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Патент USA US2406631

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Patented Aug. 27, 1946 -
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2,406,631
UNITED "STATES PATENT oFncE PRODUCTION OF CYCLO-OIJEFIVNIC HYDRO
CARBONS AND AROMA'TIC GHYDROCAR
'BONS
Herman Pines and Vladimir N. Ipatieff, r-Cl'licago,
111., assignors to Universal ‘Oil Products Com
pany, Chicago, Ill, a corporation of Delaware
‘No‘Drawing. Application‘December 15, 1944,
Serial No. 568,391
8 Claims.‘ (01. zco+cesl
.1
Glycols, alsoknow-n as dihydric alcohols, uti
This invention relates to a process ‘for produc
ing cyclic hydrocarbons. More speci?cally, the
invention-relates 'toa process forproducing cyclo
lizable in our process contain at least 4 carbon
atoms :per ‘molecule and have two hydroxyl
groups, these groups being preferable in the beta,
ole?ns by condensing a glycol of at least 4 carbon
atoms iper'molecule with-a ,monohydric alcohol.
5 gamma, and delta positions to each other. Also
cyclic glycols ‘such :as 13- Band 1,4-cyclohexane
An object of this invention is the condensation
diols are utilizable in our process. Ole?nic alco
of an aliphatic monohydric alcohol with a gly
hols or partially dehydrated glycols such as '2
col containing at least 4 carbon atoms per mole
cule.
methylpentene-1-o1-4, are also useful raw mate
.
Another object of this invention is the produc 10 rials for our vcjondensatipn process.
Monohydric alcohols utilizable also as starting
tion of a cyclohexene hydrocarbon by condensing
an 'alkanol with :a glycol vcontaining at least 4
materials in the process of our invention are gen
carbon atomsper molecule.
erally those :of the aliphatic series and prefer
ably are saturated aliphatic carbinols which are
A further object of this invention is the pro
duction of a cyclohexene hydrocarbon by the con 15 also known as alkanols. Alkanols which do not
contain :a quaternary carbon atom are particu
densation of a glycol containingat least 4 car
larly 'desirablecfor condensationwith a glycol as
bon atoms per molecule with an alcohol selected
herein set forth as alkanols which contain a
from the group consisting of primary and sec
quaternary carbon atom sometimes yield a sub
A still further object of this invention is the 20 stantial proportion of a teritary‘ ole?n rather
than the condensation product desired.
production of 1,3,5-trimethylcyclohexene by con
Although our IJI'OOESS is sometimes carried out
densing 2-methyl-2;4-.p.en;tanediol with a, propyl
in the absence of. an added catalyst at suitable
alcohol.
operating conditions of temperature and pres
One speci?c embodiment of this invention re
sure, we prefer to utilize catalytic materials to
lates to a process for producing a cyclo-ole?n
assist in the condensation of a glycol containing
which comprises condensing an alkanol and a
at least 4 carbon atoms per molecule and an al
glycol having at least 4 carbon atoms per mole
cohol, preferably an alkanol, and more particu
cule in the presence of an acid-acting catalyst at
larly an alkanol which does not contain a quater
a temperature of from about 150° to about 400° C.
nary carbon atom. Catalysts utilizable in our
A further embodiment of this invention relates
process are acid-acting materials and comprise
to a process for producing a benzene hydrocar
activated alumina, hydrated silica, acid-treated
bon which comprises condensing an alkanol and
clays; synthetically prepared composites com
a glycol containing at least 4 carbon atoms per
prising silica-alumina, silica-alumina-zirconia,
molecule to produce a cyclohexene hydrocarbon,
ondary alkanols.
hydrogenating said cyclohexene hydrocarbon to
alumina-zirconia, silica-alumina-thoria;
a cyclohexane hydrocarbon, dehydrogenating said
cyclohexane hydrocarbon to a benzene hydrocar
bon and hydrogen, and utilizing at least a por
tion of said hydrogen in the hydrogenation of
such as hydrochloric acid, hydrobromic acid, a
phosphoric acid, sulfuric acid, a, heteropoly acid
as phosphotungstic 0r posphomolybdic acid, etc;
and also aqueous solutions of hydrolyzable salts
.40 such as ferric chloride, magnesium chloride, zinc
said cyclohexene hydrocarbon.
chloride, ammonium chloride, magnesium acid
Cyclohexene and di?erent alkyl cyclohexene
hydrocarbons which are obtainable by the process
of our invention may be hydrogenated to cyclo
hexane hydrocarbons, or be dehydrogenated to
benzene and alkyl benzene hydrocarbons.
By the term “condensation” used in this speci
?cation and. in the claims, we mean the chemi
cal combination of a dih'ydric alcohol having at
phosphate, sodium acid sulfate, etc.
process are acid-acting in the sense that an aque
ous solution or suspension thereof in Water has
a pH below 7.
Our process may be carried out using either
batch or continuous types of operation, although
the latter is preferable. The process is carried
hydric alcohol accompanied by thesplitting out i
of water. Thus, we have found that 2-methyl
2,4-pentanediol and isopropyl alcohol react at
an elevated temperature to produce 1,3,5-tri
methylcyclohexene and water as the principal
'
These ma
terials which we may employ as catalysts in our
least 4 carbon atoms per molecule and a mono
condensation products.
acids
55
out at a temperature of from about 150° to about
400° 0., but preferably at a‘ temperature of from
about 175° to about 300° C. The process is pref
erably e?ected at a pressure of about 1 atmos
phere or higher and is generally not in excess of
about 100 atmospheres.
7
7
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_
2,406,631
3
4
an alkanol at a temperature of from about 150°
to about 400° C. and at a pressure of from about
character of results obtainable by the process of
1 to about 100 atmospheres.
our invention, although the example is not in
4. A process for producing a cyclo-ole?nic hy
troduced with the intention of restricting unduly
(Fl drocarbon which comprises ‘reacting a glycol
the broad scope of the invention.
The following example is given to illustrate the
1.3 molecular proportions of isopropyl alcohol
having at least 4 carbon atoms per molecule and
and 1 molecular proportion of 2-methyl-2,4-pen- .
tanediol are commingled and charged to an au
an alkanol in the presence of an acid-acting cat_
about 5% by weight of ferric chloride dissolved
in water and the volume of this solution is ap
proximately equal to that of the mixture of gly
col and alcohol introduced thereto. The charged
drocarbon which comprises reacting a glycol
having at least 4 carbon atoms per molecule and
alyst at a temperature of from about 150° to
about 400° C.
toclave containing a solution of ferric chloride in
5. A‘process for producing a cyclo-ole?nic hy
water. The aqueous solution 50 utilized contains 10
an alkanol in the presence of an acid-acting cat
alyst ‘at a temperature of from about 150° to
autoclave is then heated at about 250° C. for a 15 about 400° C. and at a pressure of from about 1
time of 2-4 hours. After cooling, the reaction
mixture contains a hydrocarbon layer compris
ing essentially 1,3,5-trimethylcyclohexene which
to about 100 atmospheres.
6. A process for producing a cyclo-ole?nic hy
drocarbon which comprises reacting a glycol
is produced in a yield of.about 30% of the theo
retical. Trimethylcyclohexene so formed is con
having at least 4 carbon atoms per molecule and
vertible into mesitylene ‘by hydrogenation- and
dehydrogenation treatments.
tion of a hydrolyzable metal salt at'a'tempera
ture of from about 150° to about 400° C. and at
an alkanol in the presence of an aqueous solu
a pressure of from about 1 to about 100 atmos
The novelty and utility of the._ process of the
pheres.
present invention are evident from the preceding
7. A process for producing a benzene hydro
speci?cation and example, although ‘neither sec 25
carbon which comprises condensing an alkanol
tion is introduced to limit unduly the broad scope
and a glycol containing at least 4 carbon atoms
of our invention.
per molecule to produce a cyclohexene hydrocar
We claim as our invention:
bon, hydrogenating said cyclohexene hydrocar
1. A process for producing a cyclo-ole?nic hy
drocarbon which comprises reacting a glycol 30 bon to a cyclohexane hydrocarbon, dehydrogen
ating said cyclohexane' hydrocarbon to a'ben
having at least 4 carbon atoms per molecule and
zene hydrocarbon and hydrogen and utilizing at
a monohydric alcohol at a su?icient temperature
least a portion of said hydrogen in the conden
and pressure that condensation of said glycol
sation of said cyclohexene hydrocarbon.
and monohydric alcohol is the principal reaction
8. A process for producing a benzene hydro
35
of the process.
carbon which comprises reacting an’alkanol and
2. A process for producing a cyclo-ole?nic hy
a glycol containing at least 4 carbon atoms per
drocarbon which comprises reacting a glycol
molecule to produce a. cyclohexene hydrocarbon
having at least 4 carbon atoms per molecule and
and dehydrogenating said cyclohexene hydrocar
an alkanol at a temperature of from about 150°
40 bon to a benzene hydrocarbon.
to about 400° C‘.
'
3. A process for producing a cyclo-ole?nic hy
drocarbon which comprises reacting a glycol
HERMAN PINES.
having at least 4 carbon atoms per molecule and
VLADIMIR N. IPATIEFF.‘ '
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