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Патент USA US2406630

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Patented Aug. 27, 1945
2,406,630
UNITED STATES PATENT OFFICE
’
2,406,630
PRODUCTION OF CYCLO-OLEFINIC HYDRO
CARBONS AND AROMATIC HYDROCAR
BON S
Herman Pines and Vladimir N. Ipaticif, Chicago, '
Ill., assignors to Universal Oil Products Com
pany, Chicago, 111., a corporation of Delaware
No Drawing. Application December 15, 1944,
Serial No. 568,390
.
8 Claims.
(01. 260-666)
V
‘
1
2
Thisinvention relates to a process for produc
atoms per molecule and have two hydroxyl
groups, these groups being preferable in the beta,
gamma, and delta positions to each other. Also
cyclic glycols such as 1,3- and 1,4-cyclohexane
ing cyclic hydrocarbons. More speci?cally, the
invention relates to a process for producing cyclo
ole?ns by condensing a glycol of at least 4 car
bon atoms with an ole?n.
An object of this invention is the condensation
of an ole?nic hydrocarbon with a glycol contain
ing at least 4 carbon atoms per molecule.
Another object of this invention is the pro
duction of a cyclohexene hydrocarbon by con
densing av mono-ole?nic hydrocarbon with a
glycol containing at least 4 carbon atoms per
molecule.
.
'
2-methyl-2,4-pentanediol
with
acting materials and comprise Activated Alumina,
hydrated silica, acid-treated clays, synthetically
' prepared composites comprising silica-alumina,
i
A further object of this invention is the pro
duction of 1,3,5-trimethylcyclohexene by con
densing
pylene.
diols are utilizable in our process. Ole?nic alco
hols or partially dehydrated glycols such as 4
methyl-4-pentene-2-ol are also useful raw mate
rials for our condensation process.
Catalysts utilizable in our process for condens
10 ing a dihydric alcohol with an ole?n are acid
pro
silica-alumina-zirconia, alumina-zirconia, silica
15 alumina-thoria; acids such as hydrochloric acid,
hydrobromic acid, a phosphoric acid, sulfuric
acid, a heteropoly acid as phosphomolybdic or
One speci?c embodiment of this invention re~ V
phosphotungstic acid, etc.; and also hydrolyzable
lates to a process for producing a cyclo-ole?n
salts such as magnesium chloride, ammonium
which comprises condensing an aliphatic mono 20 chloride, ferric chloride, etc. These materials
ole?n and a glycol having at least 4 carbon atoms
per molecule in the presence of an acid-acting
utilizable as catalysts in our process are acid
acting in the sense that an aqueous solution or a
catalyst at a temperature of from about 150° to
suspension thereof in Water has a pH below 7 .
about 400° C. The reaction is preferably car
Our process may be carried out using either '
ried out at pressures from about 1 to about 100 25 batch or continuous types of operation, although
atmospheres.
the latter is preferable. The process is carried
A further embodiment of this invention relates
out at a temperature of from about 150° to about
to a process for producing a benzene hydrocar
400° C. but preferably at a temperature of from
about 150° to about 275° C. Superatmospheric
bon which comprises condensing a mono-ole?nic
hydrocarbon and a glycol containing at least 4
pressures are recommended but this pressure is
generally not in excess of about 100 atmospheres.
carbon atoms per molecule in the presence of an
acid-acting catalyst to produce a cyclohexene hy
The following example is given to illustrate the
drocarbon, hydrogenating said cyclohexene hy
character of results obtainable by the process of
drocarbon to a cyclohexane hydrocarbon, dehy
our invention although the example is not intro
drogenating the latter hydrocarbon to a benzene
duced with the intention of unduly restricting
hydrocarbon and hydrogen, and utilizing at least
the broad scope of the invention.
a portion of said hydrogen in the hydrogenation
1.5 molecular proportions of propylene and 1
of said cyclohexene hydrocarbon.
molecular proportion of 2-methyl-2,4-pentane
Cyclohexene and di?erent alkyl cyclohexene
diol are mixed and introduced to an autoclave
hydrocarbons which are obtainable by the process 40 containing a 5% solution of magnesium chloride
of our invention may be hydrogenated to cyclo
hexane hydrocarbons, or be dehydrogenated to
in Water. The volume of the magnesium chloride
solution is approximately equal to that of the
benzene and alkylated benzene hydrocarbons.
reaction mixture introduced thereto. The entire
By the term “condensation” used in this speci
reaction mixture is heated at about 250° C. for
?cation and in the claims, We mean the chemical 45 about 2 hours. After cooling, the reaction mix
combination of a dihydric alcohol having at least
ture yields a. hydrocarbon layer containing about
4 carbon atoms per molecule and a mono-ole?nic
hydrocarbon accompanied by the splitting out of
water. Thus, we have found that 2-methyl-2,4
35% of normally liquid hydrocarbon material
' comprising essentially 1,3,5—trimethylcyclohexene.
This trimethylcyclohexene is convertible by de
pentanediol and ethylene react at an elevated 50 hydrogenation into mesitylene.
temperature in the presence of an acid-acting
The novelty and utility of the process of the
catalyst to produce 1,3-dimethylcyclohexene and,
present invention are evident from the preceding
water as the condensation products.
speci?cation and example, although neither sec
Glycols, also known as dihydric alcohols, util
tion is introduced to limit unduly the broad
izable in our process contain at least 4 carbon 55 scope of our invention.
2,406,630
3
4
cyclohexene which comprises reacting 2-methyl
2,4-pentanediol and propylene in the presence of
We claim as our invention:
1. A process for producing a cyclo-ole?nic hy
an aqueous solution of a hydrolyzable metal salt
drocarbon which comprises reacting a glycol hav
at a temperature of from about 150° to about
ing at least 4 carbon atoms per molecule and a
mono-ole?nic hydrocarbon in the presence of an Gr 400° C,
acid-acting'catalyst at a su?icient temperature
and pressure that condensation of said mono
ole?nic hydrocarbon and glycol is the principal
reaction of the process.
2. A process for producing a cyclo-ole?nic hy
drocarbon which comprises reacting a glycol hav
ing at least 4 carbon atoms per molecule and a
mono-ole?nic hydrocarbon in the presence ofan
acid-acting catalyst at a temperature of from
about 150° to about 400° C.
3. A process for producing a cyclo-ole?nic hy~
drocarbon which comprises reacting a glycol hav
ing at least 4 carbon atoms per molecule and a
mono-ole?nic hydrocarbon in the presence of an
acid-acting catalyst at a temperature of from
about 150° to about 400° C. and. at a pressure of
from about 1 to about 100 atmospheres.
4. A process for producing a cyclo-ole?nic hy
drocarbon which comprises reacting more than 1
molecular proportion of a mono-ole?nic hydro
carbon and 1 molecular proportion of a glycol
having’at least¢1 carbon atoms per molecule in
the presence of an acid-acting catalyst at a ternperature of from about 150° to about 400° C. and
at .a pressure of from about 1 to about 100 at
mospheres.
I 5. A process for producing 1,3,5-trimethyl
6.v A process‘ for producing 1,3,5-trimethyl
cyclohexene which comprises reacting 2-methy1
2,4-pentanediol and propylene in the presence of
an aqueous solution of a hydrolyzable metal salt
10 at a temperature of from about 150° to about 400°
C. and at apressure of from about 1 to about 100
atmospheres.
r
.
7. A process for producing a benzene hydro
' carbon which comprises reacting a mono-ole?nic
hydrocarbon and a glycol containing at least 4
carbon atoms per molecule in the presence of an
acid-acting catalyst to produce a cyclohexene hy~
drocarbon, hydrogenating said cyclohexene hy
drocarbon to a cyclohexane hydro-carbon, dehy
drogenating said cyclohexane hydrocarbon to a
benzene hydrocarbon and hydrogen, and utilizing
at least a portion of said hydrogen in the hydro
genation of said cyclohexene hydrocarbon.
8. A process for producing a benzene hydro
carbon which comprises reacting a mono-ole?nie
hydrocarbon and a glycol containing at least 4
carbon atoms per molecule in the presence of an
acid-acting catalyst to produce a cyclohexene hy
drocarbon and dehydrogenating said cyclohexene
hydrocarbon to a benzene hydrocarbon.
HERMAN PINES.
_
VLADIMIR N_ IPATIEFF. ,
_
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