Note: Descriptions are shown in the official language in which they were submitted.
1086333
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The invention relates to a process for the
hydration of unsaturatecl compounds and with the products
so prepared.
It is known to prepare alcohols by hydrating
~lefinically unsaturcted compounds, at fairly high
temperatures, in the presence of hydration catalysts
and various solvents. For example, it is known from
UK 973,832, US 3,257,469 and (3erman Offenlegungsschrift
2,041,954 to hydrate olefins in the presence of hydration
catalyists and solvents such as alcohols, ethers,
ketones and acids.
Known solvents for the hydration of olefins
usually suffer from one or more disadvantages which
makes them unsuitable for use in a commercial plant.
For example, some solvents are not sufficiently stable
under the optimum hydration conditions and some solvents
~I have boiling points cloæe to and/or below the boiling
;l point of the product alcohol which makes the separation
thereof from such solvents difficult or expensive.
Moreover, the use of some æolvents does not result in
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any appreciable increase in yield of alcohols.
The Applicants have now discovered that s~lphones
are particularly useful solvents for hydration reactions.
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- It has been found that sulphones are remarkably stable
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;' 25 solvents under hydration conditions.
Accordingly, the present invention is concerned
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with a process for the preparation of one or more alcohols
comprising reacting one or more mono-olefinically unsaturated
hydrocarbons having 2 to 12 carbon atoms per molecule, with water
in the presence of a hydration catalyst and a solvent, characterized
in that the solvent is a sulphone having the formula:
O -:
wherein R and Rl are aliphatic groups which may be joined together
to form a cyclic sulphone.
Suitable acyclic sulphones are those of the above formula
wherein R and Rl represent the same or different alkyl groups such
as Cl to Cl2 alkyl groups. Specific examples include dimethyl,
diethyl, dipropyl, dibutyl, methylethyl and methylbutylsulphones.
' Preferred cyclic sulphones are sulpholane and alkyl-
- substituted sulpholanes, such as those sulpholanes substituted by
at least one Cl to C8 alkyl group. Specific examples include 2-
methylsulpholane, 3-methylsulpholane, 3-butylsulpholane, 3-
isopropylsulpholane and 2-methyl-4-butylsulpholane.
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~~ The amount of sulphone used in the present invention ~
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may vary between wide limits e.g. from 1 to 99 %w, based
on the ~eight of sulphone and water. ~enerally, the
amount of sulphone used will be from 15 to 97 %w, preferably
; from 50 to 95 %w.
Any hydration catalyst may be used in the present
invention. Usuall~ such catalysts are acidic and may
be liquid (homogeneous) or solid (heterogeneous) under
the reaction conditions, with solid hydration catalysts
being preferred. $uitable liquid hydration catalysts
include sulphuric acid, alkane- or fluoroalkane sulphonic
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acids, e.g. methane sulphonic acid or trifluorome~hane ;-
sulphonic acid, aromatic sulphonic acids e.g. para-toluene
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-~ sulphonic acids, phosphoric acid or hydrofluoric acid,
;`, with sulphuric acid being preferred. ~ -
Suitable solid catalysts include zeolite alumino-
silicates alumina, thoria, zirconia, aluminium sulphate,
kaolin, titania, blue oxide of tungsten, tungsten sulphide,
nickel sulphide, unsupported nickel-tungsten sulphide
,.; .
`~ and supported nickel-tungsten sulphide. ~referred catalysts
, 20 are the acidic ion-exchange resins such as the sulphonated
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ion-exchange resins i.e. those containing a plurality
of sulphonic acid groups. Examples of such resins include
sulphonated styrene-divinylbenzene copolymers, sulphonated
phenol-formaldehyde resins and sulphonated benzene-formaldehyde
resins. The resin may be of the gel or macroreticular
type. The exchange capacity of the sulphonated resin
is preferably at least 2.0 meq/g dry ~eight with exchange
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capacities in the range of from 3.0 to 5.5 meq/g dry
weight being particularIy preferred.
Specific examples of suitable resins include Amberlite
IR 120H, Amberlite A252, Amberlite XE 307, Amberlyst
15H, Dowex 50-X-4, Dowex MSC-lH, ~uolite C-20, Permutit
- QH and Chempro C-20 (Amberlite, Amberlyst, Dowex, Duolite,
Permutit and Chempro are registered Trade ~arks).
Various olefinically unsaturated compounds may
be hydrated by the present inventicn. Such compounds
j 10 may be linear, branched or cyclic and may be alpha-
,
or internal olefins. Suitable compounds are the C
!f to C12, preferably C2 to C8, mono-olefinically unsaturated
-, hydrocarbons. Mixtures of olefins may be used. Specific -
examples include propylene, butenes, pentenes, hexenes, -
cyclohexenes, heptenes, octenes etc. The present invention
is particularly advantageous for hydratin~ cyclic olefins
such as cyclohexene or linear olefins such as propylene,
butene-1 or butene-2. Olefinically unsaturated compounds
"~f . in admixture with non-olefinic material e.g. alkanes
';J 20 may also be used, and a useful feedstock for the present
'~f ~ ~ invention is the so-called BB or butane/butene stream
,j which is mainly a mixture of isomeric butanes with
isomeric butenes. Such mixtures, whether fresh feedstock
or recycle mixtures, may be contacted, in an absorber,
with a sulphone/water mixture in order to differentially
~086333
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absorb the butenes from such mixtures. The sulphone/ ;~
water/butene mixture may then be fed to the reactor.
Sulpholane is a particularly useful solvent to differentially
absorb the butenes from such mixtures.
The products of the present invention are the alcohols
corresponding to the hydration product of the olefinically
unsaturated material used. The invention is particularly
useful for preparing secondary butylalcohol from butene-1
and/or butene-2.
The amounts of reactants and sulphone used in the
, present invention may vary between wide limits and
the preferred amounts depend upon whether the process
is a ba~ch or a continuous process. For a batch process ;
~ having a reaction time of from 0.1 to 100 hours it is
:J 15 preferred that the amount of catalyst is from 1 to 60 %w,
... .
the amount of olefinically unsaturated compound is from
1 to 25 %w with the remainder being sulphone and water,
the percentages being based on the weight of the total
j reaction mixture including sulphone. For a continuous
process using a solid catalyst, which is the preferred
process, the total amount of sulphone and water is suitably
from 0.2 to 50 litres/kg catalyst (dry weight)/hour
with amounts of from 1 to 25 litres/kg catalyst (dry
weight)/hour being preferred. For such a continuous
process the amount of olefinically unsaturated compound
is suitably from 0.05 to 10 kg/kg catalyst (dry weight)/hour
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with amounts of from 0.1 to 5 kg/kg catalyst (dry weight)/hour
being preferred. For a continuouc, process using a liquid
catalyst tne concentration of the catalyst is suitably
from 1 to 60 %w based on the total reaction mixture
including sulphone, and the total amount of sulphone
and water, and the amount of olefinically unsaturated
compound, are suitably from 0.05 to 12.5 litres/litre
reactor volume/hour and from 0.02 to 2.5 kg/litre reactor
~ volume/hour respectively. In order to avoid the formation ;;
-1 10 of undesirable amounts of ether by-products it is preferred
that the molar ratio of water to olefinically unsaturated
compound is at least 0.5, e.g. from 0.5 to 50:1.
The process may be carried out at elevated temperatures
e.g. at above 40C and is particularly suitable for
hydration reactions at temperatures of above 100C
e.g. from 100 to 220C. The reaction pressure is such
so as to malntain the sulphone and -~ater in the liquid
state. The olefinic material may be in the liquid or
gaseous state (trickle-flow operation). Suitable reaction
pressures are from 1 to 200 bars, preferably from 10 -
to 100 bars. ~`
The reaction product may be worked-up by any convenient
technique. For example the hydration reaction product ~ --
mixture may be stripped to remove unreacted olefinically
unsaturated compound and any non-olefinic material present.
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1~86333
The removed material may be recycled directly to the hydration
reactor or, if desirable, indirectly via an absorber as discussed
above. The stripped reaction product mixture may then be distilled
to obtain an overhead alcohol/water azeotrope and a sulphone/water
mixture. The azeotrope may be split, if desired, to recover
substantially pure alcohol and the sulphone/water mixture may be
recycled directly to the hydration reactor or, if desired,
indirectly via an absorber as discussed above.
The invention will be illustrated by reference to the
following Examples.
EXAMPLES I AND II
A reaction column (30x0.5 cm) was packed with 1.7 g dry
weight of a sulphonated styrene/divinylbenzene ion-exchange resin
(Amberlite XE307*) having an exchange capacity of about 3.9 meq/g
dry weight. Butene-l and water or a water/solvent mixture ~20:80
" ~-eight ratio) were passed over the catalyst bed to produce
secondary butyl alcohol (SBA). The reaction conditions and the
reslllts obtained are given in Table 1.
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EXAMPLES III and IV
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The procedure of Examples I and II, using water or a ~ .
. water/sulpholane mixture (20:80 weight ratio), was repeated using
;: propene and cyclohexene to produce isopropanol and cyclohexanol
:~ respectively. The reaction conditions are given in Table II.
-` The catalyst used for the hydration of propene was Amberlite XE307*
and the catalyst used for the hydration of cyclohexene was
. Amberlite A252* (a sulphonated styrene/divinylbenzene ion-exchange
~'! resin having an exchange capacity of about 4.8 meq/g dry - .
' 10 weight). The results are given in Table II.
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1~86333
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; EXAMPLE V
The procedure of Example I and II, using water or
a water~dimethylsulphone mixture (20:80 weight ratio),
was repeated. The reaction conditions and the results
are given in Table III.
Table III
Rxample
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Solvent None ~imethyl-
sulphone -~
Pressure (bar) 25 25
Temperature (C) 140 140 -~
Liquid hourly s~ace
velocity (l.kg- .h-1)* 11.7 11.7
Butene space velocitY
(kg,kg-l.h-~1.5 1.5
%w SBA in liquid phase* 1.21.8
Space time yield of SBA
(kg~kg-1.h-1) 0.14 0. 25
Butene conversion (%) 7 12
=======_===_===========
*liquld refers to water or water/dimethylsulphone mixture.
EXAMPLES VI to VIII-
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The procedure of Examples I and II, using water
or various water/sulpholane concentrations (expressed
~ as %w of sulpholane based on weight of water/sulpholane -
; mixture) was repeated. The reaction conditions and the
results are given in Table IV.
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10#6333
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EXAMPLE IX
The procedure of Example I and II using water or
Z a water/sulpholane mixture (5:95 weight ratio) was repeated.
: The reaction conditions and the results are given in
Table V.
Table V
Example
(l) IX
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Solvent None sulpholane
- Pressure (bar) 35 35
Temperature (C) 140 140
Liquid hourly space velocity ~
(l.kg-l.h-1)* 2.9 2.9 ~ .
Butene space velocity .
(kg.kg-l.h-l) 0.71 0.71
%w SBA in liquid phase * 1.7 4.8
15Space time yield of SBA
.,(kg.kg-l.h-l) O 0.19
~Butene conversion (%) 5 20
=================================================
* liquid refers to water or water sulpholane mixture :
EXAMPLE X
.
An autoclave was filled with 500 g of water (Example (j))
or 500 g of a water/sulpholane mixture (20:80 weight
ratio) (Example X), 72 g of butene-2 and 41 g of 100 ~w
sulphuric acid. The mixture was heated for 10 hours
at 140C and 37 bar (Example (j)) or 30 bar (Rxample
X). The smounts o~ recovered secondsry butylalcohol
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: were 11.5 g (Example (,i)) and 27.4 g (Example X) respectlvely.
The conversions of butene-2 were 12.1% (Example (,i))
and 28.8% (Example X) respectively.
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