59. pump GI
and meter 62 and through pipe 63 with the oil
55 absorber 58 thereby forming a cyclic arrangement
for the reuse of the denuded oil from ?ash
chamber 55. A suitable reservoir 68 may be pro—
vided for maintaining a constant supply of oil in
the system.
In dotted lines on the drawing there is shown
a system wherein the oil distillation may be
operated at a higher range of pressures, which
system has some advantage. Instead of reducing
the pressure on the oil at 5| to atmospheric con
ditions, a pressure is maintained in the apparatus
through elements 52, 54, 55, 55, 51, 58 and 54.
This pressure is lower than the pressure main
tained in oil absorber 58 (but only low enough
70 to cause the oil and gases to follow their pre
scribed courses). A pipe ‘Il may be provided for
connecting the trap 64 too. booster compressor
12. A by-pass 13 having a valve ‘ll may be pro
vided for conducting the gases around the booster
75 compressor 12. A pipe 15 may be provided to
Example
15
Butane in liquid condition and in amount
equivalent to one part by volume of gas (one part
by weight) is passed through the heating coil 5
where it is heated to 300° F. Water equivalent to
60 volumes of steam (18.5 parts by weight) is in 20
troduced through the pipe 2 and is heated in I!
then sent to the mixer l'l where it is mixed with
10 parts by volume of air (5 parts by weight) in
troduced thereto by means of the pipe 3. The
mixture of the three gases passes through the 25
mixer 11 where the temperature is maintained
at 550° F. The mixture of air and steam and
the butane are caused to travel at high velocity
to the point I‘! where they are mixed at high
turbulence and the butane is immediately raised 30
to the reaction temperature. This mixture is
then passed to the reaction chamber is and is
removed after reaction and quenched by water
from the pipe 22, to below the temperature of
decomposition, e. g. 300° F., the total time em 35
ployed for the reaction being about .3 second.
The mixture is then introduced into the cooler
25 and absorber 28 where it is scrubbed and
cooled by water introduced by pipe 21, the un
condensed gases passing out through the pres 40
sure release pipe 28, while the water and con
densed oxygenated compounds leave through
the pipe 32 and liquid release valve 8| to the
still 35.
Owing to release of pressure in the still 35, 45
upon the addition of suiilcient heat it necessary,
oxygenated products, such as acetaldehyde,
methyl alcohol, acetone, propyl and butyl alco
hol, pass off as vapors through the line 88 and
after condensation in the condenser 48 are col 50
lected in storage tanks 42. This mixture can
be readily separated into the individual com
ponents by fractional distillation, and may then
be puri?ed by suitable chemical treatment if
necessary.
The water carrying formadehyde and organic
acids leave the chamber 36 by pipe 31 to storage
55
and may be treated to recover and separate its
components.
For every part by volume—-or weight-butane
injected at 4, about seven parts by volume of
recycle gas are returned to It by line l5 alter
its recovery from the vent gases leaving absorber
28 by line 28. By way of illustration, it may be
stated that the gases leaving absorber 28 are 65
made up of the following:
1.6.“... CO:
16.0____ CaHa and C4Hl0
8.2______ CIiHG and Cal-Is 70.0__.._. N:
3.6"... 02
1.0---- CO
70
After leaving absorber 28 the gases (still un
der pressure) pass to oil-absorber 58. At this
point the oil soluble constituents are absorbed
from the N2, C0, C02, etc., and conducted to dis
tillation unit 55.
The gases are distilled from 75
2, 128,909
the oil absorbent and pass overhead through line
56 to gasometer B1 and then are returned to l6
where they are mixed with fresh butane and sent
to the reacting zone for reaction with Oz. The
unabsorbed N2, CO and C0; are vented at 45.
By way of illustration and recycling gases may
have the following constituents:
Per cent
CH4
__________ .._
Cal-‘Is __________ __
8.0
by volume
C4H1o __________ __ 47.0
14.63 02 _____________ __
CsHs __________ .._ 13.41 CO:
CsHs __________ __
1.0
___________ __
1.5
14.0
And the vent gases may have the following con
stituents and about 10 volumes are vented for
every volume of fresh butane injected:
Per cent
20
by volume
hydrocarbons in the vapor phase to oxidation
under super-atmospheric pressure with free oxy
gen in the presence of at least 30 volumes of 10
steam for each volume of hydrocarbon vapor and
in the absence of oxidation catalysts, and rapidly
cooling the products.
5. The method of producing oxygenated or
ganic compounds, which comprises subjecting ali 15
phatic hydrocarbons in the vapor phase to oxi
dation under super-atmospheric pressure with
free oxygen in the presence of at least 30 volumes
of steam for each volume of hydrocarbon vapor
and in the absence of oxidation catalysts, rap 20
CO: ___________________________________ __
1.5
idiy cooling the products, separating hydrocar
CO ___________________________________ __
3.8
bone from the products, and returning them to
02 ____________________________________ __
2.0
the oxidation zone.
6. The method of producing oxygenated or
N: ____________________________________ __ ‘92.0
By way of illustration of the nature and yield
of the products produced, it may be stated that
for each 100 pounds of butane treated by the
foregoing process, there are produced 23.0
pounds of acetaldehyde. 10 pounds of acetone, 3
30
pounds of methyl alcohol, 3 pounds of propyl al
cohol, 3 pounds of butyl alcohol, 7 pounds of
organic acids and 15 pounds of formaldehyde.
The acetaldehyde may be oxidized to form acetic
35
free oxygen in the presence of at least 30 volumes
of steam for each volume of hydrocarbon vapor
and in the absence of oxidation catalysts.
5
4. Method of producing oxygenated organic
compounds, which comprises subjecting aliphatic
Per cent
by volume
10
phatic hydrocarbons in the vapor phase to oxi
dation under super-atmospheric pressure with
acid in a subsequent process.
As an example and not as an illustration, there
may be used a, volume ratio of one part of butane
to 10 parts of air to '70 parts of steam which has
a weight ratio of 1/5/21.7. This weight of steam,
21.7 pounds, will absorb 11 B. t. u. per degree
Fahrenheit. The proportion and temperature of
the steam has among other functions, the func
tions of being a diluting or controlling agent,
of acting as a heat carrier by which the heat
‘necessary to initiate the reaction is delivered to
45 the mixture of air and hydrocarbon under the
most favorable circumstances and of a protec
tive agent to retard decomposition of the inter
mediate products, particularly acetaldehyde. after
they have ?rst been formed. Other substances
may replace steam for some of these functions.
It is, however, preferable to use a suiiicient quan
tity of steam to produce all these functions,
It is to be understood that the foregoing de
tailed description is given merely by way of illus
55 tration and many variations may be made there
in without departing from the spirit of my in
vention.
‘Having described my invention, what I desire
to secure by Letters Patent is:
60
1. The method of producing oxygenated or
ganic compounds, which comprises subjecting ali
phatic hydrocarbons in the vapor phase to oxida
tion with free oxygen in the presence of at least
30 volumes of steam for each volume of hydro
65 carbon vapor and in the absence of oxidation
catalysts.
2. The method of producing oxygenated organic
compounds, which comprises subjecting aliphatic
hydrocarbons in the vapor phase to oxidation
70 with free oxygen in the presence of at least 30
volumes oi’ steam for each volume of hydrocarbon
vapor and in the absence of oxidation catalysts,
and rapidly cooling the products. _
‘ 3. The method of producing oxygenated or
75 ganic compounds, which comprises subjecting all
ganic compounds, which comprises mixing, in 25
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and a gas com
prising iree oxygen at a temperature below that
at which the hydrocarbon reacts substantially
with free oxygen, with at least 30 volumes of 30
steam for each volume of hydrocarbon vapor, the
temperature of the steam being such that the
hydrocarbon is raised to a temperature at which
it reacts with free oxygen.
7. The method of producing oxygenated or
ganic compounds, which comprises mixing, in
35
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and a gas com
prising free oxygen at a temperature below that
at which the hydrocarbon reacts substantially 40
with free oxygen, with at least 30 volumes of
steam for each volume of hydrocarbon vapor, the
temperature of the steam being such that the
hydrocarbon is raised to a temperature at which
it reacts with free oxygen, and after an interval 45
of 0.3 to 0.5 seconds rapidly cooling the mixture.
8. The method of producing oxygenated or
ganic compounds, which comprises mixing, in
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and air, at a
temperature below that at which the hydrocar
bon reacts substantially with free oxygen and
under super-atmospheric pressure, with steam in
amount at least 30 times the volume of the hy
drocarbon, also under pressure and at a tempera
ture such that the hydrocarbon is raised to a 55
temperature at which it reacts with free oxygen,
and after an interval of 0.3 to 0.5 seconds rapidly
cooling the mixture.
9. The method of producing oxygenated or
60
ganic compounds, which comprises mixing, in
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and air, at a
temperature below that at which the hydrocar~
bon reacts substantially with free oxygen and 65
under superatmospheric pressure, with steam in
amount at least 30 times the volume of the hy
drocarbon, also under pressure and at a tempera
ture such that the hydrocarbon is raised to a
temperature at which it reacts with free oxygen, 70
after an interval of 0.3 to 0.5 seconds rapidly
cooling the mixture, separating hydrocarbons
from the mixture, and returning them to the
oxidation zone.
10. The method of producing oxygenated or
75
9,129,909
ganic compounds, which comprises mixing, in
the absence oi’ oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and. air, at a
temperature below that at which the hydrocarbon
reacts substantially with tree oxygen and under
super-atmospheric
pressur ,
with
steam
in
amount at least 30 times the volume of the hy
drocarbon, also under pressure and at a tempera
ture such that the hydrocarbon is raised to a
temperature at which it reacts with free oxygen,
and after an interval or 0.1 to 3 seconds rapidly
cooling the mixture.
' 11. The
method
_
of
producing
oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
the vapor oi’ one or more of the lower homo
logues of methane and 'l to 14 volumes of air at
a temperature below that at which the hydro
carbons react substantially with iree oxygen and
20 under a pressure between 50 and 200 pounds per
square inch, with 30 to 200 volumes or steam
under a similar pressure and at a temperature
such that the hydrocarbons are raised to a tem
perature at which they react with tree oxygen,
and after an interval of 0.3 to 0.5 seconds rapidly
cooling the mixture.
12. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
the vapor of one or more of the lower homo
logues of methane and '1 to 14 volumes of air at
a temperature below that at which the hydro
carbons react substantially with free oxygen and
under a pressure between 50 and 200 pounds per
square inch, with 30 to 200 volumes of steam
under a similar pressure and at a temperature
being such that the butane is raised to a tem
perature at which they react with free oxygen,
after an interval of 0.3 to 0.5 seconds rapidly
40 cooling the mixture, separating hydrocarbons
from the mixture, and returning them in vapor
iorm to the oxidation zone in amount about '7
times the volume of fresh hydrocarbon entering
the zone.
45
13. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
butane at a temperature 01 at most about 320° F.
and ‘I to 14 volumes of air with 30 to 200 volumes
a of steam. all under a pressure of 20 to 500 pounds
per square inch, the temperature at the steam
being such that the butane is raised to a tem
perature of 550° to 850° F., and after an interval
of 0.1 to 3 seconds rapidly cooling the mixture.
14. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume
of butane at a temperature of at most about
320° F. and 7 to 14 volumes of air with 30 to 200
volumes of steam, all under a pressure of 20 to
500 pounds per square inch, the temperature of 10
the steam being such that the butane is raised
to a temperature of 550° to 850° F., after an in
terval of 0.1 to 3 seconds rapidly cooling the
mixture, separating hydrocarbons from the mix
ture and returning them in vapor form to the
oxidation zone, in amount about 7 times the
volume of fresh butane entering the zone.
15. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume
of butane at a temperature of at most about
320° F. and 7 to 14 volumes of air, with 50 to 100
volumes of steam, all under a pressure of 50 to
200 pounds per square inch, the temperature of
the steam being such that the butane is raised
to a temperature 01’ 750° to 800° F., after an
interval of 0.1 to 3 seconds rapidly cooling the
mixture, separating hydrocarbons from the mix
ture and returning them in vapor form to the
oxidation zone, in amount about '7 times the 30
volume of fresh butane entering the zone.
16. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and a gas com
prising free oxygen at a temperature below that
at which the hydrocarbon reacts substantially
with free oxygen, with at least 30 volumes of
steam for each volume of hydrocarbon vapor, the
temperature of the steam being such that the .
hydrocarbon is raised to a temperature at which
it reacts with free oxygen, ?ashing o? vapors and
gases from the resulting products, absorbing the
soluble constituents of the ?ashed vapors and
gases in an oil, venting from the system the un
absorbed fraction of the vapors and gases, heat
ing the oil to liberate the absorbed materials,
and returning the liberated materials with fresh
hydrocarbon, air and steam to the oxidation
zone.
50
JOSEPH ELLIO'I'I‘ BLUDWORTH.
CERTIFICATE OF CORRECTION .
September 6, i958
Patent No. 2,128,909. ,
JOSEPH ELLIOTT BLUDWO RTH.
It is hereby certified that error appears in the printed specification
of the above numbered. patent requiring correction as follows: Page 5, first
column, line 57, claim 12, strike out the word "being" and for "butane is"
read hydrocarbons ar‘e: and that the said Letters Patent should be read with
this correction therein that the same may conform to the record of the case
in the Patent Office.
Signed and sealed this 25th day of October, A. D. 1958.
Henry _Van Aredale
(Seal)
Acting Commissioner of Patents.
9,129,909
ganic compounds, which comprises mixing, in
the absence oi’ oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and. air, at a
temperature below that at which the hydrocarbon
reacts substantially with tree oxygen and under
super-atmospheric
pressur ,
with
steam
in
amount at least 30 times the volume of the hy
drocarbon, also under pressure and at a tempera
ture such that the hydrocarbon is raised to a
temperature at which it reacts with free oxygen,
and after an interval or 0.1 to 3 seconds rapidly
cooling the mixture.
' 11. The
method
_
of
producing
oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
the vapor oi’ one or more of the lower homo
logues of methane and 'l to 14 volumes of air at
a temperature below that at which the hydro
carbons react substantially with iree oxygen and
20 under a pressure between 50 and 200 pounds per
square inch, with 30 to 200 volumes or steam
under a similar pressure and at a temperature
such that the hydrocarbons are raised to a tem
perature at which they react with tree oxygen,
and after an interval of 0.3 to 0.5 seconds rapidly
cooling the mixture.
12. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
the vapor of one or more of the lower homo
logues of methane and '1 to 14 volumes of air at
a temperature below that at which the hydro
carbons react substantially with free oxygen and
under a pressure between 50 and 200 pounds per
square inch, with 30 to 200 volumes of steam
under a similar pressure and at a temperature
being such that the butane is raised to a tem
perature at which they react with free oxygen,
after an interval of 0.3 to 0.5 seconds rapidly
40 cooling the mixture, separating hydrocarbons
from the mixture, and returning them in vapor
iorm to the oxidation zone in amount about '7
times the volume of fresh hydrocarbon entering
the zone.
45
13. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume of
butane at a temperature 01 at most about 320° F.
and ‘I to 14 volumes of air with 30 to 200 volumes
a of steam. all under a pressure of 20 to 500 pounds
per square inch, the temperature at the steam
being such that the butane is raised to a tem
perature of 550° to 850° F., and after an interval
of 0.1 to 3 seconds rapidly cooling the mixture.
14. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume
of butane at a temperature of at most about
320° F. and 7 to 14 volumes of air with 30 to 200
volumes of steam, all under a pressure of 20 to
500 pounds per square inch, the temperature of 10
the steam being such that the butane is raised
to a temperature of 550° to 850° F., after an in
terval of 0.1 to 3 seconds rapidly cooling the
mixture, separating hydrocarbons from the mix
ture and returning them in vapor form to the
oxidation zone, in amount about 7 times the
volume of fresh butane entering the zone.
15. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, one volume
of butane at a temperature of at most about
320° F. and 7 to 14 volumes of air, with 50 to 100
volumes of steam, all under a pressure of 50 to
200 pounds per square inch, the temperature of
the steam being such that the butane is raised
to a temperature 01’ 750° to 800° F., after an
interval of 0.1 to 3 seconds rapidly cooling the
mixture, separating hydrocarbons from the mix
ture and returning them in vapor form to the
oxidation zone, in amount about '7 times the 30
volume of fresh butane entering the zone.
16. The method of producing oxygenated
organic compounds, which comprises mixing, in
the absence of oxidation catalysts, an aliphatic
hydrocarbon in the vapor phase and a gas com
prising free oxygen at a temperature below that
at which the hydrocarbon reacts substantially
with free oxygen, with at least 30 volumes of
steam for each volume of hydrocarbon vapor, the
temperature of the steam being such that the .
hydrocarbon is raised to a temperature at which
it reacts with free oxygen, ?ashing o? vapors and
gases from the resulting products, absorbing the
soluble constituents of the ?ashed vapors and
gases in an oil, venting from the system the un
absorbed fraction of the vapors and gases, heat
ing the oil to liberate the absorbed materials,
and returning the liberated materials with fresh
hydrocarbon, air and steam to the oxidation
zone.
50
JOSEPH ELLIO'I'I‘ BLUDWORTH.
CERTIFICATE OF CORRECTION .
September 6, i958
Patent No. 2,128,909. ,
JOSEPH ELLIOTT BLUDWO RTH.
It is hereby certified that error appears in the printed specification
of the above numbered. patent requiring correction as follows: Page 5, first
column, line 57, claim 12, strike out the word "being" and for "butane is"
read hydrocarbons ar‘e: and that the said Letters Patent should be read with
this correction therein that the same may conform to the record of the case
in the Patent Office.
Signed and sealed this 25th day of October, A. D. 1958.
Henry _Van Aredale
(Seal)
Acting Commissioner of Patents.
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