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Патент USA US2406632

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2,406,632
Patented Aug. 27, 1946
; UNl-TED-’_ STA-res PATENT
‘
‘2,406,632
PRODUCTION OF CYCLO-OLEFINIC "HYDRO
CABBONS AND .AROMATIC @HYDROCAR
_
BONS
‘Herman Pines and ‘Vladimir-"N. Ipatie?’, Chicago,
111., assignors v‘to ‘Universal Oil Products Com
vfpany, ‘Chicago, 111., ‘a corporation of Delaware
.No Drawing. .. Applica'tionDecember15,.1944,
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1
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I‘Seri'a'l'No. 568,392
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essiproceeds ‘preferably with conjugated ‘dio‘l‘e?ns,
of a monohydric alcohol with a conjugated di
other diole?ns ‘are sometimes usable, ‘particularly
when rearrangement occurs at ‘the conditions ‘of
'ole?nic hydrocarbon containing :at least 1i ‘carbon
"
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Another object of ‘this invention is ‘the pro
duction of a cyclohexene/hydrocarbon by con;
densing analkanol with a'oonjugated diole?n.
A ‘further-object of this ‘invention is the pro
duction of a cyclohexene hydrocarbon by the con
densation of a conjugated diole?n with an alcohol
selected from the group consisting of primary and
secondary alkanols.
alternate single and double bonds ‘including .two
double bonds. Althoughthe reaction of ourproc
‘
An‘ object of this 'i'nvention'is the condensation
atoms‘per molecule.
.
ess‘ contain ‘at ‘least :4 carbon ‘atoms per molecule
and are preferably “conjugated ‘diole?ns in‘that
each of said hydrocarbons contains a'system' of
ole?ns by condensing a diole?nic Thydrocarbon
having at least “4 carbon atoms'per molecule with
,
vDiole?n'ic hydrocarbons ‘utilizable in our proc
invention ‘relates’ .to a ‘process for vproducing cyclo
alcohol.
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f'l'hisjinvention relates to ‘a process ‘for produc
ing cyclic hydrocarbons. More speci?pally,v the
amonohydric
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the reaction.
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, Monohydric alcohols utilizable also as starting‘
vmaterials ‘in vthe‘ process "of ‘our invention "are
generally those of the;aliphatic-“seriesand ~‘pref
erably are‘saturated’aliphatic carbinols which
15 are also known as alkanols.
Alkanols which do
not contain a quaternary carbon atom are par
ticularly desirable for condensation with a di
ole?nic hydrocarbon as herein set forth as al-_.
kanols which contain a quaternary carbon atom
A still further object of this invention is the
production of 1,3,5-trimethylcyclohexene by con 20 sometimes yield a substantial proportion of a ter
densing 2~methyl-1,3-pentacliene and isopropyl
tiary ole?n rather than the condensation product
alcohol.
desired.
One speci?c embodiment of this invention re
Although our process issometimes carried out
lates to a process for producing a cyclo-ole?n
in the absence of an added catalyst at suitable op
which comprises condensing an alkanol and a di
erating conditions of temperature and pressure,
ole?nic hydrocarbon having, at least 4 carbon
we prefer to utilize certain catalytic materials
atoms perv molecule in the presence of an acid
to assist in vthe condensation of a diole?nic hy
acting catalyst at a temperature of from about
drocarbon and a monohydric alcohol. Catalysts
150° to about 400° C.
so utilizable are acid-acting materials and com
A further embodiment of this invention relates 30 prise activated alumina,‘ ‘hydrated silica, acid
to a process for producing a benzene hydrocarbon
which comprises condensing an alkanol and a
conjugated diole?n to produce a cyclohexene hy
treated clays; synthetically prepared composites
including silica-alumina, silica-alumina-zirconia,
alumina-zirconia, silica-alumina-thoria, etc.;.
drocarbon, hydrogenating said cyclohexene hy
acids such as hydrochloric acid, hydrobromic acid,
drocarbon to a cyclohexane hydrocarbon, dehy 35 a phosphoric acid, sulfuric acid, or a heteropoly
drogenating said cyclohexane hydrocarbon to a
acid as phosphotungstic or phosphomolybdic acid;
benzene hydrocarbon and hydrogen, and utilizing
and also aqueous solutions of hydrolyzable salts
at least a portion of said hydrogen in the hydro
such as ferric chloride, magnesium chloride, zinc
genation of said cyclohexene hydrocarbon.
chloride, ammonium ‘chloride, magnesium acid
cyclohexene and di?erent alkyl cyclohexene 40 phosphate, sodium acid sulfate, etc. These ma
hydrocarbons which are obtainable by the process
of our invention may be hydrogenated to cyclo
terials which we employ as catalysts in our process
are acid-acting in the sense that an aqueous solu
hexane hydrocarbons or they may be dehydro
tion or suspension thereof in water has a pH
genated to benzene and alkyl benzene hydrocar
.below 7.
bons.
4.5 Our process may be carried out using either
By the term “condensation” used inthis speci?
batch or continuous types of operation, although
cation and in the claims, we mean the chemical
the latter is preferable. The process is carried
combination of a diole?nic hydrocarbon having at
out at a temperature of from about 150° to about
least 4 carbon atoms per molecule and a mono
400° 0., but preferably at a temperature of from
hydric alcohol accompanied by the splitting out 50 about 175° to about 300° C. The process may
of water. Thus, 2-methyl-1,3-pentadiene and
be conducted at atmospheric pressure but is pref
isopropyl alcohol react at an elevated tempera
erably effected at a superatmospheric pressure
ture and preferably in the presence of an acid
acting catalyst to produce 1,3,5-trimethylcyclo
hexene and water as the principal products of the
process.
.
which is generally not in excess of about 100 at
mospheres.
The following example is given to illustrate the
character of results obtainable by the process
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drocarbon which comprises condensing a diole
?nic hydrocarbon having at least 4 carbon atoms
of our invention, although the example is not in
troduced with the intention of restricting unduly
per molecule with an alkanol at a temperature
the broad scope of the invention.
1.6 molecular proportions of isopropyl alcohol
of‘from
1; 3. A process
about150°
forto
producing
abouti400‘fa;CA.
cycloiole?nic
I _‘ v
hy
and l molecularrv proportion =‘of; Z-methyl-l?s
drocarbon which comprises condensing a diole
pentadiene are commlngled and charged to an
autoclave containing a 5% by weight solution of _
ammonium chloride in Water.
id-?nic hydrocarbon having at least 4 carbon atoms
per molecule with an alkanol at a temperature
of’ from about 150° to about 400° C. and at a
the ammonium
mixture of achloride
diole?nic
solution
hydrocarbon-‘and
is
The
about
volume
thatof'.
iso-W
of 10 pressure of from about 1 to about 100 atmos
propyl alcohol introduced thereto. After the
autoclave and contents are heated atabout 250°
pheres.
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4. A, process fornproducing a cyclo-ole?nic hy
C. for 3 hours, the heating is discontinued and ‘ V - drocarbon which comprises condensing a diole
the reaction mixture is permitted to 'cool.,,.After
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drocarbon layer comprising 1,3,5-trimethylcyclo-=I'~jn
cooling, the reaction mixture, contains an 113’
hexene in an amount corresponding to‘about "
35% of the theoretical yield based upon’ the di-, '
ole?n charged.
‘
,JI'lie novelty and utility of theprocess of the 20
present invention are ‘evident from'the preceding
speci?cation‘v and example, although neither sec
tion is introduced to'lir'nit’unduly' the broad scope
of our inventionljl
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‘?nic hydrocarbon having at least 4 carbon atoms
per molecule with an alkanol in the presence of
‘an’ acid-‘acting catalyst at a temperature of from
about 150° to about 400° C.
_5. Aiprocess for producing a cyclo-ole?nic hy
drocarbon which comprises condensing a diole
?nic hydrocarbon having‘ at least 4 carbon atoms
per molecule with an, alkanol'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.
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6. A process for producing a cyclo-ole?nic hy
drocarbon ‘which comprises condensing a conju
will; process for producing'a cyclo-ole?nic hy
gated diole?nic hydrocarbon with an alkanol in
drocarbon which'compri'ses reacting a diolefinic
the presence of an aqueous solution of a hydro
hydrocarbon having at least 4 carbon atoms' per
molecule and a monohy'dric alcohol at a sufficient , , lyzablei metal salt at a temperature of from’about
1' We claim as our invention!
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temperature and pressure that condensation of
said diole?m'c hydrocarbonua’nd monohydric al
cohol is the principal reaction of theprocess.
ZJA process jorproducing a cyclo-ole?nic hy
30 150° to about 400° C. and at a pressure of from
about 1 to aboutlOO atmospheres.
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HERMAN
PINES.
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VLADIMIR N. IPA'I'IEFF.
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