close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2410445

код для вставки
Patented Nov. 5, v1946
2,410,445 -
UNITED STATES .PATENT, OFFICE
2,410,445
PRODUCTION OF DIOLEFINIC HYDROCAR
BON S BY REACTION OF AN ALCOHOL
WITH AN ACETYLENIC HYDROCARBON
Vladimir N. Ipatieif and Herman Pin'es, Riverside,
Ill., assignors to Universal Oil Products Com
pany, Chicago, 111., a corporation of Delaware
No Drawing. Application Novcmber25, 1942,
1
Serial No. 466,923
10 Claims. (Cl. 260-681)
2
This invention relates to a process for pro
drogen from an outside source in order to satis
ducing butadiene and other diole?nic hydrocar
bons from materials which are more readily avail
able. More speci?cally, it is concerned with a
process for producing butadiene in a single stage
tactorily control the reaction and to prevent ex
cessive polymerization of diole?nic hydrocarbons
and other unsaturated products formed by the
process.
process in the presence of a solid catalyst.
One of the most important sources of synthetic
rubber is butadiene, a hydrocarbon whichis
I
While the process of this invention may be ef
fected in batch type operation, it is preferable to
utilize a continuous process for reacting alcohols
found in relatively small quantities in re?nery
with acetylenes to produce relatively high yields
gases and in hydrocarbon gases resulting from 10 of diole?nic hydrocarbons.
various other processes. Accordingly, processes
Thus, ethyl alcohol and many higher alcohols
which can produce butadiene in high yields from
may be reacted with acetylene itself or with other
relatively common and cheap starting materials
acetylenic hydrocarbons to produce butadiene
are highly meritorious and‘ particularly at the
and other diole?nic hydrocarbons of higher mo
present time.
15 lecularweight than butadiene as we1l,as certain "
We have found that butadiene and other diolei
amounts of mono-ole?nic hydrocarbons which
?ns, also called alkadienes, may be produced
probably result from hydrogenation of diole?ns,
readily from alcohols and acetylenic hydrocar
the hydrogen being derived from dehydrogena
bons by a relatively simple catalytic process which
tion of ethyl alcohol to acetaldehyde. However,
- not only results in the formation of high yields of 20 reactions involving di?erent alcohols and differ
- diole?n but also in the production of other prod
ent acetylenic hydrocarbons are not necessarily
ucts, particularly ole?ns which may be separated
from diole?ns by fractionation methods.
carried out under the same conditions of opera
For
example, we have found by experimentation that
it is possible to react ethyl alcohol with acetylene 25
in the presence of a catalyst to form substantial
yields of butadiene and butenes.
In one speci?c embodiment, the present inven
tion relates to a process for preparing dlole?ns
which comprises reacting an alcohol and an 30
acetylenic hydrocarbon in the presence of a cata
lyst having both dehydrating and dehydrogenat
ing activities.
'
According to the process of the present in
vention, an alcohol and an acetylenic hydrocar
bon are reacted at a temperature of from about
200° to about 600° _C., under a pressure of less
than about 20 atmospheres in the presence of a
tion to produce good yields of diole?nic hydro
carbon.
'
a
The following speci?c example is given to il
lustrate the process of the invention, although
these data are‘ introduced with no intention of
unduly limiting its generally broad scope.
Acetylene at a rate of 10 liters of gas per hour
and ethyl alcohol at a rate of 40 cc. of liquid per
hour were passed under atmospheric pressure
during a period of two hours over 50 cc. of Acti
vated Alumina in the form of 3 x 3 mm. pellets
contained in a Pyrex glass tube maintained at a
The reaction products
were conducted through a receiver cooled to
35 temperature of 475° C.
—'I8° C. to a gas holder in which uncondensed
gases
were collected for analysis and measured.
catalyst having both dehydrating and dehydro
genating activities. Alcohols and particularly al 40 Condensible gases which were collected, as a liquid
in the receiver at 578° C. had a gaseous volume
kanols which may be so utilized include ethyl
alcohol, also known as ethanol, and its homologs
of higher molecular weight. Acetylenic hydro
l
carbons also referred to as alkynes and utilizable
as herein set forth comprise acetylene itself and 45
of 5625 cc. under standard conditions and con- 7
include alumina, thoria, magnesia, silica, etc.,
tained 19.3 mole per cent of acetylene, 22.4% of
1,3-butadiene and 24.3% butenes, the remainder
of the gases consisting mainly of ethylene and
propylene. The non-condensible gases which
amounted to about 28 liters contained 26.5 mole
per cent of acetylene, 48.1% of ethylene, 36.2% of
either alone or in combination with one another,
I hydrogen, and 7.4% of propylene and higher ole
higher boiling monoalkyl and dialkyl acetylenes.
Catalysts suitable for use in the present process
these catalysts having both dehydrating and de
hydrogenating properties. If desired their de
The value of the present process is evident from '
hydrogenating properties may be improved by the
consideration of the preceding speci?cation and
addition of small proportions of dehydrogenat
example -'presented, although neither section
ing catalysts such as cadmium, zinc, cobalt, etc.
should be' construed as imposing undue limita
In some instances, it may be desirable to add hy 56 tions upon the broad scope of the invention.‘
2,410,445 a
3
,
.
4
v
8. A process for producing 1,3-butadiene which
,We claim as our invention:
1. A process for producing a diole?n which
comprises reacting an alkanol and an alkyne at a.
temperature of from about 200° to about 600° C.,~
under a pressure or less than about 20 atmos
pheres in the presence 01 a metal oxide catalyst
comprises reacting ethanol and acetylene at a
temperature of from about 200° to about 600° 0.,
in the presence of magnesia.
'7. A process for producing 1,3-butadiene which
comprises reacting ethanol and acetylene in the
presence of magnesia at a temperature of from
about 200° to about 600° 0., and under a pres
activities and consisting of at least one oxide
sure of less than about 20 atmospheres.
selected from the group consisting of alumina,
8. A process for producing a diole?n which
10
thoria, magnesia. and silica.
comprises reacting an alcohol and an acetylenic
2. A process for producing 1,3-butadiene which
having both dehydrating and 'dehydrogenating‘
comprises reacting ethanol and acetylene at a
temperature of from about 200° to about 600° 0.,
' hydrocarbon at a temperature of from about 200°
having both dehydrating‘ and dehydrogenating
sisting of alumina, thoria, magnesia and silica.
C‘. to about 600° C. in the presence of a dehydrat
i118 and dehydrogenating catalyst consisting of
under a pressure of less than about 20 atmos
pheres in the presence of a metal oxide catalyst 15 at least one oxide selected from the group con
activities and consisting of at least one oxide
9. A process for producing a. diole?n which
comprises reacting an alkanol and an alkyne at a
genating catalyst consisting of at least one oxide
comprises reacting an alkanol and an allwne at a
selectedeirom the group consisting of alumina,
temperature
of from about 200° to about 600° 6.,
thoria, magnesia and silica.
(
3. A process for producing a diole?n which .20 in the presence of a dehydrating and dehydro
i '
selected from the group consisting of alumina,
temperature of from about 200° to about 600° C.
thoria, magnesia and silica.
in the presence of alumina.
10. A process _for producing 1,3-butadiene
4. A process for producing 1,3-butadiene which
comprises reacting ethanol and acetylene at a 25 which comprises reacting ethanol and acetylene
at a temperature of from about 200° to about 600°
temperature of from about 200° to about 600° (3.,
C., in the presence of a dehydrating and dehy
in the presence of alumina.
drogenating catalyst consisting of at least one
5. A process for producing 1,-3-butadiene which
oxide selected from the group consisting of alu
comprises reacting ethanol and acetylene in the
presence of alumina at a temperature of from 30 mina, thoria, magnesia and silica.
'
VLADIMIR N. IPATIEFF.
about 200° to about 600° C., and under a pressure
of less than about 20 atmospheres.
‘
PINES.
Документ
Категория
Без категории
Просмотров
0
Размер файла
233 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа