CA1086333A - Hydration reactions - Google Patents
Hydration reactionsInfo
- Publication number
- CA1086333A CA1086333A CA277,005A CA277005A CA1086333A CA 1086333 A CA1086333 A CA 1086333A CA 277005 A CA277005 A CA 277005A CA 1086333 A CA1086333 A CA 1086333A
- Authority
- CA
- Canada
- Prior art keywords
- sulphone
- sulpholane
- water
- olefinically unsaturated
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A B S T R A C T
A process for the preparation of one or more alcohols comprising reacting one or more olefinically unsaturated compounds with water in the presence Or a hydration catalyst and a sulphone as solvent. In particular butenes can be converted to secondary butylalcohol using an acidic ion-exchange resin as catalyst and sulpholane as solvent.
A process for the preparation of one or more alcohols comprising reacting one or more olefinically unsaturated compounds with water in the presence Or a hydration catalyst and a sulphone as solvent. In particular butenes can be converted to secondary butylalcohol using an acidic ion-exchange resin as catalyst and sulpholane as solvent.
Description
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
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 ..... .
any appreciable increase in yield of alcohols.
The Applicants have now discovered that s~lphones are particularly useful solvents for hydration reactions.
'. :"1 - It has been found that sulphones are remarkably stable . . s ;' 25 solvents under hydration conditions.
Accordingly, the present invention is concerned ~ '.
- : . : . :. , .. . . , , 1~)86333 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.
,~1 ~~ The amount of sulphone used in the present invention ~
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i()86333 , 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 . ,,,~
acids, e.g. methane sulphonic acid or trifluorome~hane ;-sulphonic acid, aromatic sulphonic acids e.g. para-toluene :!
-~ 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 .. :, .
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 ~;
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 , ~
: ~ .
' ~(~86333 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
.
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 ; 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 ( ~: ) V
__________ ___________ ~ .
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-~ , .
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 -` -- 14 --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
_______ , :
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 , :` .
.
: 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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.
:
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 ..... .
any appreciable increase in yield of alcohols.
The Applicants have now discovered that s~lphones are particularly useful solvents for hydration reactions.
'. :"1 - It has been found that sulphones are remarkably stable . . s ;' 25 solvents under hydration conditions.
Accordingly, the present invention is concerned ~ '.
- : . : . :. , .. . . , , 1~)86333 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.
,~1 ~~ The amount of sulphone used in the present invention ~
` ~ ':
., : ,, .
.`~, .' ~.
, ~ ~ 3 ~ ~'`'~
i()86333 , 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 . ,,,~
acids, e.g. methane sulphonic acid or trifluorome~hane ;-sulphonic acid, aromatic sulphonic acids e.g. para-toluene :!
-~ 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 .. :, .
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 .
:' ' ' ' `. ' ' 1l~#6333 ` 5 . .
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 ~;
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 , ~
: ~ .
' ~(~86333 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.
'.
: ':
, .
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.
.
* Trade mark ~, i~86333 . .
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EXAMPLES III and IV
.
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.
.
* Trade mark ;
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1~86333 ; 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 ( ~: ) V
__________ ___________ ~ .
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-~ , .
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.
`~ 1086333 .~ - 13 - .
.~ :
.-~ "
O , . ~-- N
~, I S O IS~ O ~1 I ~ o~ N J ~I N 11 g H I
.- 1~ 1 11 ~., ~' ..
:~
I ,~ o L~ O ~1 0 N O Ot) I! ~ `
H ! i ~d N
.; , I I h O 11 :~ , XH I 'i ~ ~ C~ , ;
~ I N ~ ~I ~I ~
. ~ ) ,~ i' 11 . ~ ' a) , h -- I a.) ~ ~ ~ ~ " j~
I ~ . . . . " ,~ :
1~ I . --~ I O I Ll~ O ~ O ~ O ~ 11 :, . I ,, :
~d . o~ ~ ~ ~ ,1 ~0 ~ ~ ~ ~ o ~ ~ ~ g ~g O ~ ~ 3 .Y O 1 1 ~ - `
~ m a~ " c~ `
O ~'g ~, ~ ,1 :~ ~ Q, ~ 11 - :::
~' `
.~ , '~
10#6333 -` -- 14 --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
_______ , :
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 , :` .
.
: 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.
. , ', .
.
:
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 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:
(I) wherein R and R1 are aliphatic groups which may be joined together to form a cyclic sulphone.
(I) wherein R and R1 are aliphatic groups which may be joined together to form a cyclic sulphone.
2. A process as claimed in claim 1, characterized in that the sulphone of formula I is an acyclic sulphone and that R and R1 are the same or different C1 to C12 alkyl groups.
3. A process as claimed in claim 2, characterized in that both R and R1 are methyl groups.
4. A process as claimed in claim 1, characterized in that the sulphone of formula I is sulpholane or an alkyl-substituted sulpholane.
5. A process as claimed in claim 4, characterized in that the alkyl-substituted sulpholane is sulpholane substituted by at least one C1 to C8 alkyl group.
6. A process as claimed in claim 5, characterized in that the sulpholane substituted by at least one C1 to C8 alkyl group is 3-methyl sulpholane.
7. A process as claimed in claim 1 characterized in that the amount of sulphone used is from 15 to 97%w, based on the weight of sulphone and water.
8. A process as claimed in claim 1, characterized in that the olefinically unsaturated compound is a C2 to C8 mono-olefinically unsaturated hydrocarbon.
9. A process as claimed in claim 8, characterized in that the C2 to C8 mono-olefinically unsaturated hydrocarbon is cyclohexene, propylene or butene-1 and/or butene-2.
10. A process as claimed in claim 1, characterized in that the hydration catalyst is a solid hydration catalyst.
11. A process as claimed in claim 10, characterized in that the solid hydration catalyst is an acidic ion-exchange resin.
12. A process as claimed in claim 11, characterized in that the acidic ion-exchange resin is a sulphonated ion-exchange resin.
13. A process as claimed in claim 12, characterized in that the sulphonated ion-exchange resin is a sulphonated styrene-divinylbenzene copolymer.
14. A process as claimed in claim 11, characterized in that the process is a continuous process.
15. A process as claimed in claim 14, characterized in that the amount of sulphone and water is from 1 to 25 liters/kg catalyst (dry weight)/hour.
16. A process as claimed in claim 14 or claim 15, characterized in that the amount of olefinically unsaturated material is from 0.1 to 5 kg/kg catalyst (dry weight)/hour.
17. A process as claimed in claim 1, characterized in that the hydration catalyst is a liquid hydration catalyst.
18. A process as claimed in claim 17, characterized in that the liquid hydration catalyst is sulphuric acid.
19. A process as claimed in claim 1, characterized in that the reaction temperature is from 100 to 220°C.
20. A process as claimed in claim 1, characterized in that the reaction pressure is sufficient to maintain the sulphone and water in the liquid state and the olefinically unsaturated material in the liquid or gaseous state.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB19767/76A GB1518461A (en) | 1976-05-13 | 1976-05-13 | Hydration of unsaturated compounds |
| GB19,767/76 | 1976-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086333A true CA1086333A (en) | 1980-09-23 |
Family
ID=10134882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,005A Expired CA1086333A (en) | 1976-05-13 | 1977-04-26 | Hydration reactions |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS537605A (en) |
| AU (1) | AU505986B2 (en) |
| BE (1) | BE854337A (en) |
| BR (1) | BR7703053A (en) |
| CA (1) | CA1086333A (en) |
| DE (1) | DE2721206A1 (en) |
| ES (1) | ES458708A1 (en) |
| FR (1) | FR2351073A1 (en) |
| GB (1) | GB1518461A (en) |
| MX (1) | MX148116A (en) |
| NL (1) | NL7705193A (en) |
| ZA (1) | ZA772811B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6058893B2 (en) | 1979-04-27 | 1985-12-23 | 東亜燃料工業株式会社 | Method for producing tertiary alcohol |
| JPS6058894B2 (en) | 1979-06-26 | 1985-12-23 | 東亜燃料工業株式会社 | Manufacturing method of tertiary alcohol |
| JPS5634643A (en) * | 1979-08-31 | 1981-04-06 | Toa Nenryo Kogyo Kk | Preparation of tertiary butyl alcohol |
| US4306101A (en) * | 1980-11-05 | 1981-12-15 | Shell Oil Company | Olefin hydration process |
| JPS6059217B2 (en) | 1980-12-25 | 1985-12-24 | 東亜燃料工業株式会社 | Method for producing secondary alcohol |
| JPS58194828A (en) * | 1982-05-10 | 1983-11-12 | Asahi Chem Ind Co Ltd | Preparation of cycloalkanol |
| US4507512A (en) * | 1983-05-31 | 1985-03-26 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for hydration of olefins |
| JPS59222432A (en) * | 1983-05-31 | 1984-12-14 | Toa Nenryo Kogyo Kk | Method for hydrating olefin |
| JPS59222431A (en) * | 1983-05-31 | 1984-12-14 | Toa Nenryo Kogyo Kk | Method for hydrating olefin |
| DE3628008C1 (en) * | 1986-08-19 | 1987-11-05 | Deutsche Texaco Ag, 2000 Hamburg, De |
-
1976
- 1976-05-13 GB GB19767/76A patent/GB1518461A/en not_active Expired
-
1977
- 1977-04-26 CA CA277,005A patent/CA1086333A/en not_active Expired
- 1977-05-06 BE BE1008115A patent/BE854337A/en not_active IP Right Cessation
- 1977-05-11 NL NL7705193A patent/NL7705193A/en not_active Application Discontinuation
- 1977-05-11 ES ES458708A patent/ES458708A1/en not_active Expired
- 1977-05-11 AU AU25076/77A patent/AU505986B2/en not_active Expired
- 1977-05-11 MX MX169089A patent/MX148116A/en unknown
- 1977-05-11 DE DE19772721206 patent/DE2721206A1/en not_active Withdrawn
- 1977-05-11 JP JP5326877A patent/JPS537605A/en active Pending
- 1977-05-11 BR BR3053/77A patent/BR7703053A/en unknown
- 1977-05-11 ZA ZA00772811A patent/ZA772811B/en unknown
- 1977-05-11 FR FR7714367A patent/FR2351073A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7705193A (en) | 1977-11-15 |
| AU505986B2 (en) | 1979-12-06 |
| ZA772811B (en) | 1978-04-26 |
| FR2351073B1 (en) | 1978-11-03 |
| JPS537605A (en) | 1978-01-24 |
| ES458708A1 (en) | 1978-08-01 |
| BR7703053A (en) | 1978-01-31 |
| MX148116A (en) | 1983-03-16 |
| GB1518461A (en) | 1978-07-19 |
| DE2721206A1 (en) | 1977-11-24 |
| BE854337A (en) | 1977-11-07 |
| FR2351073A1 (en) | 1977-12-09 |
| AU2507677A (en) | 1978-11-16 |
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