CA1154014A - Proton-catalysed reactions in which water is not a stoichiometer reactant catalysed by metal cation- exchanged layered clays - Google Patents
Proton-catalysed reactions in which water is not a stoichiometer reactant catalysed by metal cation- exchanged layered claysInfo
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- CA1154014A CA1154014A CA000367156A CA367156A CA1154014A CA 1154014 A CA1154014 A CA 1154014A CA 000367156 A CA000367156 A CA 000367156A CA 367156 A CA367156 A CA 367156A CA 1154014 A CA1154014 A CA 1154014A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/64—Preparation of compounds containing amino groups bound to a carbon skeleton by disproportionation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to the use of metal cation-exchangeable layered clays in organic reactions catalysed by protons in which water is not a stoichiometric reactant, Such organic reactions include the reaction of an olefin with a carboxylic acid in the liquid or vapour phase to produce an ester, e.g. reaction of ethylene with acetic acid to produce ethyl acetate, reaction of an alkanol with linear olefin at temperatures above 100°C to produce an ether, the conversion of primary or secondary aliphatic alcohols or polyols into ethers, the conversion of primary or secondary amines into secondary and tertiary a?ites respectively and the reaction of an olefin with benzene to produce an alkyl benzene.
The invention relates to the use of metal cation-exchangeable layered clays in organic reactions catalysed by protons in which water is not a stoichiometric reactant, Such organic reactions include the reaction of an olefin with a carboxylic acid in the liquid or vapour phase to produce an ester, e.g. reaction of ethylene with acetic acid to produce ethyl acetate, reaction of an alkanol with linear olefin at temperatures above 100°C to produce an ether, the conversion of primary or secondary aliphatic alcohols or polyols into ethers, the conversion of primary or secondary amines into secondary and tertiary a?ites respectively and the reaction of an olefin with benzene to produce an alkyl benzene.
Description
Case 4905Cog. ~1~40i4 P~OTO~-CATALYSED REACTIONS IN WHICH WATER IS NOT A STOICHIOMETRIC
REACTANT CATALYSED BY METAL CATION-EXCHAN OED LAYERED CLAYS
The present invention relates generally to proton-catalysed organic reactions in which interlamellar water is not one of the stoichiometric reactants and in particular to the use of a cation-e~changeable layered clay in which the exchangeable cation is a metal S cation as catalysts in ~uch reactions.
Y,any different types of organic reaction are catalysed by protons or, to give them another name, hydrogen ions. Typical of such reactions are olefin hydration in which the product is an alcohol, esterification of an alcohol with an acid in which the product is an ester and the decomposition of organic hydroperoxides, e.g. cumene h~droperoxide in which the products are phenol and acetone. Generally t~e protons are provided by the dissociation of a strong mineral acid or a strong organic acid. Thus sulphuric acid and para-toluene sulphonic acid have been used extensively as catalysts in the industrial production of esters, and phosphoric acit, usually supported on silica, is a catalyst commonly employed in the commercial production of ethanol. Comparatively recently hydrogen ion-exchanged resins have been employed as catalysts in, for example, the production of alkanols.
ZO In the Journal of Physical Chemistry, Volume 44, No. 2, February, 194OJ PP 180 to 184, there is disclosed the preparstion of an acid bentonite by electrodialyzing a 4 per cent suspension of Wyoming bentonite in a cell of the Mattson type until the catholyte liquor is no looger alkaline, followed by ion-exchange of the acid bentonite vith an aqueous solution of a metal salt to produce a metal cation-e~changet bentonite and the use of the metal cation-exchanged bentonite so-prepared as catalyst in the decomposition of hydrogen peroside. ~ ~ ~
' ' ' ',:
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~154Vl~
Thereafter in the Journal of Catalysis 58, 238-252 (1979) Adams et al disclosed that metal cation-exchanged water-intercalated clays such as metal cation-exchanged water-intercalated montmorillonites will convert alkenes to thecorresponding bis-sec-alkyl ethers. In some circumstances 100~ conversion of usable intercalated water to ether was achieved but it was not possible to make the reaction self-sustaining by the addition of water to the reaction.
We have now found that cation-exchangeable layered clays in which the exehangeable cation is a metal cation catalyse organic reactions which are catalysed by protons in which intercalated water is not one of the stoichiome-tric reactants. An example of such a reaction is the direct reaction of olefins with acids to make esters.
Accordingly the present invention provides a process for carrying out a proton-catalysed organic reaction in which intercalated water is not one of the stoichiometric reaetants employing as catalyst a metal eation-exehangeable material eharaeterized in that as the eation-exehangeable material there is used a layered clay in which the exchangeable cation is a metal cation.
A layered clay within the con-text of the present specification is a clay having a lamellar structure with interlamel]ar spaces disposed between the lamellar layers. Typical of such clays is montmorillonite which has an ideal-ized stoichiometric composition corresponding to NaO 67[A13 33Mgo 67](Si8)O20(OH)4.
Structurally it comprises a central octahedral eo-ordincltion layer containinq aluminiarm and magnesi~un c~xides .Illd hyclroxLdt3s sanclw:Lched bt~twean two tetrahedral eo-ordination layers corrtainillg silicon oxide. Normally irl nature cations arepresent to compensate for the charge imbalance caused by isomorphous subs-titu-tion of Mg for Al in the octahedral layer, and/or Al or other ions for Si in -the tetrahedral layers. The octahedral and tetrahedral regions are tightly bound together to form a lamellar layer. The space between the lamellar .~
~ - 2 -'.
" - '~
layers, i.e. the interlamellar space, is normally occupied by exchangeable Ca or ~a ions. The distance between the interlamellar layers can be substantiallyincreased by absorption of a variety of polar molecules such as water, ethylene glycol, amines etc., which enter the - 2a -, 1~4014 inter1a~ellar space and in doing so push apart the lamellar layers.
rne interlamellar spaces tend to collapse when the molecules occupying the s?ace are removed, for example by heating the clay at a high temperature. Both natural and synthetic clays having a layered structure are well known and may be used in the process of the - invention both before and after exchange of the metal cations normally associated therewith with other metal cations. Besides montmorillonites such as bentonite and Fullers Earths J other types of suitable clays include hectorites, beidellites, vermiculites and nontronite. A preferred clay is a bentonite, such as Wyoming bentonite.
'.s hereinbefore described the clays in their natural state norma'ly contain exchangeable sodium or calcium ions in the interla~ellar space. Such clays have some catalytic activity in the process of the present invention. In order to bestow increased catal~tic activity on the clay it is necessary to exchange some or all of the exchangeable metal cations with cations of one or more other suitable metals. Examples of suitable metals include chromium, a1u~inium, cobalt, nickel, iron, copper and vanadium, of which chrom~u~ and aluminium are preferred.
Ion-exchange itself is a technique well known in the art.
Although any of the variants of that technique may be used in the preparation of catalysts useful in the process of the present invention the metal cation-exchanged clay is preferably prepared by exchanging the sodium or calciwm or other exchangeable cations in a natural clay ~ith an aqueous solution of a metal salt rather than by exchanging with ammonium ions from an aqueous solution of an ammonium compound to form the ammonium ion-exchanged clay, followed by calcination of the ammonium ion-exchanged clay to form the hydrogen-ion e~changed clay and subsequent exchange with an aqueous solution ofa metal salt to produce the metal cation-exchanged clay. This preference arises from the desirability of avoiding excessively high temjperatures, such as those obtaining during calcination because their use tents to collapse the lamellar structure of the clay and lead to inactive catalysts.
... .. . . .
:: .
.
,: : -,, ;
.
, l~S4014 ., Techniques for separating the metal cati~n-exchanged clay from~~
the ion-exchange media and excess ions are well known. Any suitable solid/liquid separation procedure can be used. Decantation or centrifugation are two preferred methods for solid/liquid separation.
After exchange the metal cation-exchanged clay is preferably washed until all extraneous metal cations are removed and dried, suitably at a temperature which does not result in collapse of the interlamellar space. The temperature will depend to some extent on the clay selected but for certain types of exchanged bentonites temperatures up to 220C, preferably from 80 to 220C are suitable.
Cation-exchangeable layered clays in which the exchangeable cation is a metal cation may be used as catalysts in all organic reactions catalysed by protons in which intercalated water is not one of the stoichiometric reactants. Advantages arising from their use are that they can be readily separated from the reaction mixture which renders them useful in continuous processes, and they are less corrosive than the strong acids conventionally employed. We have found the clays to be particularly useful catalysts in certain specific organic reactions, such as the production of esters by the reaction of an olefin with a carboxylic acid and the production of ethers by reaction of an alcohol and certain alkenes.
In a particular aspect therefore the present invention provides a process for the production of esters which process comprises reacting one or more olefins with one or re carboxylic acids in the presence as catalyst of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation under reaction conditions which result in the formation of an ester.
With regard to the olefin reactant any suitable olefin may be employed. Suitable olefins include ethylene, propylene, butenes, pentenes and hexenes, diolefins such as butadieneand cyclic olefins such as cyclohexene. Mixtures of olefins such as those commonly encountered in refinery streams may also be used iE so desired. The amount of olefin employed may be greater or less than the stoichiometric amount required to react completely with the acid.
Both aromatic and aliphatic carboxylic acids may be used.
~154~ ~
Suitable 21iphatic acids include formic, acetic, propionic and butyric acids. Of the aromatic acids phthalic acids, especially ortho-pkthalic acid, may be employed. Mixtures of acids may also be used.
Preferably the olefin is ethylene, the carboxylic acid is acetic acid and the ester produced is ethyl acetate.
A preferred metal cation-exchanged layered clay for use in this process is a chromium or aluminium ion-exchanged sodium benton;te.
~he catal~st ~ay suitably be activated before use by heating in air at a temperature up to 220C, preferably from 80 to 220C.
The process ~ay be carried out in the liquid phase or in the vapour phase, preferably in the liquid phase. Reaction conditions which result in the formation of esters will depend on whether the process is carried out in the liquid or the vapour phase and to some e~tent on the nature of the reactants.
In the liquid phase the pressure is suitably that pressure which maintains a liquid phase at the reaction temperature. In the case of olefins with suitably high boiling points, e.g. hexene-l, the reaction may for e~.ample be conveniently carried out at the reflux temperature o. the reactants and under atmospheric pressure, or at higher temperatures and pressures if so desired. In the case of ethylene, for example, initial pressures in the range 25 to 150 bar may suitably be employed. Generally the temperature may suitably be in the range 100 to 300C, preEerably 150 to 250C. Solvents may be employed if desired. Suitable solvents include hydrocarbons, e.g. alkanes such as ethane, hexane and octane.
In the ~apour phase the conditions must be chosen so that the reactants do not liquefy, for example acetic acid must be fed at atmospheric or slightly higher pressure otherwise it would liquefy at higher pressures. Generally the temperature will suitably be in the range lZ0 to 180C, preferably 140 to 160C. The residence time, ~hich is defined as:-~olume of catalyst in mls ~apour flow rate (in mls/sec at NTP) may suitably be in the range 10 to 60 secs, preferably 20 to 40 secs.
The process may be carried out batchwise or continuously, preferably continuously. The batchwise liquid phase production of ethyl acetate, for example, may conveniently be carried out by charging acetic acid and catalyst to an autoclave, pressurising the autoclave with ethylene and maintaining the autoclave at the reaction temperature. The reaction time should not be unduly protracted otherwise the selectivity for the conversion of acetic acid to ethyl acetate may be adversely affected. Thus at an approximately 2:1 molar ratio of ethylene to acetic acid, an initial ethylene pressure of 55 bar and a temperature of 200C, the reaction time should preferably not exceed 5 hours. At the completion of the reaction the catalyst may be recovered from the product, suitably by filtration, centrifugation or decantation and the product worked up in known manner to recover ethyl acetate therefrom. The catalyst may thereafter be re-used in a further batch reaction with or without intervening treatment.
The invention also provides a process for the production of ethers which process comprises reacting at a temperature above lOODC
and in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation one or more alcohols with one or more olefins having the structure:-Rl CH=CHR2wherein Rl and R2 are independently H, alkyl or aryl or are bonded together to form a ring.
Suitable alcohols include methanol, ethanol, propanols, butanols, pentanols and hexanols.
With regard to the olefin any suitable olefin may be employed.
Suitable olefins include ethylene, propylene, butenes, pentenes and hexenes, diolefins such as butadiene and cyclic olefins such as cyclohexene. Preferably the olefin i9 a C3 to C6 olefin. Mixtures of olefins such as those commonly encountered in refinery streams may also be used if so desired. l`he amount of olefin employed may be greater or less than the stoiGhiometric amount required to react completely with the alcohol.
A preferred catalyst for use in this process is an aluminium or chromium ion-exchanged sodium bentonite. The catalyst may suitably be .
1~54014 a_tivated before use by heating in air at a temperature up to 200C, p-eferably from 80 to i60C.
Ihe process may be carried out in the liquid phase or in the vepour phase, preferably in the liquid phase. Reaction conditions 5 ~--,ich result in the formation of an ether will depend on whether the p:ocess is carried out in the liquid or the vapour phase and to some e~tent on the nature of the reactants.
In the liquid phase the pressure is suitably that pressure which maintains a liquid phase at the reaction temperature. In the case of oIe~~ins with suitsbly high boiling points the reaction may for example be co~veniently carried out at the reflux temperature of the reactants a~d under atmospheric pressure, or at higher temperatures and p-essures if so desired. Generally the temperature may be between 100 ald 300C, preferebly 150 to 250C. The particular temperature e-ployed within the aforesaid ranges will depend upon the nature of tie olefins. Sol~ents may be employed if so desired. Suitable solvents include hydrocarbons, e.g. alkanes such as ethane, hexane and o~tane.
The process may be carried out batchwise or continuously, p eferably continuously.
Other proton-catalysed reactions of interest which are catalysed b~ cation-exchangeable layered clays in which the exchangeable cation is a ~etal cation include:-(i) the production of ethers by reacting at elevated temperature and a pressure such that the reactants are maintained in the liquid phase one or more primary or secondary aliphatic alcohols or polyols in the presence of a metal cation-exchangeable lsyered clay in Yhich the exchangeable cation is a metal cation.
The ethers are believed to be produced by condensation of two alcohol functions accompanied by elimination of water.
With regard to the primary aliphatic alcohol reactant suitable alcohols~include methanol, ethanol, propan-l-ol, butan-l-ol, pentan-l-ol, hexan-l-ol, heptan-l-ol and octan-l-ol.
The principal ether in the product resulting from the reaction of a primary aliphatic alcohol in the presence of the lamellar clays is the corresponding l,l-ether, though the corresponding 11~01~. .
1,2-ether, may also be formed. Alkenes and alkene dimers may also be formed. Generally the proportion of alkene in the product increases as the carbon number of the reactant alcohol increases.
With regard to the secondary aliphaeic alcohol reactant suitable alcohols include straight-chain alcohols such as propan-2-ol, butan-2-ol, pentan-2-ol, hexan-2-ol and hexan-3-ol,and cyclohexanol, of which propan-2-ol and butan-2-ol are preferred. The ethers predominating in the product resulting from the reaction of alkan-2-ol and alkan-3-ols are the 2,2- and 3,3- ethers respectively. Alkenes and alkene dimers are also formed.
The reactant may also be a polyol such as an alkylene glycol. A suitable alkylene glycol is ethylene glycol which produces a mixture of dioxan, and di-, tri-, tetra- etc., ethylene glycol. A preferred alkylene glycol is diethylene glycol which produces dioxan in high conversions in the presence of the lamellar clay. Additionally mixtures of alcohols and/or polyols may be used if so desired.
The elevated temperature may suitably be in the range from . 100 to 300C, preferably from 150 to 225C.
(ii) the production of ethers by reacting one or mo~e epoxides in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
Thus for example reaction of ethylene oxide yields - 1,4-dioxane and 2 methyl-1,3-dioxan. Other epoxides produce cyclic ethers but alpha, betà-ùnsaturAted aldehyde9 may al~o be formed. The proportion of the un~aturated aldehyde generally tends to increase with the carbon number of the epoxide.
(iii) the formation of esters by reacting one or more epoxides with one or more carboxylic acids in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation as catalyst.
Thus for example ethylene glycol diacetate and 2-hydroxy ethyl acetate can be obtained by reaction of ethylene oxide and liS4014 acetic acid.
(iv) the formation of ethers by reacting one or more epoxides ~ith one or more alcohols, polyols or polysaccharides in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
rnus for example 2-ethoxy ethanol, diethylene glycol nonoethyl ether, ethylene glycol diethyl ether and diethylene gl~col diethyl ether can be obtained by reaction of ethylene oxide and ethanol.
~0 (v) the formation of alpha, beta-unsaturated aldehydes by reac.ing aldehydes with a cation exchangeable layered clay in ~hic~ the exchangeable cation is a metal cation.
Thus for example but-2-en-1-al can be obtained by reaction of acetaldehyde.
tvi) the production of a secondary or a tertiary amine by reacting at elevated temperature a primary or a secondary amine having a methylene group adjacent to an amino group in the presence as catalyst of a metal cation-exchangeable layered clay, reaction of a primary amine resulting in the formation of a secondary amine and reaction of a secondary amine resulting in the formation of a tertiary amine.
Provided there is a methylene group adjacent to the amino group the primary amine may be an aliphatic, cycloaliphatic or aromatic amine. Examples of suitable primary amines which may be ~5 employed in the process of the invention include hexan-l-amine, benzylamine and cyclohexylamine. The products are believed to be formed by condensation of two molecules of the primary amine accoh2anied by the elimination of a single molecule of ammonia.
Thus, for example, in the ca~e of benzylamine the reaction may be represented as follows:-~.
.
'-.
~lS~3~, .
H2NH2 H2NH2 Elevate ~ CH2 ~ N CH
~ +~ = e Catalyst The secondary amine having a methylene group adjacent to an amino group is preferably a heterocyclic compound such as, for example, pyrrolidine or piperidine. In the case of cyclic secondary amines the products are believed to be formed by a mechanism involving ring-opening and condensation with the elimination of ammonia. Thus, for example, in the case of pyrrolidine the reaction may be represented as follows:-Elevated ~ ~Temperatur~e ~ ~ H
H Catalyst (I) (II~
The process may suitably be carried out at a temperature in the range 150 to 275C, preferably in the range 175 to 2500CA The reaction time in a batch process in which the amine and catalyst are charged to a reactor and maintained at elevated temperature may suitably be in the range from 5 to 120 hours, preferably from 30 to 120 hours.
(vii) the production of polyphenylenemethylene by reacting benzyl alcohol in the presence as catalyst of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
The polymer contain9 repeat unit9 of the type:
-C~c~
in which the average value of n is 10.
(vii) the production of thioethers by reacting alkanthiols at elevated temperature in the presence of a cation-~, 10 , .
:' ' , :: . . , .' ~lS4014 exchangeable layered clay in which the exchangeable cation is a metal cation.
tix) the production of alkyl aromatic compounds by reacting one or m~re olefins, e.g. the production of ethylbenzene by reacting benzene with ethylene, and isopropylbenzene by reacting benzene with propylene, at elevated temperatures suitably up to 250C
preferably in the range 175 to 250C and elevated temperature and atmospheric or elevated pressure.
(xi) the production of alcohols by the hydration of olefins at elevated temperature and pressure where the water reactant consumed is more than the intercalated water contained in the clay.
The invention will now be illustrated by reference to the following Examples.
All analytical results were determined using gas chro~atography and the identity of the products were confirmed by comparison with authentic materials, mass spectroscopy or nuclear ~agnetic resonance spectroscopy.
Pæ PARATION OF METAL CATION-EXCHANGED LAYERED CLAY
-Pinally divided sodium bentonite was cation exchanged with 0.5 M
aqueous solutions of appropriate salts for periods of approximately 24 hours (the chromium salt employed was Cr2(SO4)3; the aluminium salt e2ployed uas A12(S04)3.16H2O~. The solutions were mechanically stirred during the first 2 hours of a period of 24 hours, after which the solid was washed repeatedly with deionised water until the excess cations had been removed. Surplus liquid was removed from the solid u~ing a teat-pipette prior to drying in a vacuum oven at 60C. When t~e clay was visibly dry it W8~ ground until it passet 140 BSS mesh sieve. The cation-exchanged clay was then equilibrated over granular a~hydrous calcium chloride in a dessicator for a minimum period of 24 hours.
PRODUCTIO~ OF ESTERS B~' REACTION OF AN OLEFIN WITH A CARBOXYLIC ACID
_ THE LIQIUD PHASE.
Example 1 Cr3~-exchanged bentonite (0.5 g), hex-l-ene (5 ml) and acetic acid (1.5 ml) were placed in a standard steel reactor of capacity 20 : ~ , , .
.
115401'~, ml. The reactor was closed by a screw cap provided with an 0-ring seal and immersed up to the screw cap in a silicone oil bath which was maintained at 200C. After 4 hours the reactor was removed from the bath~ cooled and its contents analysed . The results in terms of the weight percentage of individual products in the product mixture (rounded to the nearest whole number) are given in Table 1.
Example 2 Example 1 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and the acetic acid was replaced by propionic acid.
Example 3 Example 1 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and acetic acid was replaced by isobutyric acid.
Example 4 Example 1 was repeated except that hex-l-ene was replaced by hept-l-ene.
Example 5 Example 1 was repeated except that hex-l-ene was replaced by oct-l-ene.
Exa~ple 6 Example l was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and hex-l-ene was replaced by 4-methylpent-l-ene.
Example 7 - Example l was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite ~nd hex-l-ene wa8 repl~ced by hex-2-ene.
The results of Examples 1 to 7 are given in Table 1.
Example 8 Acetic acid (80 g) and A13+-exchanged Wyoming Bentonite catalyst (10 g, 9.4~ wt Al) were charged to a 100 ml stirred autoclave. The autoclave was charged with ethylene to a pressure of 55 bar tethylene:acetic acid le ratio 2:1). The temperature of the autoclave was raised to 250C and maintained at this temperature for
REACTANT CATALYSED BY METAL CATION-EXCHAN OED LAYERED CLAYS
The present invention relates generally to proton-catalysed organic reactions in which interlamellar water is not one of the stoichiometric reactants and in particular to the use of a cation-e~changeable layered clay in which the exchangeable cation is a metal S cation as catalysts in ~uch reactions.
Y,any different types of organic reaction are catalysed by protons or, to give them another name, hydrogen ions. Typical of such reactions are olefin hydration in which the product is an alcohol, esterification of an alcohol with an acid in which the product is an ester and the decomposition of organic hydroperoxides, e.g. cumene h~droperoxide in which the products are phenol and acetone. Generally t~e protons are provided by the dissociation of a strong mineral acid or a strong organic acid. Thus sulphuric acid and para-toluene sulphonic acid have been used extensively as catalysts in the industrial production of esters, and phosphoric acit, usually supported on silica, is a catalyst commonly employed in the commercial production of ethanol. Comparatively recently hydrogen ion-exchanged resins have been employed as catalysts in, for example, the production of alkanols.
ZO In the Journal of Physical Chemistry, Volume 44, No. 2, February, 194OJ PP 180 to 184, there is disclosed the preparstion of an acid bentonite by electrodialyzing a 4 per cent suspension of Wyoming bentonite in a cell of the Mattson type until the catholyte liquor is no looger alkaline, followed by ion-exchange of the acid bentonite vith an aqueous solution of a metal salt to produce a metal cation-e~changet bentonite and the use of the metal cation-exchanged bentonite so-prepared as catalyst in the decomposition of hydrogen peroside. ~ ~ ~
' ' ' ',:
'.
~154Vl~
Thereafter in the Journal of Catalysis 58, 238-252 (1979) Adams et al disclosed that metal cation-exchanged water-intercalated clays such as metal cation-exchanged water-intercalated montmorillonites will convert alkenes to thecorresponding bis-sec-alkyl ethers. In some circumstances 100~ conversion of usable intercalated water to ether was achieved but it was not possible to make the reaction self-sustaining by the addition of water to the reaction.
We have now found that cation-exchangeable layered clays in which the exehangeable cation is a metal cation catalyse organic reactions which are catalysed by protons in which intercalated water is not one of the stoichiome-tric reactants. An example of such a reaction is the direct reaction of olefins with acids to make esters.
Accordingly the present invention provides a process for carrying out a proton-catalysed organic reaction in which intercalated water is not one of the stoichiometric reaetants employing as catalyst a metal eation-exehangeable material eharaeterized in that as the eation-exehangeable material there is used a layered clay in which the exchangeable cation is a metal cation.
A layered clay within the con-text of the present specification is a clay having a lamellar structure with interlamel]ar spaces disposed between the lamellar layers. Typical of such clays is montmorillonite which has an ideal-ized stoichiometric composition corresponding to NaO 67[A13 33Mgo 67](Si8)O20(OH)4.
Structurally it comprises a central octahedral eo-ordincltion layer containinq aluminiarm and magnesi~un c~xides .Illd hyclroxLdt3s sanclw:Lched bt~twean two tetrahedral eo-ordination layers corrtainillg silicon oxide. Normally irl nature cations arepresent to compensate for the charge imbalance caused by isomorphous subs-titu-tion of Mg for Al in the octahedral layer, and/or Al or other ions for Si in -the tetrahedral layers. The octahedral and tetrahedral regions are tightly bound together to form a lamellar layer. The space between the lamellar .~
~ - 2 -'.
" - '~
layers, i.e. the interlamellar space, is normally occupied by exchangeable Ca or ~a ions. The distance between the interlamellar layers can be substantiallyincreased by absorption of a variety of polar molecules such as water, ethylene glycol, amines etc., which enter the - 2a -, 1~4014 inter1a~ellar space and in doing so push apart the lamellar layers.
rne interlamellar spaces tend to collapse when the molecules occupying the s?ace are removed, for example by heating the clay at a high temperature. Both natural and synthetic clays having a layered structure are well known and may be used in the process of the - invention both before and after exchange of the metal cations normally associated therewith with other metal cations. Besides montmorillonites such as bentonite and Fullers Earths J other types of suitable clays include hectorites, beidellites, vermiculites and nontronite. A preferred clay is a bentonite, such as Wyoming bentonite.
'.s hereinbefore described the clays in their natural state norma'ly contain exchangeable sodium or calcium ions in the interla~ellar space. Such clays have some catalytic activity in the process of the present invention. In order to bestow increased catal~tic activity on the clay it is necessary to exchange some or all of the exchangeable metal cations with cations of one or more other suitable metals. Examples of suitable metals include chromium, a1u~inium, cobalt, nickel, iron, copper and vanadium, of which chrom~u~ and aluminium are preferred.
Ion-exchange itself is a technique well known in the art.
Although any of the variants of that technique may be used in the preparation of catalysts useful in the process of the present invention the metal cation-exchanged clay is preferably prepared by exchanging the sodium or calciwm or other exchangeable cations in a natural clay ~ith an aqueous solution of a metal salt rather than by exchanging with ammonium ions from an aqueous solution of an ammonium compound to form the ammonium ion-exchanged clay, followed by calcination of the ammonium ion-exchanged clay to form the hydrogen-ion e~changed clay and subsequent exchange with an aqueous solution ofa metal salt to produce the metal cation-exchanged clay. This preference arises from the desirability of avoiding excessively high temjperatures, such as those obtaining during calcination because their use tents to collapse the lamellar structure of the clay and lead to inactive catalysts.
... .. . . .
:: .
.
,: : -,, ;
.
, l~S4014 ., Techniques for separating the metal cati~n-exchanged clay from~~
the ion-exchange media and excess ions are well known. Any suitable solid/liquid separation procedure can be used. Decantation or centrifugation are two preferred methods for solid/liquid separation.
After exchange the metal cation-exchanged clay is preferably washed until all extraneous metal cations are removed and dried, suitably at a temperature which does not result in collapse of the interlamellar space. The temperature will depend to some extent on the clay selected but for certain types of exchanged bentonites temperatures up to 220C, preferably from 80 to 220C are suitable.
Cation-exchangeable layered clays in which the exchangeable cation is a metal cation may be used as catalysts in all organic reactions catalysed by protons in which intercalated water is not one of the stoichiometric reactants. Advantages arising from their use are that they can be readily separated from the reaction mixture which renders them useful in continuous processes, and they are less corrosive than the strong acids conventionally employed. We have found the clays to be particularly useful catalysts in certain specific organic reactions, such as the production of esters by the reaction of an olefin with a carboxylic acid and the production of ethers by reaction of an alcohol and certain alkenes.
In a particular aspect therefore the present invention provides a process for the production of esters which process comprises reacting one or more olefins with one or re carboxylic acids in the presence as catalyst of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation under reaction conditions which result in the formation of an ester.
With regard to the olefin reactant any suitable olefin may be employed. Suitable olefins include ethylene, propylene, butenes, pentenes and hexenes, diolefins such as butadieneand cyclic olefins such as cyclohexene. Mixtures of olefins such as those commonly encountered in refinery streams may also be used iE so desired. The amount of olefin employed may be greater or less than the stoichiometric amount required to react completely with the acid.
Both aromatic and aliphatic carboxylic acids may be used.
~154~ ~
Suitable 21iphatic acids include formic, acetic, propionic and butyric acids. Of the aromatic acids phthalic acids, especially ortho-pkthalic acid, may be employed. Mixtures of acids may also be used.
Preferably the olefin is ethylene, the carboxylic acid is acetic acid and the ester produced is ethyl acetate.
A preferred metal cation-exchanged layered clay for use in this process is a chromium or aluminium ion-exchanged sodium benton;te.
~he catal~st ~ay suitably be activated before use by heating in air at a temperature up to 220C, preferably from 80 to 220C.
The process ~ay be carried out in the liquid phase or in the vapour phase, preferably in the liquid phase. Reaction conditions which result in the formation of esters will depend on whether the process is carried out in the liquid or the vapour phase and to some e~tent on the nature of the reactants.
In the liquid phase the pressure is suitably that pressure which maintains a liquid phase at the reaction temperature. In the case of olefins with suitably high boiling points, e.g. hexene-l, the reaction may for e~.ample be conveniently carried out at the reflux temperature o. the reactants and under atmospheric pressure, or at higher temperatures and pressures if so desired. In the case of ethylene, for example, initial pressures in the range 25 to 150 bar may suitably be employed. Generally the temperature may suitably be in the range 100 to 300C, preEerably 150 to 250C. Solvents may be employed if desired. Suitable solvents include hydrocarbons, e.g. alkanes such as ethane, hexane and octane.
In the ~apour phase the conditions must be chosen so that the reactants do not liquefy, for example acetic acid must be fed at atmospheric or slightly higher pressure otherwise it would liquefy at higher pressures. Generally the temperature will suitably be in the range lZ0 to 180C, preferably 140 to 160C. The residence time, ~hich is defined as:-~olume of catalyst in mls ~apour flow rate (in mls/sec at NTP) may suitably be in the range 10 to 60 secs, preferably 20 to 40 secs.
The process may be carried out batchwise or continuously, preferably continuously. The batchwise liquid phase production of ethyl acetate, for example, may conveniently be carried out by charging acetic acid and catalyst to an autoclave, pressurising the autoclave with ethylene and maintaining the autoclave at the reaction temperature. The reaction time should not be unduly protracted otherwise the selectivity for the conversion of acetic acid to ethyl acetate may be adversely affected. Thus at an approximately 2:1 molar ratio of ethylene to acetic acid, an initial ethylene pressure of 55 bar and a temperature of 200C, the reaction time should preferably not exceed 5 hours. At the completion of the reaction the catalyst may be recovered from the product, suitably by filtration, centrifugation or decantation and the product worked up in known manner to recover ethyl acetate therefrom. The catalyst may thereafter be re-used in a further batch reaction with or without intervening treatment.
The invention also provides a process for the production of ethers which process comprises reacting at a temperature above lOODC
and in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation one or more alcohols with one or more olefins having the structure:-Rl CH=CHR2wherein Rl and R2 are independently H, alkyl or aryl or are bonded together to form a ring.
Suitable alcohols include methanol, ethanol, propanols, butanols, pentanols and hexanols.
With regard to the olefin any suitable olefin may be employed.
Suitable olefins include ethylene, propylene, butenes, pentenes and hexenes, diolefins such as butadiene and cyclic olefins such as cyclohexene. Preferably the olefin i9 a C3 to C6 olefin. Mixtures of olefins such as those commonly encountered in refinery streams may also be used if so desired. l`he amount of olefin employed may be greater or less than the stoiGhiometric amount required to react completely with the alcohol.
A preferred catalyst for use in this process is an aluminium or chromium ion-exchanged sodium bentonite. The catalyst may suitably be .
1~54014 a_tivated before use by heating in air at a temperature up to 200C, p-eferably from 80 to i60C.
Ihe process may be carried out in the liquid phase or in the vepour phase, preferably in the liquid phase. Reaction conditions 5 ~--,ich result in the formation of an ether will depend on whether the p:ocess is carried out in the liquid or the vapour phase and to some e~tent on the nature of the reactants.
In the liquid phase the pressure is suitably that pressure which maintains a liquid phase at the reaction temperature. In the case of oIe~~ins with suitsbly high boiling points the reaction may for example be co~veniently carried out at the reflux temperature of the reactants a~d under atmospheric pressure, or at higher temperatures and p-essures if so desired. Generally the temperature may be between 100 ald 300C, preferebly 150 to 250C. The particular temperature e-ployed within the aforesaid ranges will depend upon the nature of tie olefins. Sol~ents may be employed if so desired. Suitable solvents include hydrocarbons, e.g. alkanes such as ethane, hexane and o~tane.
The process may be carried out batchwise or continuously, p eferably continuously.
Other proton-catalysed reactions of interest which are catalysed b~ cation-exchangeable layered clays in which the exchangeable cation is a ~etal cation include:-(i) the production of ethers by reacting at elevated temperature and a pressure such that the reactants are maintained in the liquid phase one or more primary or secondary aliphatic alcohols or polyols in the presence of a metal cation-exchangeable lsyered clay in Yhich the exchangeable cation is a metal cation.
The ethers are believed to be produced by condensation of two alcohol functions accompanied by elimination of water.
With regard to the primary aliphatic alcohol reactant suitable alcohols~include methanol, ethanol, propan-l-ol, butan-l-ol, pentan-l-ol, hexan-l-ol, heptan-l-ol and octan-l-ol.
The principal ether in the product resulting from the reaction of a primary aliphatic alcohol in the presence of the lamellar clays is the corresponding l,l-ether, though the corresponding 11~01~. .
1,2-ether, may also be formed. Alkenes and alkene dimers may also be formed. Generally the proportion of alkene in the product increases as the carbon number of the reactant alcohol increases.
With regard to the secondary aliphaeic alcohol reactant suitable alcohols include straight-chain alcohols such as propan-2-ol, butan-2-ol, pentan-2-ol, hexan-2-ol and hexan-3-ol,and cyclohexanol, of which propan-2-ol and butan-2-ol are preferred. The ethers predominating in the product resulting from the reaction of alkan-2-ol and alkan-3-ols are the 2,2- and 3,3- ethers respectively. Alkenes and alkene dimers are also formed.
The reactant may also be a polyol such as an alkylene glycol. A suitable alkylene glycol is ethylene glycol which produces a mixture of dioxan, and di-, tri-, tetra- etc., ethylene glycol. A preferred alkylene glycol is diethylene glycol which produces dioxan in high conversions in the presence of the lamellar clay. Additionally mixtures of alcohols and/or polyols may be used if so desired.
The elevated temperature may suitably be in the range from . 100 to 300C, preferably from 150 to 225C.
(ii) the production of ethers by reacting one or mo~e epoxides in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
Thus for example reaction of ethylene oxide yields - 1,4-dioxane and 2 methyl-1,3-dioxan. Other epoxides produce cyclic ethers but alpha, betà-ùnsaturAted aldehyde9 may al~o be formed. The proportion of the un~aturated aldehyde generally tends to increase with the carbon number of the epoxide.
(iii) the formation of esters by reacting one or more epoxides with one or more carboxylic acids in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation as catalyst.
Thus for example ethylene glycol diacetate and 2-hydroxy ethyl acetate can be obtained by reaction of ethylene oxide and liS4014 acetic acid.
(iv) the formation of ethers by reacting one or more epoxides ~ith one or more alcohols, polyols or polysaccharides in the presence of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
rnus for example 2-ethoxy ethanol, diethylene glycol nonoethyl ether, ethylene glycol diethyl ether and diethylene gl~col diethyl ether can be obtained by reaction of ethylene oxide and ethanol.
~0 (v) the formation of alpha, beta-unsaturated aldehydes by reac.ing aldehydes with a cation exchangeable layered clay in ~hic~ the exchangeable cation is a metal cation.
Thus for example but-2-en-1-al can be obtained by reaction of acetaldehyde.
tvi) the production of a secondary or a tertiary amine by reacting at elevated temperature a primary or a secondary amine having a methylene group adjacent to an amino group in the presence as catalyst of a metal cation-exchangeable layered clay, reaction of a primary amine resulting in the formation of a secondary amine and reaction of a secondary amine resulting in the formation of a tertiary amine.
Provided there is a methylene group adjacent to the amino group the primary amine may be an aliphatic, cycloaliphatic or aromatic amine. Examples of suitable primary amines which may be ~5 employed in the process of the invention include hexan-l-amine, benzylamine and cyclohexylamine. The products are believed to be formed by condensation of two molecules of the primary amine accoh2anied by the elimination of a single molecule of ammonia.
Thus, for example, in the ca~e of benzylamine the reaction may be represented as follows:-~.
.
'-.
~lS~3~, .
H2NH2 H2NH2 Elevate ~ CH2 ~ N CH
~ +~ = e Catalyst The secondary amine having a methylene group adjacent to an amino group is preferably a heterocyclic compound such as, for example, pyrrolidine or piperidine. In the case of cyclic secondary amines the products are believed to be formed by a mechanism involving ring-opening and condensation with the elimination of ammonia. Thus, for example, in the case of pyrrolidine the reaction may be represented as follows:-Elevated ~ ~Temperatur~e ~ ~ H
H Catalyst (I) (II~
The process may suitably be carried out at a temperature in the range 150 to 275C, preferably in the range 175 to 2500CA The reaction time in a batch process in which the amine and catalyst are charged to a reactor and maintained at elevated temperature may suitably be in the range from 5 to 120 hours, preferably from 30 to 120 hours.
(vii) the production of polyphenylenemethylene by reacting benzyl alcohol in the presence as catalyst of a cation-exchangeable layered clay in which the exchangeable cation is a metal cation.
The polymer contain9 repeat unit9 of the type:
-C~c~
in which the average value of n is 10.
(vii) the production of thioethers by reacting alkanthiols at elevated temperature in the presence of a cation-~, 10 , .
:' ' , :: . . , .' ~lS4014 exchangeable layered clay in which the exchangeable cation is a metal cation.
tix) the production of alkyl aromatic compounds by reacting one or m~re olefins, e.g. the production of ethylbenzene by reacting benzene with ethylene, and isopropylbenzene by reacting benzene with propylene, at elevated temperatures suitably up to 250C
preferably in the range 175 to 250C and elevated temperature and atmospheric or elevated pressure.
(xi) the production of alcohols by the hydration of olefins at elevated temperature and pressure where the water reactant consumed is more than the intercalated water contained in the clay.
The invention will now be illustrated by reference to the following Examples.
All analytical results were determined using gas chro~atography and the identity of the products were confirmed by comparison with authentic materials, mass spectroscopy or nuclear ~agnetic resonance spectroscopy.
Pæ PARATION OF METAL CATION-EXCHANGED LAYERED CLAY
-Pinally divided sodium bentonite was cation exchanged with 0.5 M
aqueous solutions of appropriate salts for periods of approximately 24 hours (the chromium salt employed was Cr2(SO4)3; the aluminium salt e2ployed uas A12(S04)3.16H2O~. The solutions were mechanically stirred during the first 2 hours of a period of 24 hours, after which the solid was washed repeatedly with deionised water until the excess cations had been removed. Surplus liquid was removed from the solid u~ing a teat-pipette prior to drying in a vacuum oven at 60C. When t~e clay was visibly dry it W8~ ground until it passet 140 BSS mesh sieve. The cation-exchanged clay was then equilibrated over granular a~hydrous calcium chloride in a dessicator for a minimum period of 24 hours.
PRODUCTIO~ OF ESTERS B~' REACTION OF AN OLEFIN WITH A CARBOXYLIC ACID
_ THE LIQIUD PHASE.
Example 1 Cr3~-exchanged bentonite (0.5 g), hex-l-ene (5 ml) and acetic acid (1.5 ml) were placed in a standard steel reactor of capacity 20 : ~ , , .
.
115401'~, ml. The reactor was closed by a screw cap provided with an 0-ring seal and immersed up to the screw cap in a silicone oil bath which was maintained at 200C. After 4 hours the reactor was removed from the bath~ cooled and its contents analysed . The results in terms of the weight percentage of individual products in the product mixture (rounded to the nearest whole number) are given in Table 1.
Example 2 Example 1 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and the acetic acid was replaced by propionic acid.
Example 3 Example 1 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and acetic acid was replaced by isobutyric acid.
Example 4 Example 1 was repeated except that hex-l-ene was replaced by hept-l-ene.
Example 5 Example 1 was repeated except that hex-l-ene was replaced by oct-l-ene.
Exa~ple 6 Example l was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite and hex-l-ene was replaced by 4-methylpent-l-ene.
Example 7 - Example l was repeated except that the Cr3+-exchanged bentonite was replaced by A13+-exchanged bentonite ~nd hex-l-ene wa8 repl~ced by hex-2-ene.
The results of Examples 1 to 7 are given in Table 1.
Example 8 Acetic acid (80 g) and A13+-exchanged Wyoming Bentonite catalyst (10 g, 9.4~ wt Al) were charged to a 100 ml stirred autoclave. The autoclave was charged with ethylene to a pressure of 55 bar tethylene:acetic acid le ratio 2:1). The temperature of the autoclave was raised to 250C and maintained at this temperature for
2.5 hr. 12 11~401~
~ .t t~2 end of the reaction period the autoclave was cooled, vented and the product analysed. The yield of ethyl acetate was 2~ and the selectivity to ethyl acet2te was greater than 99%, b~th yield and selectivity being based on acetic acid.
Ex2Gple 9 ~ xa~ple 8 was repeated except that the autoclave was pressurised t~ 150 ba~ ~ith ethylene and the temperature ~as reduced to 200C.
e yield of ethyl acetate was 35% and the selectivity greater than 9g~ . 0 F~a~ple_10 xample 8 was repeated except that the temperature was reduced to 2~0CC. ~ne yield of ethyl acetate was 18~ at a selectivity greater t~a~ g9~.
E2:a~?le 1 1 rxample 10 was repeated except that the catalyst was activated before use by heating in air at 200C.
The yield of ethyl acetate was increased from 18% to 28%.
E~a~ple 12 Example 11 was repeated except that the catalyst heat treatment wes carried out above 300C. This treatment led to substantial catal~st ceactivation. The yield of ethyl acetate was about 4 compared ~ith 18Z in Example lO.
E~a~le 13 Pxample lO was repeated using less catalyst (3 g).
The yield of ethyl acetate was reduced and this was also found to be the case eve~ ~en the reaction time was increased.
P~OD~CTIO~ OF ET~ERS BY REACTING AN ALRANOL WITH AN OLEFIN.
E~a~ple 14 The procedure described in Example 1 was followed except that the Cs3+ - exchanged bentonite was replaced by Al31 - exchanged bentonite a~d the hex-l-ene/acetic acid was replaced by a 50:50 v/v mixture (5 ~l) of hexan-l-ol and ~ex-l-ene. Analysis of the product mixture sho~ed:-llS4Vl~
wt_% of product mixture ~-Hexene 53 Hexanol 8 l,l-ether 9 1,2 + 1,3 - ethers 4 Example 15 .
5 g of the dry aluminium ion-exchanged Wyoming bentonite, hex-l-ene (25 g) and methanol (19 g) were sealed in a Baskerville 100 ml stainless steel autoclave fitted with a stirrer. The autoclave was heated at 200C for 2.5 hours, and then cooled. The liquid products (32.0 g, 73% weight recovered) were recovered and shown to contain 2-methoxyhexane (10.2%) and dimethyl ether (4.9%) as the two major new products. The product percentages are based on peak areas shown on a fla~e ionisation gas chromatograph. The gaseous products were not examined.
Example 16 5 g of the dry aluminium ion-exchanged Wyoming bentonite and methanol (19 g) were cooled to -20C in the bottom-half of a 8askerville 100 ml stainless steel autoclave. But-1-ene (ca 20 ml of condensed iiquid in a cardice cold trap) was added and the autoclave sealed. The autoclave was flushed with nitrogen and stirred at 200C
for 2.5 hours, and allowed to cool. The liquid products (7 g, 10%
weight recovered) were recovered and shown to contain 2-methoxybutane (34.7%), and C4 dimers (56.2%) as the two major new peaks. The product percentages are based on peak areas shown on a flame ionisation gas chromatograph. The gaseous products were not examined.
PRODUCTION OF ETHERS BY REACTION OF A PRIMARY OR SECONDARY ALIPHATIC
ALCOHOL OR A POL~OL
Example 17 A13+-exchanged bentonite (0.5 g) and butan-l-ol were placed in a standard steel reactor of capacity 20 ml. The reactor was closed by a screw cap provided with an O-ring seal and immersed up to the screw cap in a silicone oil bath maintained at 200C. After 4 hours the reactor was removed from the bath, cooled and its contents analysed.
~S'~O~
_~a=~le 18 Ex2-?le 17 W25 repeated except that butan-l-ol was replaced by ?entan-l-ol.
_~a=?le 19 _xa~le 17 was repeated except that butan-l-ol was replaced by hex2D-l-ol.
E~a~ple 20 Fxample 17 was repeated except that butan-l-ol was replaced by heptan-l-ol.
0 E~ æ ple 21 ExamDle 17 was repeated except that butan-l-ol was replaced by o^tan-l-ol.
_~a_ple 22 _xa~m?le 17 was repeated except that butan-l-ol was replaced by 5 3-met~.ylbutan-1-ol.
E~ æ ple 23 Example 17 was repeated except that butan-l-ol was replaced by
~ .t t~2 end of the reaction period the autoclave was cooled, vented and the product analysed. The yield of ethyl acetate was 2~ and the selectivity to ethyl acet2te was greater than 99%, b~th yield and selectivity being based on acetic acid.
Ex2Gple 9 ~ xa~ple 8 was repeated except that the autoclave was pressurised t~ 150 ba~ ~ith ethylene and the temperature ~as reduced to 200C.
e yield of ethyl acetate was 35% and the selectivity greater than 9g~ . 0 F~a~ple_10 xample 8 was repeated except that the temperature was reduced to 2~0CC. ~ne yield of ethyl acetate was 18~ at a selectivity greater t~a~ g9~.
E2:a~?le 1 1 rxample 10 was repeated except that the catalyst was activated before use by heating in air at 200C.
The yield of ethyl acetate was increased from 18% to 28%.
E~a~ple 12 Example 11 was repeated except that the catalyst heat treatment wes carried out above 300C. This treatment led to substantial catal~st ceactivation. The yield of ethyl acetate was about 4 compared ~ith 18Z in Example lO.
E~a~le 13 Pxample lO was repeated using less catalyst (3 g).
The yield of ethyl acetate was reduced and this was also found to be the case eve~ ~en the reaction time was increased.
P~OD~CTIO~ OF ET~ERS BY REACTING AN ALRANOL WITH AN OLEFIN.
E~a~ple 14 The procedure described in Example 1 was followed except that the Cs3+ - exchanged bentonite was replaced by Al31 - exchanged bentonite a~d the hex-l-ene/acetic acid was replaced by a 50:50 v/v mixture (5 ~l) of hexan-l-ol and ~ex-l-ene. Analysis of the product mixture sho~ed:-llS4Vl~
wt_% of product mixture ~-Hexene 53 Hexanol 8 l,l-ether 9 1,2 + 1,3 - ethers 4 Example 15 .
5 g of the dry aluminium ion-exchanged Wyoming bentonite, hex-l-ene (25 g) and methanol (19 g) were sealed in a Baskerville 100 ml stainless steel autoclave fitted with a stirrer. The autoclave was heated at 200C for 2.5 hours, and then cooled. The liquid products (32.0 g, 73% weight recovered) were recovered and shown to contain 2-methoxyhexane (10.2%) and dimethyl ether (4.9%) as the two major new products. The product percentages are based on peak areas shown on a fla~e ionisation gas chromatograph. The gaseous products were not examined.
Example 16 5 g of the dry aluminium ion-exchanged Wyoming bentonite and methanol (19 g) were cooled to -20C in the bottom-half of a 8askerville 100 ml stainless steel autoclave. But-1-ene (ca 20 ml of condensed iiquid in a cardice cold trap) was added and the autoclave sealed. The autoclave was flushed with nitrogen and stirred at 200C
for 2.5 hours, and allowed to cool. The liquid products (7 g, 10%
weight recovered) were recovered and shown to contain 2-methoxybutane (34.7%), and C4 dimers (56.2%) as the two major new peaks. The product percentages are based on peak areas shown on a flame ionisation gas chromatograph. The gaseous products were not examined.
PRODUCTION OF ETHERS BY REACTION OF A PRIMARY OR SECONDARY ALIPHATIC
ALCOHOL OR A POL~OL
Example 17 A13+-exchanged bentonite (0.5 g) and butan-l-ol were placed in a standard steel reactor of capacity 20 ml. The reactor was closed by a screw cap provided with an O-ring seal and immersed up to the screw cap in a silicone oil bath maintained at 200C. After 4 hours the reactor was removed from the bath, cooled and its contents analysed.
~S'~O~
_~a=~le 18 Ex2-?le 17 W25 repeated except that butan-l-ol was replaced by ?entan-l-ol.
_~a=?le 19 _xa~le 17 was repeated except that butan-l-ol was replaced by hex2D-l-ol.
E~a~ple 20 Fxample 17 was repeated except that butan-l-ol was replaced by heptan-l-ol.
0 E~ æ ple 21 ExamDle 17 was repeated except that butan-l-ol was replaced by o^tan-l-ol.
_~a_ple 22 _xa~m?le 17 was repeated except that butan-l-ol was replaced by 5 3-met~.ylbutan-1-ol.
E~ æ ple 23 Example 17 was repeated except that butan-l-ol was replaced by
3-methylpentan-1-ol.
E~a~ple 24 Example 17 was repeated except that butan-l-ol was replaced by propan-2-ol E2a~ple 25 Example 17 was repeated except that butan-l-ol was replaced by butan-2-ol.
E~anple 26 - Example 17 was repeated except that butan-l-ol was replaced by pentan-2-ol.
E~a~ple 2?
Example 17 was repeated except that butan-l-ol was replaced by hexan-2-ol.
E~a~ple 28 Example 17 was repeated except that butan-l-ol was replsced by 2-methylbutan-2-ol. This example is included to illustrate the fact that tertiary alkanols yield only alkene and alXene dimers. Identical results have been obtained form 2-methylpropan-2-ol; 2-methyl-llS401~
pentan-2-ol and 3-methylpentan-3-ol.
The results of Examples 17 to 28 in terms of the wt. % of individiual products in the product mixture (rounded to the nearest whole number) are given in Table 2 Example 29 Example 17 was repeated except that butan-l-ol was replaced by diethylene glycol.
Analysis of the product showed:-wt % product mixture Unreacted diethylene glycol57 Dioxan 20 Ethylene glycol 8 Triethylene glycol 14 Others Example 30 . .
Example 17 was repeated except that butan-l-ol was replaced by butan-l-thiol.
Analysis of the product showed:-wt % product mixture Unreacted thiol 51 Thioether 30 Disulphide 15 Others 4 Example 31 Cr3+-exchanged bentonite (0.5 g) and benzylamine (5 ml) were placed in the standard steel reactor described in Example 1. The reactor was heated for 12 hours in a silicone oil bath maintained at 200C. It was then cooled a~d its contents analysed.
Example 32 Example 31 was repeated except that benzylamine was replaced by cyclohexylamine and the reaction time was extended to 9 hours.
Example _ Example 31 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+ - exchanged bentonite, benzylamine was replaced by hexan-l-amine and the reaction time was extended to 22 hours.
..;. .
, llS~Ol~
rne results of Examples 31 to 33 in terms of the wt. % of i-dividual products in the product mixture (rounded to the nearest ~--ole nu~ber) are given in Table 3.
- ~2=ple 34 Fxam?le 31 was ~epeated except that the Cr3+-exchanged bentonite ~-as replaced by A13+-exchanged bentonite, benzylamine was replaced by p.rrolidine and the reaction time was extended to 36 hours.
r.nalysis of the product showed:-wt. % of product mixture rnreacted pyrollidine 33 L-(l-pyrrolidyl)butanamine 40 1,4-di-(1-pyrrolidyl)butane 26 Others E~ æ~le 35 , ~thylene oxide (5 ml) and aluminium-exchanged bentonite (0.5 g3 were placed in a steel reactor of capacity 20 ml. The reactor was seaLed with a screw cap and heated to 110C. After 6 hours the r~actor was covered and the contents analysed. The product contained 1,4-dioxan (68%) and 2 methyl-1,3-dioxolane (16%) together with u-changed reactants and some unidentified minor components.
E~a le 36 Ethylene oxide (5 ml), acetic acid (2.5 ml) and aluminium-e~changed bentonite (0.5g) were placed in a steel reactor of capacity 2~ ~1. The reactor was sealed with a screw cap and heated to 100C.
A~ter 60 minutes the reactor was cooled and the contents analysed.
The product contained 114-dioxan (35%), ethylene glycol diacetate (17~), 2-hydroxyethylacetate (11%), 2-methyl-1,3,dioxol~ne(7%) and but-2-en-1-al (3%) together with unchanged reactants and some unidentified minor components.
E~ æple 37 Ethylene oxide (2.5 ml) ethanol (2.5 ml) and aluminium exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml.
The reactor was sealed with a screw cap and heated to 110C. After 4 hours the reactor was cooled and the contents analysed. The product contained diethyl ether (2%), ethylene glycol diethyl ether (1%), ., 11540~
and diethylene glycol mono-ethylether (21%) together with unchanged reactants and some unidentified minor components.
Example 38 Propylene oxide (5 ml) and aluminium-exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml. The reactor was sealed with a screw cap and heated to 200C. After 8 hours the reactor was cooled and the contents analysed. The product contained dimethyl-1,4-dioxane (4%), 2-methyl-2-pentanol (35%) and 1,3-dioxolanes (16%) together with unchanged reactant and some unidentified minor components.
Example 39 Acetaldehyde (5 ml) and aluminium-exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml. The reactor was sealed and heated at 110C. After 8 hours the ractor was cooled and the contents analysed. The product contained but-2-en-1-al (24%) together with unchanged reactant and some unidentified minor components.
19 1~L~4U11~
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E~a~ple 24 Example 17 was repeated except that butan-l-ol was replaced by propan-2-ol E2a~ple 25 Example 17 was repeated except that butan-l-ol was replaced by butan-2-ol.
E~anple 26 - Example 17 was repeated except that butan-l-ol was replaced by pentan-2-ol.
E~a~ple 2?
Example 17 was repeated except that butan-l-ol was replaced by hexan-2-ol.
E~a~ple 28 Example 17 was repeated except that butan-l-ol was replsced by 2-methylbutan-2-ol. This example is included to illustrate the fact that tertiary alkanols yield only alkene and alXene dimers. Identical results have been obtained form 2-methylpropan-2-ol; 2-methyl-llS401~
pentan-2-ol and 3-methylpentan-3-ol.
The results of Examples 17 to 28 in terms of the wt. % of individiual products in the product mixture (rounded to the nearest whole number) are given in Table 2 Example 29 Example 17 was repeated except that butan-l-ol was replaced by diethylene glycol.
Analysis of the product showed:-wt % product mixture Unreacted diethylene glycol57 Dioxan 20 Ethylene glycol 8 Triethylene glycol 14 Others Example 30 . .
Example 17 was repeated except that butan-l-ol was replaced by butan-l-thiol.
Analysis of the product showed:-wt % product mixture Unreacted thiol 51 Thioether 30 Disulphide 15 Others 4 Example 31 Cr3+-exchanged bentonite (0.5 g) and benzylamine (5 ml) were placed in the standard steel reactor described in Example 1. The reactor was heated for 12 hours in a silicone oil bath maintained at 200C. It was then cooled a~d its contents analysed.
Example 32 Example 31 was repeated except that benzylamine was replaced by cyclohexylamine and the reaction time was extended to 9 hours.
Example _ Example 31 was repeated except that the Cr3+-exchanged bentonite was replaced by A13+ - exchanged bentonite, benzylamine was replaced by hexan-l-amine and the reaction time was extended to 22 hours.
..;. .
, llS~Ol~
rne results of Examples 31 to 33 in terms of the wt. % of i-dividual products in the product mixture (rounded to the nearest ~--ole nu~ber) are given in Table 3.
- ~2=ple 34 Fxam?le 31 was ~epeated except that the Cr3+-exchanged bentonite ~-as replaced by A13+-exchanged bentonite, benzylamine was replaced by p.rrolidine and the reaction time was extended to 36 hours.
r.nalysis of the product showed:-wt. % of product mixture rnreacted pyrollidine 33 L-(l-pyrrolidyl)butanamine 40 1,4-di-(1-pyrrolidyl)butane 26 Others E~ æ~le 35 , ~thylene oxide (5 ml) and aluminium-exchanged bentonite (0.5 g3 were placed in a steel reactor of capacity 20 ml. The reactor was seaLed with a screw cap and heated to 110C. After 6 hours the r~actor was covered and the contents analysed. The product contained 1,4-dioxan (68%) and 2 methyl-1,3-dioxolane (16%) together with u-changed reactants and some unidentified minor components.
E~a le 36 Ethylene oxide (5 ml), acetic acid (2.5 ml) and aluminium-e~changed bentonite (0.5g) were placed in a steel reactor of capacity 2~ ~1. The reactor was sealed with a screw cap and heated to 100C.
A~ter 60 minutes the reactor was cooled and the contents analysed.
The product contained 114-dioxan (35%), ethylene glycol diacetate (17~), 2-hydroxyethylacetate (11%), 2-methyl-1,3,dioxol~ne(7%) and but-2-en-1-al (3%) together with unchanged reactants and some unidentified minor components.
E~ æple 37 Ethylene oxide (2.5 ml) ethanol (2.5 ml) and aluminium exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml.
The reactor was sealed with a screw cap and heated to 110C. After 4 hours the reactor was cooled and the contents analysed. The product contained diethyl ether (2%), ethylene glycol diethyl ether (1%), ., 11540~
and diethylene glycol mono-ethylether (21%) together with unchanged reactants and some unidentified minor components.
Example 38 Propylene oxide (5 ml) and aluminium-exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml. The reactor was sealed with a screw cap and heated to 200C. After 8 hours the reactor was cooled and the contents analysed. The product contained dimethyl-1,4-dioxane (4%), 2-methyl-2-pentanol (35%) and 1,3-dioxolanes (16%) together with unchanged reactant and some unidentified minor components.
Example 39 Acetaldehyde (5 ml) and aluminium-exchanged bentonite (0.5 g) were placed in a steel reactor of capacity 20 ml. The reactor was sealed and heated at 110C. After 8 hours the ractor was cooled and the contents analysed. The product contained but-2-en-1-al (24%) together with unchanged reactant and some unidentified minor components.
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~ ~ l +l l l +l +l .
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, , . ......... o ~ ~
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., .
wt. ~ of product mixture ~ ?le Layered Clay Amine . .
., Unreacted Secondary Others , . amine amine 31 Cr3+-bentonite Benzylamine 71 21 5 . .~
32 Cr3+-bentonite Cyclohexylamine 81 18 1 _ 33 A13+-bentonite Hexan-l-amine _ 2 .
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., .
wt. ~ of product mixture ~ ?le Layered Clay Amine . .
., Unreacted Secondary Others , . amine amine 31 Cr3+-bentonite Benzylamine 71 21 5 . .~
32 Cr3+-bentonite Cyclohexylamine 81 18 1 _ 33 A13+-bentonite Hexan-l-amine _ 2 .
'' ' ' ' :
.
.
.
,
Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for carrying out a proton-catalysed organic reaction in which intercalated water is not one of the stoichiometric reactants employing as catalyst a metal cation-exchangeable material characterized in that as the cation-exchangeable material there is used a layered clay in which the exchange-able cation is a metal cation.
2. A process according to claim 1 wherein the layered clay is a bentonite.
3. A process according to claim 1 wherein some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
4. A process according to claim 1 or 2 wherein some or all of the exchange-able cations are exchanged with cations of chromium or aluminium.
5. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting one or more olefins with one or more carboxylic acids under reaction conditions which result in the formation of an ester.
6. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting ethylene, propylene, a butene, a pentene, a hexene or cyclohexane with one or more carboxylic acids under reaction conditions which result in the formation of an ester.
7. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting one or more olefins with formic acid, acetic acid, propionic acid, butyric acid or a phthalic acid under reaction conditions which result in the formation of an ester.
8. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting ethylene with acetic acid under reaction conditions which result in the formation of ethyl acetate.
9. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting one or more olefins with one or more carboxylic acids under reaction conditions which result in the formation of an ester, and wherein the layered clay is a bentonite and some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
10. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting one or more olefins with one or more carboxylic acids under reaction conditions which result in the formation of an ester, and wherein the olefin is contacted with the carboxylic acid in the liquid phase at a temperature in the range from 100 to 300°C and a pressure which maintains a liquid phase at the reaction temperature.
11. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of esters by reacting one or more olefins with one or more carboxylic acids under reaction conditions which result in the formation of an ester, and wherein the olefin is contacted with the carboxylic acid in the vapour phase at a temperature in the range from 120 to 180°C and a residence time in the range from 10 to 60 seconds.
12. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of ethers by reacting at a temperature above 100°C one or more alcohols with one or more olefins having the structure:
R1CH = CHR2 wherein R1 and R2 are independently H, alkyl or aryl or are bonded together to form a ring.
R1CH = CHR2 wherein R1 and R2 are independently H, alkyl or aryl or are bonded together to form a ring.
13. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of ethers by reacting,at a temperature above 100 C, methanol, ethanol, a propanol, a butanol, a pentanol or a hexanol with one or more olefins having the structure:
R1CH = CHR2 wherein R and R are independently H, alkyl or aryl or are bonded together to form a ring.
R1CH = CHR2 wherein R and R are independently H, alkyl or aryl or are bonded together to form a ring.
14. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of ethers by reacting, at a temperature above 100 C, one or more alcohols with ethylene, propylene, a butene, a pentene or a hexene.
15. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of ethers by reacting at a temperature above 100 C one or more alcohols with one or more olefins having the structure:
R1CH = CHR2 wherein R and R are independently H, alkyl or aryl or are bonded together to form a ring, and wherein the alcohol is contacted with the olefin in the liquid phase.
R1CH = CHR2 wherein R and R are independently H, alkyl or aryl or are bonded together to form a ring, and wherein the alcohol is contacted with the olefin in the liquid phase.
16. A process according to claim 1, 2 or 3 wherein the proton-catalysed organic reaction is the production of ethers by reacting at a temperature above 100 C one or more alcohols with one or more olefins having the structure:
R1CH = CHR2 wherein R1 and R2 are independently H, alkyl or aryl or are bonded together to form a ring, and wherein the layered clay is a bentonite and some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
R1CH = CHR2 wherein R1 and R2 are independently H, alkyl or aryl or are bonded together to form a ring, and wherein the layered clay is a bentonite and some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
17. A process according to claim 1, 2 or 3 wherein the catalyst is acti-vated before use by heating in air at a temperature in the range 80 to 220 C.
18. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of ethers by reacting at elevated temperature and a pressure such that the reactants are maintained in the liquid phase a primary or secondary aliphatic alcohol or a polyol.
19. A process according to claim 18 wherein the layered clay is a bento-nite and some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
20. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of an alkyl aromatic compound by reacting one or more aromatic compounds with one or more olefins.
21. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of ethyl benzene by reacting ethylene with benzene.
22. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of isopropyl benzene by reacting propylene with benzene.
23. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of an alkyl aromatic compound by reacting one or more aromatic compounds with one or more olefins, and wherein the layered clay is a bentonite and some or all of the exchangeable cations are exchanged with cations of one or more of the metals chromium, aluminium, cobalt, nickel, iron, copper and vanadium.
24. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of ethers by reacting one or more epoxides.
25. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of esters by reacting one or more epoxides with one or more carboxylic acids.
26. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of ethers by reacting one or more epoxides with one or more alcohols, polyols or polysaccharides.
27. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the production of esters by reacting one or more alcohols with one or more carboxylic acids.
28. A process according to claim 1, 2 or 3 wherein the proton-catalysed reaction is the hydration of olefins.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7944315 | 1979-12-22 | ||
| GB79/44315 | 1979-12-22 | ||
| GB80/16384 | 1980-05-17 | ||
| GB8016384 | 1980-05-17 | ||
| GB80/22101 | 1980-07-05 | ||
| GB8022101 | 1980-07-05 | ||
| GB80/26028 | 1980-08-09 | ||
| GB8026028 | 1980-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1154014A true CA1154014A (en) | 1983-09-20 |
Family
ID=27449153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367156A Expired CA1154014A (en) | 1979-12-22 | 1980-12-19 | Proton-catalysed reactions in which water is not a stoichiometer reactant catalysed by metal cation- exchanged layered clays |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US4499319A (en) |
| EP (1) | EP0031252B1 (en) |
| AU (2) | AU6579781A (en) |
| CA (1) | CA1154014A (en) |
| DE (1) | DE3066326D1 (en) |
| NZ (1) | NZ195920A (en) |
| WO (1) | WO1981001845A1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6351060B2 (en) * | 1979-12-22 | 1988-10-12 | Buriteitsushu Pitorooriamu Co Plc Za | |
| IN158310B (en) * | 1981-08-21 | 1986-10-18 | British Petroleum Co | |
| US4542250A (en) * | 1982-01-09 | 1985-09-17 | The British Petroleum Company, P.L.C. | Use of stabilized pillared interlayered clays as catalyst in alkylation reactions |
| US4806658A (en) * | 1982-11-15 | 1989-02-21 | The Dow Chemical Company | Cleavage of polyethylene glycol ethers by hydrolysis |
| JPS6177654A (en) * | 1984-09-20 | 1986-04-21 | トヨタ自動車株式会社 | Heat-resistant high expansion sheet matter for catalyst carrier support and manufacture |
| GB8512775D0 (en) * | 1985-05-21 | 1985-06-26 | British Petroleum Co Plc | Chemical process |
| GB8614909D0 (en) * | 1986-06-19 | 1986-07-23 | British Petroleum Co Plc | Production of glycol ethers |
| GB8621263D0 (en) * | 1986-09-03 | 1986-10-08 | British Petroleum Co Plc | Proton catalysed reactions |
| US5003121A (en) * | 1989-08-28 | 1991-03-26 | Uop | Production of alkyl aromatic compounds |
| US5160032A (en) * | 1990-02-22 | 1992-11-03 | Uop | Hydrocarbon conversion process using alumina clay compositions |
| US5114895A (en) * | 1990-02-22 | 1992-05-19 | Uop | Alumina clay compositions |
| US5034564A (en) * | 1990-04-12 | 1991-07-23 | Uop | Production of alkyl aromatic compounds |
| US5126489A (en) * | 1991-05-06 | 1992-06-30 | Uop | Acylation of aromatic compounds by acid anhydrides using solid acid catalysts |
| US5744113A (en) * | 1993-05-27 | 1998-04-28 | Siemens Aktiengesellschaft | Process and catalyst for decomposing oxides of nitrogen |
| DE4321871A1 (en) * | 1993-07-01 | 1995-02-23 | Basf Ag | Process for the preparation of alkoxy-carboxylic acid esters |
| US5409597A (en) * | 1993-10-12 | 1995-04-25 | Uop | Hydrocarbon conversion process using a pillared clay containing fluorided pillars |
| US5389593A (en) * | 1993-10-12 | 1995-02-14 | Uop | Pillared clay containing fluorided pillars |
| US5733439A (en) * | 1994-03-18 | 1998-03-31 | Uop | Hydrocarbon conversion processes using substituted fluoride smectite clays |
| US6100223A (en) * | 1997-12-30 | 2000-08-08 | Chevron Chemical Company Llc | Method of converting olefins into mixtures of secondary esters, products and uses thereof |
| US5973193A (en) * | 1998-07-16 | 1999-10-26 | Mobil Oil Corporation | Ethyl acetate synthesis from ethylene and acetic acid using solid acid catalysts |
| EP1013632B1 (en) * | 1998-12-24 | 2003-09-03 | Council Of Scientific And Industrial Research | Process for production of esters |
| DE19935914A1 (en) | 1999-07-30 | 2001-02-01 | Sued Chemie Ag | Process for the preparation of catalysts by acid activation |
| US20090023959A1 (en) * | 2006-06-16 | 2009-01-22 | D Amore Michael B | Process for making dibutyl ethers from dry 1-butanol |
| US20080045754A1 (en) * | 2006-06-16 | 2008-02-21 | D Amore Michael B | Process for making butenes from dry 1-butanol |
| US20080132734A1 (en) * | 2006-12-01 | 2008-06-05 | Leo Ernest Manzer | Process for making dibutyl ethers from dry 2-butanol |
| US20080132730A1 (en) * | 2006-12-01 | 2008-06-05 | Leo Ernest Manzer | Process for making butenes from dry 2-butanol |
| US8084384B2 (en) * | 2008-10-03 | 2011-12-27 | Chevron U.S.A. Inc. | Magnesium aluminosilicate clays—synthesis and catalysis |
| US8518239B2 (en) * | 2008-10-03 | 2013-08-27 | Chevron U.S.A. Inc. | Hydrocracking catalyst and process using a magnesium aluminosilicate clay |
| WO2023057358A1 (en) * | 2021-10-07 | 2023-04-13 | Basf Se | Process for the production of bis(pyrrolidino)butane in the liquid phase |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1069583B (en) * | 1959-11-26 | Süd-Chemie A.G., München 2 | Process for the production of catalysts from bentonite | |
| FR710846A (en) * | 1930-06-11 | 1931-08-29 | Ig Farbenindustrie Ag | Process for the production of oxygenated organic compounds |
| US2242960A (en) * | 1938-08-27 | 1941-05-20 | Socony Vacuum Oil Co Inc | Production of motor fuel |
| US2564488A (en) * | 1948-12-17 | 1951-08-14 | Phillips Petroleum Co | Alkylation of toluene by propylene catalyzed by acid activated montmorillonite clay |
| US2930820A (en) * | 1957-09-16 | 1960-03-29 | Robert S Aries | Alkylation of toluene |
| GB905854A (en) * | 1960-05-14 | 1962-09-12 | Distillers Co Yeast Ltd | Production of t-butyl acetate |
| NL296301A (en) * | 1962-08-08 | |||
| BE656771A (en) * | 1963-12-09 | |||
| US3313860A (en) * | 1964-03-06 | 1967-04-11 | Mobil Oil Corp | Producing para- and meta-tertiary-butyltoluenes |
| FR1482271A (en) * | 1965-05-24 | 1967-05-26 | Celanese Coatings Co | New process for reacting a carboxyl functional derivative with an oxirane functional derivative |
| US3578609A (en) * | 1967-10-02 | 1971-05-11 | Mobil Oil Corp | Ion exchange resin containing zero-valent metal |
| JPS49100016A (en) * | 1973-02-03 | 1974-09-20 | ||
| US3965043A (en) * | 1974-09-06 | 1976-06-22 | Nl Industries, Inc. | Catalyst for alkylating aromatic hydrocarbons therefor |
| US3979331A (en) * | 1974-09-06 | 1976-09-07 | Nl Industries, Inc. | Catalyst for alkylating aromatic hydrocarbons |
| US3962361A (en) * | 1974-09-06 | 1976-06-08 | Nl Industries, Inc. | Process for alkylating aromatic hydrocarbons |
| US4193454A (en) * | 1976-03-15 | 1980-03-18 | Mobil Oil Corporation | Super-active clay catalyst and use thereof |
| US4078991A (en) * | 1976-03-15 | 1978-03-14 | Mobil Oil Corporation | Treatment of clay materials to form super-active catalyst |
| JPS6351060B2 (en) * | 1979-12-22 | 1988-10-12 | Buriteitsushu Pitorooriamu Co Plc Za | |
| ZA815144B (en) * | 1980-08-01 | 1983-03-30 | British Petroleum Co | Method for promoting the activity of cation-exchangeable layered clay and zeolite catalysts in proton-catalysed reactions |
| DE3105399A1 (en) * | 1981-02-14 | 1982-10-21 | EC Erdölchemie GmbH, 5000 Köln | Process for the preparation of carboxylic acid esters |
| IN158310B (en) * | 1981-08-21 | 1986-10-18 | British Petroleum Co |
-
1980
- 1980-12-19 EP EP80304620A patent/EP0031252B1/en not_active Expired
- 1980-12-19 CA CA000367156A patent/CA1154014A/en not_active Expired
- 1980-12-19 DE DE8080304620T patent/DE3066326D1/en not_active Expired
- 1980-12-19 AU AU6579781A patent/AU6579781A/en active Pending
- 1980-12-19 AU AU65797/80A patent/AU543680B2/en not_active Ceased
- 1980-12-19 WO PCT/GB1980/000219 patent/WO1981001845A1/en unknown
- 1980-12-22 NZ NZ195920A patent/NZ195920A/en unknown
-
1982
- 1982-09-09 US US06/416,387 patent/US4499319A/en not_active Expired - Lifetime
-
1986
- 1986-06-18 US US06/878,385 patent/US4749808A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| NZ195920A (en) | 1983-07-15 |
| US4499319A (en) | 1985-02-12 |
| DE3066326D1 (en) | 1984-03-01 |
| US4749808A (en) | 1988-06-07 |
| EP0031252A1 (en) | 1981-07-01 |
| AU543680B2 (en) | 1985-04-26 |
| WO1981001845A1 (en) | 1981-07-09 |
| AU6579781A (en) | 1981-07-22 |
| EP0031252B1 (en) | 1984-01-25 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |