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Патент USA US2385300

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Patented Sept. 18, 1945
, ‘
UNITED ' STATES2,385,300
Herman Pines‘and Vladimir N. Ipatie?, River
side, 111., assignors to ‘Universal Oil Products
Company, Chicago, 111., a corporation or Dela.
No Drawing. Application January 29, 1043,
~ Serial No. 478,972
7 Claims. (01. 260-666)
carbons and para?lnic hydrocarbons of lower mo
This invention relates to a process for eiiect
lecular weight than those charged to the proc
ing hydrocarbon conversions and more particu
larly to a process for converting alkyl cyclopen
tane hydrocarbons into alkyl cyclohexanes by re
acting said alkyl cyclopentane hydrocarbons with
paraiilnic hydrocarbons in the presence of a cat
The present process is a contribution to‘the art -
of producing reactions between different types or
hydrocarbons to synthesize other hydrocarbon
compounds or increasing molecular weight. Var
ious alkylated eyclopentane hydrocarbons can be
illustrated by adding alkyl radicals to the base
member oi this series, namely cyclopentane.
However, the actual syntheses of diiierent alkyl
The ease with l~which. the above reaction oc
curs is probably due to' the presence of a tertiary
' carbon atom in the alkyl cyclopentane molecule.
Because of the di?iculty in following thevcharac
ter 01 such reactions and the possible formation
of certain proportions of intermediate addition
compounds with the catalyst in reactions of the
present type. the above explanation is not of
iered as being entirely adequate. It also omits mention of the formation of small amounts oi
.gaseous hydrocarbons of low molecular weight
such as‘methane and ethane which sometimes
occurs to a minor extent. However, under prop
cyclopentane and alkyl cyclohexane hydrocarbons
erly controlled "conditions, decomposition reac
tions to undesired gaseous hydrocarbons may be
do not follow such a simple mechanism.
One speci?c embodiment of the present in-'
kept low and the alkylation may be regulated by
cyclopentane hydrocarbon .with a para?inic hy 20 controlling the temperature, the nature and
amount or the catalyst. the proportion of par
drocarbon in the presence of an alkylating cat;
a?lnic hydrocarbons to alkyl cyclo'pentane hydro
alyst to form a substantial yield of alkylated and
vention comprises a process for reacting an alkyl
polyalkylated cyclohexane hydrocarbons.
carbons, etc., so that'high yields of the desired
compounds will be produced.
The present process is particularly concerned
with a simultaneous cleavage or breaking of a 26
paramnic hydrocarbon and the alkylation of an
alkyl cyclopentane with fragments resulting
We have discovered that isomerization and -
alkylation of’ alkyl cyclopentane hydrocarbons
can be accomplished simultaneously and more
advantageously by the process of the present in
vention than- by isomerization alone. In this
ization can accompany alkylation when an alkyl 30 process, the alkyl cyclopentanes are reacted with
straight and/or branched chain para?ins in the
cyclopentane hydrocarbon is destructively al
presence or an alkylating catalyst including sul
iwlated with a paramnic hydrocarbon. The fol
i'uric acid, hydrogen ?uoride, mixtures of hydro
lowing equahlon illustrates the destructive alkyla
gen ?uoride and boron ?uoride, and Friedel
tion of methyl cyclopentane with iso-octane:
Crafts type metal halides together with a hydro
gen. halide.» Under the preferred conditions of
irom said cleavage or breaking of a para?inic hy
drocarbon. Furthermore, it appears that isomer
operation, which are discussed hereinafter in re
lation to the di?erent aikylating catalysts, an al
mlation productis formed consisting not of more
highly alkylated‘ cyclopentane hydrocarbons but
of alkylated cyclohexane hydrocarbons. In other
words, isomerization occurred either before, after,
or during the alkylation reaction. By this proc
ess, the alkylation of alkyl cyclopentane hydro
45 carbons with para?inic hydrocarbons, including
isoparaf?ns and normal para?ins, to form alkyl
cyclohexane hydrocarbons is accomplished rap
under operating conditions which are rela
The ‘above equation indicates that methyl cy
tively easy to control.
cyclopentane may be reacted with 2,2,4-trimethyl
pentane to form 1,2-dimethyl-4-ethyl‘cyclohex 50 Another advantage of the process is the fact
that nearly complete conversion of the alkyl cy
are together with isobutane. Other branched
clopentane hydrocarbons into alkyl cyclohexanes
chain para?inic hydrocarbons and less-branched
can be obtained. Furthermore, the cyclohexane
chain para?inic hydrocarbons can also undergo
hydrocarbons formed by this process may be
a similar reaction under suitable conditions of
operation to form alkylated cyclohexane hydro- 5s separated from unconverted cyclopentane by
drocarbons and dehydrogeuated catalytically or
thermally into alkyl benzene hydrocarbons while
the unconverted or incompletely converted alkyl
cyclopentane hydrocarbons are returned to fur
ther treatment with para?inic hydrocarbons in
the presence of an alkylating catalyst as herein
set forth.
The di?erent allwl cyclopentane hydrocarbons
and paraiilnic hydrocarbons employed in the
the rate of undesirable reactions which fre
quently result in deposition and/or degradation
7 of the desired alkylation product.
While the process of the present invention may
be eii'ected in either batch or continuous types of
operation, it is usually carried out on a continuous
basis by withdrawing from the reaction zone a
complex mixture of excess unreacted alkyl cyclo
pentanes, desired alkylated cycloh'exanes, higher
process need not be entirely pure as any hydro 10 boiling hydrocarbons, and catalyst; said complex
carbon fraction or fractions containing alm cy
mixture being withdrawn at substantially the
clopentane hydrocarbons and paramnic hydro
same rate as that at which the hydcarbons
~ carbons may be utilized in the process. Thus, a
charged are supplied to the alkylation reactor.
hydrocarbon fraction containing substantial
At least a portion or the recovered_used catalyst
amounts of methyl-, ethyl-, and higher alkyl 15 and unreacted alkyl cyclopentanes may be re
cyclopentanes in admixture with straight ‘and
cycled to further treatment with para?lnic hy
branched chain paraiiins may be converted as
drocarbons in the presence of some freshly added
alkylating catalyst.
herein set forth to obtain substantial yields of
alkyl cyclohexane hydrocarbons.
Batch type operation of the present process
The catalysts employed in the process of the 20 may be carried out by gradually introducing a
present invention are not necessarily equiva
para?inic hydrocarbon fraction or a para?in con
lent in their action and accordingly. the condi
taining fraction to a reaction vessel containing
tions of operation and particularly the reaction
a mixture of the alkyl cyclopentane hydrocarbon
temperature are dependent upon the catalyst
and the catalyst. The reaction vessel is prefer
employed in a particular reaction. Thus, with 25 ably equipped with an eflicient mixing or stirring
7 hydrogen ?uoride or mixtures of hydrogen ?uo
device so as to insure intimate contact of the re
ride and boron ?uoride, a reactor temperature of
acting hydrocarbons and catalyst. Upon com
. from about -20° to about 200° C. is employed at
pletion of the alkylation reaction, a hydrocarbon
a pressure of generally not more than about 35
product is separated from the catalyst and said
atmospheres; while sulfuric acid is utilizable gen 80 hydrocarbon product is further fractionally dis
eralhr at a temperature of from about —5‘‘ to
tilled to separate alkylated cyclohexane hydro
about 120° C. when employing catalysts con
carbons from unconverted or incompletely con
taining an acid of phosphorus, such as solid phos
verted paraiilnic and cyclopara?lnic hydrocarbons
phoric acid, the temperature utilized is from
which are returned to further treatment in the
about 100° to about 450° C. and the pressure is 35 presence of an alkylating catalyst as hereinabove
generally between about 1 and 70 atmospheres.
set forth.
Catalysts of the Friedel-Crafts type are utilizable
The following example indicates results ob
under dii’ferent conditions of operation depend
tainable by the present process, although it is in
ing upon the particular Frledel-Crafts type cata
troduced with no intention of limiting the scope
lyst employed. 'I'hus, aluminum chloride may be 40 of the invention in exact correspondence thereto.
utilized at a temperature of from about —'l0° to
4 molecular proportions of methyl cyclopen
about 150° C. while ferric chloride requires a
tane are reacted with 0.5 molecular proportions
somewhat higher average temperature and zinc
of 2,2,4-trimethyl pentane in the presence. of hy
chloride is utilizable only at still higher temper
drogen ?uoride at a temperature 010100“ C. The
atures and particularly at a temperature of from 45 resultant reaction mixture, after separation
about 150° to about 450° C.
therefrom of unconverted methyl cylclopentane
The details of operation of the present process
and 2,2,4-trimethyl pentane, contains substantial
are relatively simple since alkyl cyclopentane
amounts of allgvlated cyclohexane hydrocarbons.
hydrocarbons are liquid under ordinary condi
The character of the present invention and its
tions of temperature and pressure. Accordingly, 50 novelty and utility in producing alkyl cyclohex
the process of the present invention is carried
out by contacting an alkyl cyclopentane hydro
carbon with ,a para?lnic hydrocarbon generally
ane hydrocarbons can be seen from the preced
ing speci?cation and example, although neither
section is intended to limit unduly its generally
containing 4 or more carbon atoms per molecule
broad scope.
in the presence of an alkylating catalyst under 55 We claim as our invention:
the preferred operating conditions until alkyla
1. A process for producing substantial yields
tion has occurred and a substantial yield of an
of alkyl cyciohexane hydrocarbons which com
essentially saturated hydrocarbon product is
prises reacting an alkyl cyclopentane hydrocar
formed containing a relativelyhigh proportion of
bon and an isopara?inic hydrocarbon in the pres
alkyl cyclohexane hydrocarbons. The molar 60 ence of an alkylating ‘catalyst while maintaining
ratio of alkyl cyclopentane hydrocarbons to par
a molar excess of alkyl cyclopentane hydrocar
a?lnic hydrocarbons should be greater than 1 and
bon to isopara?inic hydrocarbon throughout the
preferably greater than 3, the exact ratio being
somewhat dependent upon the particular
2. A process for producing substantial yields of
alkyl cyclopentane and para?inic hydrocarbons 65 alkyl cyclohexane hydrocarbons which comprises
charged to the process. The ratio of alkyl cyclo
reacting an alkyl cyclopentane hydrocarbon and
pentane hydrocarbon to parailinic hydrocarbons
an isopara?inic hydrocarbon in the presence of
charged is subject to some variation and is af
an alkylating catalyst comprising sulfuric acid
fected considerably by the method of introducing
as its essential active ingredient.
c hydrocarbon, the e?iciency of mix 70 3. A process for producing substantial yields
of alkyl cyclohexane hydrocarbons which com
prises reacting an alkyl cyclopentane hydrocar
bon and an isopara?lnic hydrocarbon in the pres
ence of an aykylating catalyst comprising hydro
peratures there is generally a marked increase in 75 gen ?uoride as its essential active ingredient.
It is advisable to carry out the process of the
present invention at as low a temperature as
possible and as is practical, since at higher tem- -
reacting an alkyl cyclcpentane hydrocarbon and 7
4. A process for producing substantial yields
or alkyl cyciohexane hydrocarbons which com
prises reacting an alkyl cyclopentane hydrocar
an isoparaiiinic hydrocarbon in the presence of an
alkylating ‘catalyst while maintaining a molar
ratio of alkyl cyclopentane hydrocarbon to iso
paramnic hydrocarbon or more than three
bon and an isoparaiiinic hydrocarbon in the pres
ence of an alkyintlng catalyst comprising a
Friedel-Craits type metal halide as its essential
active ingredient.
throughout the reaction.
7. A process for producing substantial yields oi’
alkyi cyclohexane hydrocarbons which comprises
5. A process for producing substantial yields
reacting an alkyl cyciopentane hydrocarbon and
oi alkyi cyclohexane hydrocarbons which com
prises reacting an alkyl cyclopentane hydrocar 10 a. paramnic hydrocarbon in the presence of an
alkylating catalyst while maintaining a molar
bon and a para?inic hydrocarbon in the presence
ratio of alkyl cyclopentane hydrocarbon to par- "
of an ‘alkylating catalyst while maintaining a mo
lar excess oi alkyl cyclopentane hydrocarbon to
para?lnlchydrocarbon throughout the entire re
6. A process for producing substantial yields of
alkyl cyciohexane hydrocarbons which comprises
aiiinic hydrocarbon of more than three through- _
out the reaction. »
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