CA1160252A - Process for producing gasoline-grade c.sub.2- c.sub.4 alcohols, from aqueous mixtures containing them - Google Patents
Process for producing gasoline-grade c.sub.2- c.sub.4 alcohols, from aqueous mixtures containing themInfo
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- CA1160252A CA1160252A CA000374128A CA374128A CA1160252A CA 1160252 A CA1160252 A CA 1160252A CA 000374128 A CA000374128 A CA 000374128A CA 374128 A CA374128 A CA 374128A CA 1160252 A CA1160252 A CA 1160252A
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- water
- olefin
- isobutene
- ethanol
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
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Abstract
A B S T R A C T O F T H E D I S C L O S U R E
An improved process is disclosed for producing gasoline-grade C2-C4 alcohols from aqueous mixtures which contai.n said alcohols: the improvement consists in that the aqueous mixture is reacted with a tertiary olefin in the presence of a catalyst having an acidic character, at a temperature of from 40°C and. 90°C and at a space velocity comprised between 5 and 25 litres of reactants per litre of catalyst in an hour. Preferred catalysts are the acidic ion-exchange resins and especially those having -SO3H groups Temperature and space velocity ranges are critical in order to minimize the parasitic ester-forming reactions.-
An improved process is disclosed for producing gasoline-grade C2-C4 alcohols from aqueous mixtures which contai.n said alcohols: the improvement consists in that the aqueous mixture is reacted with a tertiary olefin in the presence of a catalyst having an acidic character, at a temperature of from 40°C and. 90°C and at a space velocity comprised between 5 and 25 litres of reactants per litre of catalyst in an hour. Preferred catalysts are the acidic ion-exchange resins and especially those having -SO3H groups Temperature and space velocity ranges are critical in order to minimize the parasitic ester-forming reactions.-
Description
57~
PROCESS FOR PRODUCI~G GASOLINE-GRADE C2-C4 ALCOHOLS
FROM AQUEOUS MIXTURES CONTAI~ING THEM
This invention relates to a process for procuding gasoline-grade (e.g. C2-C~) alcohols from aqueous mixtures containing them.
It is known long since that ethanol has very appreciable octane-number characteristics so that it can be used as such in the formulation of fuel mixtures to reduce the percentage of lead-al,kyl additives, or, as in alter-native, to reduce the aromatics conten-t in gasolines.
Ethanol is conventionally produced on a commer-cial scale by fermentation oE carbohydrates: in these procedures, the percentage of alcohol in the fermentation products of sugar-containing juices is below 10~. The subsequent steps directed to recovering alcohol comprise a sequence of distillation steps which permit to arrive at a water-ethanol azeotropic mixture, which, under atmo-spherical pressures, has a water content of 4.4% by weight.
However, this kind of ethanol still contains too much water for enabling it to be employed directly in fuels, so that further dehydration stages become necessary.
The rectification stages and, more particularly, the final dehydration step, have a negative bearing on the first cost of gasoline-grade ethanol.
This circumstance has been conducive to a number of studies dealing with the optimization of the heat recovery in the conventional systems and also to a series of suggestions for alternative dehydration procedures.
Absolute ethanol is obtained in the present times by azeotropic distillation with benzene.
25;~
Alternati.ve suggestions have been made recently, however, which are based on the.strippin.g of water by selective absorption on starchy substances and preferenti.al absorptions on textile fibers, extractions with solvents in cri-tical phase, use of membranes which are impervious to either component, absorption on molecular sieves having pore dimensions sufficient to retain water and finally distillation procedures under reduced pressu-res.
All the suggested approaches, however, are affec-ted by the serious drawback that they involve a decrease of the liquid product yield and substantially re~uire high running costs and special apparatus so that also the first costs are high.
It has now been found that it is possible to produce gasoline-grade (e.g. C2-C4) alcohols without resorting to any conventional technique, while concurrently achieving considera-ble economical advantages on account of the simplicity of the operations proposed herein and also of the improvement of the liquid yield.
The present invention in particular provides a process for preparing alcohol mixtures which can be added to gasoline without causing phase demixing, which process comprises reacting a water-ethanol azeotropic mixture with a tertiary olefin, or an olefin cut containing same, in the presence of a catalys-t for the hydration of the olefin selected Erom the group consisting of mineral acids, Lewis' acids and ion-exchallge resins of the acid type, said tertiary olefin being used in a molar excess over the amount of water contained in the mixture, and said reaction being carried out at a temperature comprised between 40C and 90C. and at a space velocity, LHS~, expressed in liters of reactants per liter of catalyst per hour, comprised between 5 and 25.
In accordance with the present invention the molar ,~ , ~6d~;2SZ
excess of tertiary olefin to water ~ay be up to about 5 -to 1.
As indicated abo~e the process o~ the presen~ inven-tion includes the step of reacting a aicohol-water mixture, coming from the relati~e production systems, with either a tertiary olefin or an olefin cut containing it by so doing, the water content is reduced since water, by reacting with the olefin concerned, produces a tertiary alcohol. The resultan-t product, upon stripping the unreac-ted olefins, makes up a mixture which can be added to the fuels in the usual rations without experien-c~ng phase-separatlons, even at temperatures below -.u C
`~ - 2 a -.
The reaction of addition of the tertiary olefin to water can be carried out with -the aid of the conventlonal catalysts as used for ole~in hydrations, such as mineral acids, Lewis' acids and ion-exchange resins, and more particularly those which support -SO3H groups on poly-styrene, divinylbenzene, and polyphenol matrices are preferred due to their greater simplicity of use.
The working conditions, instead, should carefully be selected, inasmuch as too high temperatures, or too low spatial velocities worsen the selectivity of the operation because the competitive reaction of formation of the corresponding ethers might predominate.
The latter reaction should be prevented as far as practicable because it substracts the tertiary olefin to its reaction with water, the result being that the production of the tertiary alcohol is decreased: the ter-tiary alcohol is appreclable since it has a solubilizing action on the water residue.
As indicated above the addition reaction can be carried out within a temperature range between 40C and 90C under a pressure whi.ch is so selected as to maintain the hydrocarbon steams being processed either in.the liquid or the gaseous phase according to the advisability of processing the streams concerned in the vapor or the liquid phase.
When working in the liquid phase, the spatial velocity ~LHSV) of the reaction, expressed in litres of feed per litre of catalyst in an hour, is comprised between 5 and 25.
FIGURE 1 of the accompanying drawing is illus-` - 3 -- 4 ~
trative of a particular e~bodiment of the process accor-ding to the present invention relative to a treatment of c~n aqueous mixture which contains ethanc,l, with an ole~ir.
fraction which contains isobutene: the alcoholic mixture, 1, and the feeding olefin lraction,3, are sent, together - with the recycled ole~ins,2, to the reactor R-1: the re-action product,5, is sent to the rectification column,C-1, rom the bottom of which e-thanol is reco~rered togeth~r with the reaction product an~ the unreacted water,~. A'.t the col~n head, the olefin fraction is recovered, which i.s partly recyc~ed -to the reactor P-1 and partly is dl]mped at 8.
~ I~URE 2 shows a diagram akin to that of FI~.1, but without olefin recycling.
A few examples v~ill now be given, which are me-rely illustrative of the invention without limi.tation.
ln Example 1 there is reported a scheme which - explains the possibiliti~s afforded by the process of this invention. As can be seen, it becomes possible to obtain a product which is perfectly miscible wi-th gasoli nes also at low temperatures, while conc-urrently achieving an improvement in the yield relative to the starting alcohol in the order of magnitude of 18~o a-t the expenses of a ga-seous product such as isobutene,which has not been directly added to gasoline, as this is not possi.ble~
The comparison between the results of ~am~ple 2 and those of Example 3 shows how important may be to li~it the conversion of ethanol. As a matter of fact, by working at a lower space velocity, a product is obtained, which, when admixed with gasoline, has a higher turbidity temperature ~60Z5Z
The comparison between the results of Examples 4, 5 and 6 shows that, the spatial velocity being the same, the reaction temperature becornes critical: in the examples reported herein, the optimum value is at 70C.
EX~MPI,F. 1 In a tubular reactor, see Fig. 1, which contains a macroporous acid-form ion-exchange resin such as Amber-lyst* 15, a mixture is reacted, which is composed by 28.20 parts by weight of ethanol (containing 7% by wt oE water), 1, 61.50 parts of a recycle oleEin fraction, 2, containing 6.4~ by wt of isobutene and 10.36 parts of an olefin frac-tion, 3, containing 50% by wt of isobutene.
The composition of the resultant mixture is as follows:
Non-reactive butenes 62.7% by wt Isobutene 9.1% do.
Ethanol 26.2% do.
Water 2.0% do.
The mixture, fed at a space velocity equal to 10 litres an hour per litre of catalyst, is caused to react at a temperature of 70C and the following reaction product, 5, is obtained:
Unreacted butenes 62.7% by wt Isobutene 4.3% do.
Ethyl tert.butyl ether 3.6% do.
Tert.butyl alcohol 3.8% do.
Ethanol 24.6% do.
Water 1.0% do.
The subsequent fractionation of the reac-tion product is carried out in a rectification column, wherein * Trade Mark.
5%
33.0 parts of a bottom product, 6, are obtained, which has the following composition:
Ethanol 74.5% by wt Water 3.0% do.
Tert.butyl alcohol 11.5% do.
Ethyl tert.butyl ether11.0% do.
and 67 parts of a head product, 7, having the following composition:
Unreacted butenes 93.6% by wt Isobutene 16.~% do.
Of this stream, 61.5 parts are recycled to the reaction, 2, and 5.5 parts, 8, are sent to subsequent uses.
The column bottom product, stream 6, can directly be admixed with gasolines without any demixing problems.
By way of comparison, there are reported here-under the values of the turbidity temperature of the etha-nol of the charge 1 (mixture A) and of the reaction product 6 (mixture B), both supplemented as the 10% by wt to a.
hydrocarbon stream containing the 30% by wt of aromatics and the 70% by wt of saturated hydrocarbons.
Turbidity temperature,C
Mixture A above +20C
Mlx-ture B under -20C
In a tubular reactor, see Fig.2, containing a macroporous acid form ion-exchange resin such as Amberlyst*
15, a mixture is caused to react, which is composed by 34.1 parts by wt of ethanol (7.3~ water) and 65.9 parts by wt of an olefin fraction, 2, containing 50.7% by wt of isobutene.
* Trade Mark Z
The composition of the resultarlt ml~ture,39 is as follows:
Non-reactive butenes 32.5% by wt Isobutene 33O4% do~
~thanol 31.6% do.
Water 2~5~o do.
The mixture, fed at a space velocity equal -to 1.5 litres an hour per litre of catal~st, is caused to react a~ a temperature o~ 60C, whereby the Iollowing - 10 reaction product, ~, is obtained:
Unreacted butenes 32.50,~ ~y wt Isobutene 2.5% doO
Ethyl tQrt.buty:l ether 45.7% do.
Tert.butyl alcohol 7.9~0 do.
Ethanol 10~7~ do.
Water 0.7~ do.
The subsequent fractionation of the reaction product is carried out in a rectifica-tion column, wherein ther~ are obtained 65 parts of a bottom product,5, havin`g the fol'owing composition:
Ethyl tert.butyl ether 70~4% by Vlt Tert.butyl alc~hol 12.1% do.
Ethanol 16.~% do~
Water 1.1% do.
The water content, referred to the s~m of the alcohols which are present, is 3.7~ by wt.
The column head stream~ 6, is composed by 35.0 parts of an olefin fraction having the following composi-tion :
s~
~nreacted butenes 92.9% by wt Isobutene 7.1% do The turbidity temperature of a mixture of 10%
by wt of the column bottom produc-t 5 with 90~ by wt of a hydrocarbon frac-tion (70% by wt of saturated hydroc. and 30% of aromatics) is -12C.
In a tubular reactor, see FIG.2, containing a macroporous acid-form ion-exchange resin such as Amberlyst*
15, there is caused -to react a mixture consisting of 34.2 parts by wt of ethanol (7.8% water cont.), l, and 65.8 parts by wt of an olefin fraction, 2, containing 48.2% by wt of isobutene.
The co~position of the resultant mixture, 3, is as follows:
Non-reactive butenes34.1% by wt Isobutene 31.7% do.
Ethanol 31.5% do.
Water 2.7% do.
This mixture, fed at a space velocity equal to 16 litres per litre of catalyst an hour, is caused to react at a temperature of 60C and the following reaction product, 4, is obtained:
Unreacted butenes 34.1% by wt Isobutene 22.9% do.
Ethyl tert.butyl ether 5.5% do.
Tert.butyl alcohol 7.9% do.
Ethanol 28.9% do.
Water 0.7% do.
The subsequent Eractionation of the reaction * Trade Mark.
zsæ
product is carried out in a rectification ~olumn, whereln there are obtained 43.0 parts of bottor~ procluctt 5, ha-ving -the following composition:
~thyl tert.butyl ether 12~o by ~ t I'ert.butyl alcohol ~8.~o do.
Ethanol G7.2% do~
Water ~.6% do.
with a eontent of ~Yater~ re~erred to the sum of -the al-eohols whieh are present, of l.~o by ~t.
~'he column head stream,6, is composed b~ 57.0 parts o~ an ole~in fraction having the following eompo sition:
Unreacted butenes 59~&~o by wt Isobutene 4Q, ~k~ do.
The turbidity tempera-ture of a mi~tuxe of ~0 by weight of column bottom preduct,5, with 9~0 by wt o~
a hydrocarbon fraction ( 70~o by wt o~ saturated hydroc.
` ~ and 30~0 by wt of aro~latics~ is under -20C.
- E x ~ m 2_~_ e ~ 20 In a tubular reaetor, see FIG.2, containing a maeroporous aeid-form ion-exchange resin sueh as Amberlyst *
15 there is caused to react a mi~-ture consisting oI 31.5 parts by wt of ethanol (7.5~0 wa-ter ccnl.), 1, and 68.5 parts o~ an ole~in fraction , 2, containing 50.8~ by ~-Jt of isobutene.
The composition o~ the resultant mixture, 3, is as follows :
Non-reaGtive butenes 33.7% by ~rt Isobutene 3~80~o do.
Ethanol 29~1% do.
Y~ater 2.470 do.
* Trade mark . ,?`
The mixture, fed at a space velocity equal to 20 litres per litres of catalyst an hour, is reacted at a temperature of 60C and the following reaction product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 25.7% do.
Ethyl tert.butyl ether 6.5% do Tert.Butyl alcohol 7.2% do Ethanol 26.2% do Water 0.7% do.
The subsequent fractionation of the reaction product is carried out in a rectification column, wherein there are obtained 40.6 parts of a bottom product, 5, having the following composition:
Ethyl tert.butyl ether 16.0% by wt Tert.butyl alcohol 17.7% do.
Ethanol 64.6% do.
Water 1.7% do.
With a content of water, referred to the sum oE
the alcohols which are present of 2.0% by wt.
The column heacl stream, 6, consists of 59.4 parts of an olefin fraction having the following composition:
Unreacted butenes 56.7% by wt Isobutene 43.3% do.
In a tubular reactor, see FIG.2, containing a macroporous acid-form ion-exchange resin such as Amberlyst*
15 there is caused to react a mixture consisting oE 31.5 parts by wt of ethanol (7.5% water cont.), 1, and 68.5 parts of an olefin fraction, 2, containing 50.8% by wt * Trade Mark.
~ -- 1 0 o~ isobutene.
The composition OI the resultant mi~:~,ure, 3, is as follows:
Non-reactive butene~ 3~.7~ by wt Isobutene 34.8~o do.
Ethanol 29.~% do.
Water 2.4~o doO
The latter miYture, fed at a space velocity of 20 litres per liter of cataiyst an hour, is cau~ed to react lO at a te~perature of 70C, whereby the ~ollowing reaotion product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 14.0~ doO
~thyl ter-t~butyl ether 27.3~ doO
Tert.butyl alcohol 8. l~o aO .
Ethanol 16.5% do.
- Water 0.4~ do.
The subsequen-t ~rsctionatiQn of the re~ction - product is carried Ollt in a rectification colwnn, wherein there are ob-tai~ea 52.3 parts of a bottom product, 59 ha-ving the following compositlon:
Ethyl tert~butyl ether 52.2% by w-t Tert.butyl alcohol 1~o5% do.
~thanol 31.5% do.
Water 0.8~o doO
Water cont.relO to the sum o~ alcohols present1.7% doO
The column head stream, G, consists of 47.7 p~rts of an ole-in f~action having the following composltion:
Unreacted butenes 70~6% by l~t Isobutene 29.4% ~o~
--;
In a tubular reactor, see FIG.2, containing a macroporous ion-exchange resin of the acid-form, such as Amberlyst* 15, a mixture is reacted, which consists oE
31.5 parts by wt of ethanol (7.5% water cont.), 1, and 68.5 parts of an olefin fraction, 2, containing 50~a% by wt of isobutene.
The composition of the resultant mixture, 3, is as follows:
1 n Non-reactive butenes 33.7% by wt Isobutene 34.8~ do.
Ethanol - 29.1% do.
Water 2.4% do The mixture, fed at a space velocity of 20 litres per litre of catalyst an hour, is reacted at a temperature of 80C, whereby the following reaction product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 9.0% do.
Ethyl tert.butyl ether 37.1% do Tert.butyl alcohol7.2% do Ethanol 12.4% do.
Water 0.6~ do.
The subsequent fractionation of the reaction product is carried out in a rectification column wherein there are obtained 57.3 parts of a bottom product, 5, having the following composition:
Ethyl tert.butyl ether - 64.7~ by wt Tert.butyl alcohol12.6% do.
Ethanol 21.6% do.
Water 1.1~ do.
;,`;~ * Trade Mark.
- - 13 - ~ z ~z ith a ~ater Gon.tent, referred to the sum of all -the al-cohols being present, o~ 3.1~ by v~t.
The colu~n head stream9 6 ,consists of ~2~7 parts of an olefin fraction having the follo~ing co~po~i-tion:
Unreacted butenes 7~.9~ by ~.t Isobutene 21.1qo do.
PROCESS FOR PRODUCI~G GASOLINE-GRADE C2-C4 ALCOHOLS
FROM AQUEOUS MIXTURES CONTAI~ING THEM
This invention relates to a process for procuding gasoline-grade (e.g. C2-C~) alcohols from aqueous mixtures containing them.
It is known long since that ethanol has very appreciable octane-number characteristics so that it can be used as such in the formulation of fuel mixtures to reduce the percentage of lead-al,kyl additives, or, as in alter-native, to reduce the aromatics conten-t in gasolines.
Ethanol is conventionally produced on a commer-cial scale by fermentation oE carbohydrates: in these procedures, the percentage of alcohol in the fermentation products of sugar-containing juices is below 10~. The subsequent steps directed to recovering alcohol comprise a sequence of distillation steps which permit to arrive at a water-ethanol azeotropic mixture, which, under atmo-spherical pressures, has a water content of 4.4% by weight.
However, this kind of ethanol still contains too much water for enabling it to be employed directly in fuels, so that further dehydration stages become necessary.
The rectification stages and, more particularly, the final dehydration step, have a negative bearing on the first cost of gasoline-grade ethanol.
This circumstance has been conducive to a number of studies dealing with the optimization of the heat recovery in the conventional systems and also to a series of suggestions for alternative dehydration procedures.
Absolute ethanol is obtained in the present times by azeotropic distillation with benzene.
25;~
Alternati.ve suggestions have been made recently, however, which are based on the.strippin.g of water by selective absorption on starchy substances and preferenti.al absorptions on textile fibers, extractions with solvents in cri-tical phase, use of membranes which are impervious to either component, absorption on molecular sieves having pore dimensions sufficient to retain water and finally distillation procedures under reduced pressu-res.
All the suggested approaches, however, are affec-ted by the serious drawback that they involve a decrease of the liquid product yield and substantially re~uire high running costs and special apparatus so that also the first costs are high.
It has now been found that it is possible to produce gasoline-grade (e.g. C2-C4) alcohols without resorting to any conventional technique, while concurrently achieving considera-ble economical advantages on account of the simplicity of the operations proposed herein and also of the improvement of the liquid yield.
The present invention in particular provides a process for preparing alcohol mixtures which can be added to gasoline without causing phase demixing, which process comprises reacting a water-ethanol azeotropic mixture with a tertiary olefin, or an olefin cut containing same, in the presence of a catalys-t for the hydration of the olefin selected Erom the group consisting of mineral acids, Lewis' acids and ion-exchallge resins of the acid type, said tertiary olefin being used in a molar excess over the amount of water contained in the mixture, and said reaction being carried out at a temperature comprised between 40C and 90C. and at a space velocity, LHS~, expressed in liters of reactants per liter of catalyst per hour, comprised between 5 and 25.
In accordance with the present invention the molar ,~ , ~6d~;2SZ
excess of tertiary olefin to water ~ay be up to about 5 -to 1.
As indicated abo~e the process o~ the presen~ inven-tion includes the step of reacting a aicohol-water mixture, coming from the relati~e production systems, with either a tertiary olefin or an olefin cut containing it by so doing, the water content is reduced since water, by reacting with the olefin concerned, produces a tertiary alcohol. The resultan-t product, upon stripping the unreac-ted olefins, makes up a mixture which can be added to the fuels in the usual rations without experien-c~ng phase-separatlons, even at temperatures below -.u C
`~ - 2 a -.
The reaction of addition of the tertiary olefin to water can be carried out with -the aid of the conventlonal catalysts as used for ole~in hydrations, such as mineral acids, Lewis' acids and ion-exchange resins, and more particularly those which support -SO3H groups on poly-styrene, divinylbenzene, and polyphenol matrices are preferred due to their greater simplicity of use.
The working conditions, instead, should carefully be selected, inasmuch as too high temperatures, or too low spatial velocities worsen the selectivity of the operation because the competitive reaction of formation of the corresponding ethers might predominate.
The latter reaction should be prevented as far as practicable because it substracts the tertiary olefin to its reaction with water, the result being that the production of the tertiary alcohol is decreased: the ter-tiary alcohol is appreclable since it has a solubilizing action on the water residue.
As indicated above the addition reaction can be carried out within a temperature range between 40C and 90C under a pressure whi.ch is so selected as to maintain the hydrocarbon steams being processed either in.the liquid or the gaseous phase according to the advisability of processing the streams concerned in the vapor or the liquid phase.
When working in the liquid phase, the spatial velocity ~LHSV) of the reaction, expressed in litres of feed per litre of catalyst in an hour, is comprised between 5 and 25.
FIGURE 1 of the accompanying drawing is illus-` - 3 -- 4 ~
trative of a particular e~bodiment of the process accor-ding to the present invention relative to a treatment of c~n aqueous mixture which contains ethanc,l, with an ole~ir.
fraction which contains isobutene: the alcoholic mixture, 1, and the feeding olefin lraction,3, are sent, together - with the recycled ole~ins,2, to the reactor R-1: the re-action product,5, is sent to the rectification column,C-1, rom the bottom of which e-thanol is reco~rered togeth~r with the reaction product an~ the unreacted water,~. A'.t the col~n head, the olefin fraction is recovered, which i.s partly recyc~ed -to the reactor P-1 and partly is dl]mped at 8.
~ I~URE 2 shows a diagram akin to that of FI~.1, but without olefin recycling.
A few examples v~ill now be given, which are me-rely illustrative of the invention without limi.tation.
ln Example 1 there is reported a scheme which - explains the possibiliti~s afforded by the process of this invention. As can be seen, it becomes possible to obtain a product which is perfectly miscible wi-th gasoli nes also at low temperatures, while conc-urrently achieving an improvement in the yield relative to the starting alcohol in the order of magnitude of 18~o a-t the expenses of a ga-seous product such as isobutene,which has not been directly added to gasoline, as this is not possi.ble~
The comparison between the results of ~am~ple 2 and those of Example 3 shows how important may be to li~it the conversion of ethanol. As a matter of fact, by working at a lower space velocity, a product is obtained, which, when admixed with gasoline, has a higher turbidity temperature ~60Z5Z
The comparison between the results of Examples 4, 5 and 6 shows that, the spatial velocity being the same, the reaction temperature becornes critical: in the examples reported herein, the optimum value is at 70C.
EX~MPI,F. 1 In a tubular reactor, see Fig. 1, which contains a macroporous acid-form ion-exchange resin such as Amber-lyst* 15, a mixture is reacted, which is composed by 28.20 parts by weight of ethanol (containing 7% by wt oE water), 1, 61.50 parts of a recycle oleEin fraction, 2, containing 6.4~ by wt of isobutene and 10.36 parts of an olefin frac-tion, 3, containing 50% by wt of isobutene.
The composition of the resultant mixture is as follows:
Non-reactive butenes 62.7% by wt Isobutene 9.1% do.
Ethanol 26.2% do.
Water 2.0% do.
The mixture, fed at a space velocity equal to 10 litres an hour per litre of catalyst, is caused to react at a temperature of 70C and the following reaction product, 5, is obtained:
Unreacted butenes 62.7% by wt Isobutene 4.3% do.
Ethyl tert.butyl ether 3.6% do.
Tert.butyl alcohol 3.8% do.
Ethanol 24.6% do.
Water 1.0% do.
The subsequent fractionation of the reac-tion product is carried out in a rectification column, wherein * Trade Mark.
5%
33.0 parts of a bottom product, 6, are obtained, which has the following composition:
Ethanol 74.5% by wt Water 3.0% do.
Tert.butyl alcohol 11.5% do.
Ethyl tert.butyl ether11.0% do.
and 67 parts of a head product, 7, having the following composition:
Unreacted butenes 93.6% by wt Isobutene 16.~% do.
Of this stream, 61.5 parts are recycled to the reaction, 2, and 5.5 parts, 8, are sent to subsequent uses.
The column bottom product, stream 6, can directly be admixed with gasolines without any demixing problems.
By way of comparison, there are reported here-under the values of the turbidity temperature of the etha-nol of the charge 1 (mixture A) and of the reaction product 6 (mixture B), both supplemented as the 10% by wt to a.
hydrocarbon stream containing the 30% by wt of aromatics and the 70% by wt of saturated hydrocarbons.
Turbidity temperature,C
Mixture A above +20C
Mlx-ture B under -20C
In a tubular reactor, see Fig.2, containing a macroporous acid form ion-exchange resin such as Amberlyst*
15, a mixture is caused to react, which is composed by 34.1 parts by wt of ethanol (7.3~ water) and 65.9 parts by wt of an olefin fraction, 2, containing 50.7% by wt of isobutene.
* Trade Mark Z
The composition of the resultarlt ml~ture,39 is as follows:
Non-reactive butenes 32.5% by wt Isobutene 33O4% do~
~thanol 31.6% do.
Water 2~5~o do.
The mixture, fed at a space velocity equal -to 1.5 litres an hour per litre of catal~st, is caused to react a~ a temperature o~ 60C, whereby the Iollowing - 10 reaction product, ~, is obtained:
Unreacted butenes 32.50,~ ~y wt Isobutene 2.5% doO
Ethyl tQrt.buty:l ether 45.7% do.
Tert.butyl alcohol 7.9~0 do.
Ethanol 10~7~ do.
Water 0.7~ do.
The subsequent fractionation of the reaction product is carried out in a rectifica-tion column, wherein ther~ are obtained 65 parts of a bottom product,5, havin`g the fol'owing composition:
Ethyl tert.butyl ether 70~4% by Vlt Tert.butyl alc~hol 12.1% do.
Ethanol 16.~% do~
Water 1.1% do.
The water content, referred to the s~m of the alcohols which are present, is 3.7~ by wt.
The column head stream~ 6, is composed by 35.0 parts of an olefin fraction having the following composi-tion :
s~
~nreacted butenes 92.9% by wt Isobutene 7.1% do The turbidity temperature of a mixture of 10%
by wt of the column bottom produc-t 5 with 90~ by wt of a hydrocarbon frac-tion (70% by wt of saturated hydroc. and 30% of aromatics) is -12C.
In a tubular reactor, see FIG.2, containing a macroporous acid-form ion-exchange resin such as Amberlyst*
15, there is caused -to react a mixture consisting of 34.2 parts by wt of ethanol (7.8% water cont.), l, and 65.8 parts by wt of an olefin fraction, 2, containing 48.2% by wt of isobutene.
The co~position of the resultant mixture, 3, is as follows:
Non-reactive butenes34.1% by wt Isobutene 31.7% do.
Ethanol 31.5% do.
Water 2.7% do.
This mixture, fed at a space velocity equal to 16 litres per litre of catalyst an hour, is caused to react at a temperature of 60C and the following reaction product, 4, is obtained:
Unreacted butenes 34.1% by wt Isobutene 22.9% do.
Ethyl tert.butyl ether 5.5% do.
Tert.butyl alcohol 7.9% do.
Ethanol 28.9% do.
Water 0.7% do.
The subsequent Eractionation of the reaction * Trade Mark.
zsæ
product is carried out in a rectification ~olumn, whereln there are obtained 43.0 parts of bottor~ procluctt 5, ha-ving -the following composition:
~thyl tert.butyl ether 12~o by ~ t I'ert.butyl alcohol ~8.~o do.
Ethanol G7.2% do~
Water ~.6% do.
with a eontent of ~Yater~ re~erred to the sum of -the al-eohols whieh are present, of l.~o by ~t.
~'he column head stream,6, is composed b~ 57.0 parts o~ an ole~in fraction having the following eompo sition:
Unreacted butenes 59~&~o by wt Isobutene 4Q, ~k~ do.
The turbidity tempera-ture of a mi~tuxe of ~0 by weight of column bottom preduct,5, with 9~0 by wt o~
a hydrocarbon fraction ( 70~o by wt o~ saturated hydroc.
` ~ and 30~0 by wt of aro~latics~ is under -20C.
- E x ~ m 2_~_ e ~ 20 In a tubular reaetor, see FIG.2, containing a maeroporous aeid-form ion-exchange resin sueh as Amberlyst *
15 there is caused to react a mi~-ture consisting oI 31.5 parts by wt of ethanol (7.5~0 wa-ter ccnl.), 1, and 68.5 parts o~ an ole~in fraction , 2, containing 50.8~ by ~-Jt of isobutene.
The composition o~ the resultant mixture, 3, is as follows :
Non-reaGtive butenes 33.7% by ~rt Isobutene 3~80~o do.
Ethanol 29~1% do.
Y~ater 2.470 do.
* Trade mark . ,?`
The mixture, fed at a space velocity equal to 20 litres per litres of catalyst an hour, is reacted at a temperature of 60C and the following reaction product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 25.7% do.
Ethyl tert.butyl ether 6.5% do Tert.Butyl alcohol 7.2% do Ethanol 26.2% do Water 0.7% do.
The subsequent fractionation of the reaction product is carried out in a rectification column, wherein there are obtained 40.6 parts of a bottom product, 5, having the following composition:
Ethyl tert.butyl ether 16.0% by wt Tert.butyl alcohol 17.7% do.
Ethanol 64.6% do.
Water 1.7% do.
With a content of water, referred to the sum oE
the alcohols which are present of 2.0% by wt.
The column heacl stream, 6, consists of 59.4 parts of an olefin fraction having the following composition:
Unreacted butenes 56.7% by wt Isobutene 43.3% do.
In a tubular reactor, see FIG.2, containing a macroporous acid-form ion-exchange resin such as Amberlyst*
15 there is caused to react a mixture consisting oE 31.5 parts by wt of ethanol (7.5% water cont.), 1, and 68.5 parts of an olefin fraction, 2, containing 50.8% by wt * Trade Mark.
~ -- 1 0 o~ isobutene.
The composition OI the resultant mi~:~,ure, 3, is as follows:
Non-reactive butene~ 3~.7~ by wt Isobutene 34.8~o do.
Ethanol 29.~% do.
Water 2.4~o doO
The latter miYture, fed at a space velocity of 20 litres per liter of cataiyst an hour, is cau~ed to react lO at a te~perature of 70C, whereby the ~ollowing reaotion product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 14.0~ doO
~thyl ter-t~butyl ether 27.3~ doO
Tert.butyl alcohol 8. l~o aO .
Ethanol 16.5% do.
- Water 0.4~ do.
The subsequen-t ~rsctionatiQn of the re~ction - product is carried Ollt in a rectification colwnn, wherein there are ob-tai~ea 52.3 parts of a bottom product, 59 ha-ving the following compositlon:
Ethyl tert~butyl ether 52.2% by w-t Tert.butyl alcohol 1~o5% do.
~thanol 31.5% do.
Water 0.8~o doO
Water cont.relO to the sum o~ alcohols present1.7% doO
The column head stream, G, consists of 47.7 p~rts of an ole-in f~action having the following composltion:
Unreacted butenes 70~6% by l~t Isobutene 29.4% ~o~
--;
In a tubular reactor, see FIG.2, containing a macroporous ion-exchange resin of the acid-form, such as Amberlyst* 15, a mixture is reacted, which consists oE
31.5 parts by wt of ethanol (7.5% water cont.), 1, and 68.5 parts of an olefin fraction, 2, containing 50~a% by wt of isobutene.
The composition of the resultant mixture, 3, is as follows:
1 n Non-reactive butenes 33.7% by wt Isobutene 34.8~ do.
Ethanol - 29.1% do.
Water 2.4% do The mixture, fed at a space velocity of 20 litres per litre of catalyst an hour, is reacted at a temperature of 80C, whereby the following reaction product, 4, is obtained:
Unreacted butenes 33.7% by wt Isobutene 9.0% do.
Ethyl tert.butyl ether 37.1% do Tert.butyl alcohol7.2% do Ethanol 12.4% do.
Water 0.6~ do.
The subsequent fractionation of the reaction product is carried out in a rectification column wherein there are obtained 57.3 parts of a bottom product, 5, having the following composition:
Ethyl tert.butyl ether - 64.7~ by wt Tert.butyl alcohol12.6% do.
Ethanol 21.6% do.
Water 1.1~ do.
;,`;~ * Trade Mark.
- - 13 - ~ z ~z ith a ~ater Gon.tent, referred to the sum of all -the al-cohols being present, o~ 3.1~ by v~t.
The colu~n head stream9 6 ,consists of ~2~7 parts of an olefin fraction having the follo~ing co~po~i-tion:
Unreacted butenes 7~.9~ by ~.t Isobutene 21.1qo do.
Claims (4)
1. A process for preparing alcohol mixtures which can be added to gasoline without causing phase demixing, which pro-cess comprises reacting a water-ethanol azeotropic mixture with a tertiary olefin, or an olefin cut containing same, in the presence of a catalyst for the hydration of the olefin selected from the group consisting of mineral acids, Lewis' acids and ion-exchange resins of the acid type, said tertiary olefin being used in a molar excess over the amount of water contained in the mixture, and said reaction being carried out at a tempe-rature comprised between 40°C. and 90°C. and at a space velocity, LHSV, expressed in liters of reactants per liter of catalyst per hour, comprised between 5 and 25.
2. Process according to claim 1, wherein the molar excess of tertiary olefin to water is up to about 5 to 1.
3. Process according to claim 1, wherein said ion-exchange resin of acidic character contains sulfone groups
4. Process according to claim l, wherein the tertiary olefin is isobutene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21068A/80 | 1980-03-31 | ||
| IT21068/80A IT1140794B (en) | 1980-03-31 | 1980-03-31 | PROCEDURE FOR THE PRODUCTION OF C2-C4 "GASOLINE" ALCOHOLS FROM AQUEOUS MIXTURES CONTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160252A true CA1160252A (en) | 1984-01-10 |
Family
ID=11176255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000374128A Expired CA1160252A (en) | 1980-03-31 | 1981-03-30 | Process for producing gasoline-grade c.sub.2- c.sub.4 alcohols, from aqueous mixtures containing them |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS56151790A (en) |
| AU (1) | AU550088B2 (en) |
| BE (1) | BE888150A (en) |
| BR (1) | BR8101872A (en) |
| CA (1) | CA1160252A (en) |
| CH (1) | CH648340A5 (en) |
| CS (1) | CS221292B2 (en) |
| DD (1) | DD157700A5 (en) |
| DE (1) | DE3112277C2 (en) |
| DK (1) | DK137281A (en) |
| ES (1) | ES501396A0 (en) |
| FR (1) | FR2479186A1 (en) |
| GB (1) | GB2072668B (en) |
| HU (1) | HU192065B (en) |
| IE (1) | IE51127B1 (en) |
| IT (1) | IT1140794B (en) |
| LU (1) | LU83265A1 (en) |
| NL (1) | NL8101594A (en) |
| NO (1) | NO811022L (en) |
| NZ (1) | NZ196606A (en) |
| PL (1) | PL230427A1 (en) |
| RO (1) | RO84498B (en) |
| SE (1) | SE8101977L (en) |
| SU (1) | SU1034610A3 (en) |
| YU (1) | YU41038B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7007764B2 (en) | 2002-12-06 | 2006-03-07 | Manitowoc Crane Companies, Inc. | Carbody to crawler connection |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0723331B2 (en) * | 1985-03-12 | 1995-03-15 | 旭化成工業株式会社 | Method for producing tertiary butanol |
| JP2007021643A (en) * | 2005-07-15 | 2007-02-01 | Amada Co Ltd | Work attracting device using permanent magnet |
| US10570071B1 (en) | 2018-12-12 | 2020-02-25 | Saudi Arabian Oil Company | Membrane-based process for butanols production from mixed butenes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL299568A (en) * | 1900-01-01 | |||
| FR1314120A (en) * | 1962-01-08 | 1963-01-04 | Bayer Ag | Process for the preparation of tert-butyl and alkyl ethers |
| DE1249844B (en) * | 1962-03-21 | 1967-09-14 | GuIf Research &. Development Company, Pittsburgh, Pa (V St A) | Process for the production of alcohols by the addition of water to the corresponding olefins in the liquid phase |
| US3822119A (en) * | 1970-11-19 | 1974-07-02 | Goodyear Tire & Rubber | Anti-pollution anti-knock gasoline |
| DE2629769C3 (en) * | 1976-07-02 | 1989-03-16 | Hüls AG, 4370 Marl | Process for the preparation of pure methyl tertiary butyl ether |
| US4087471A (en) * | 1977-05-20 | 1978-05-02 | Petro-Tex Chemical Corporation | Fixed bed process for the production of t-butanol |
-
1980
- 1980-03-31 IT IT21068/80A patent/IT1140794B/en active
-
1981
- 1981-03-18 IE IE602/81A patent/IE51127B1/en unknown
- 1981-03-19 GB GB8108640A patent/GB2072668B/en not_active Expired
- 1981-03-24 NZ NZ196606A patent/NZ196606A/en unknown
- 1981-03-26 DK DK137281A patent/DK137281A/en not_active Application Discontinuation
- 1981-03-26 FR FR8106118A patent/FR2479186A1/en active Granted
- 1981-03-26 NO NO811022A patent/NO811022L/en unknown
- 1981-03-26 BR BR8101872A patent/BR8101872A/en unknown
- 1981-03-27 SE SE8101977A patent/SE8101977L/en not_active Application Discontinuation
- 1981-03-27 DE DE3112277A patent/DE3112277C2/en not_active Expired
- 1981-03-27 BE BE0/204278A patent/BE888150A/en not_active IP Right Cessation
- 1981-03-30 PL PL23042781A patent/PL230427A1/xx unknown
- 1981-03-30 CH CH2146/81A patent/CH648340A5/en not_active IP Right Cessation
- 1981-03-30 AU AU68903/81A patent/AU550088B2/en not_active Ceased
- 1981-03-30 JP JP4566881A patent/JPS56151790A/en active Pending
- 1981-03-30 CA CA000374128A patent/CA1160252A/en not_active Expired
- 1981-03-30 SU SU813266251A patent/SU1034610A3/en active
- 1981-03-30 YU YU828/81A patent/YU41038B/en unknown
- 1981-03-30 HU HU81810A patent/HU192065B/en unknown
- 1981-03-30 RO RO103858A patent/RO84498B/en unknown
- 1981-03-30 LU LU83265A patent/LU83265A1/en unknown
- 1981-03-31 CS CS812393A patent/CS221292B2/en unknown
- 1981-03-31 NL NL8101594A patent/NL8101594A/en not_active Application Discontinuation
- 1981-03-31 ES ES501396A patent/ES501396A0/en active Granted
- 1981-03-31 DD DD81228774A patent/DD157700A5/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7007764B2 (en) | 2002-12-06 | 2006-03-07 | Manitowoc Crane Companies, Inc. | Carbody to crawler connection |
Also Published As
| Publication number | Publication date |
|---|---|
| HU192065B (en) | 1987-05-28 |
| LU83265A1 (en) | 1981-10-29 |
| JPS56151790A (en) | 1981-11-24 |
| IT8021068A0 (en) | 1980-03-31 |
| YU82881A (en) | 1983-02-28 |
| IE51127B1 (en) | 1986-10-15 |
| GB2072668A (en) | 1981-10-07 |
| SU1034610A3 (en) | 1983-08-07 |
| BE888150A (en) | 1981-09-28 |
| NL8101594A (en) | 1981-10-16 |
| CH648340A5 (en) | 1985-03-15 |
| BR8101872A (en) | 1981-10-06 |
| PL230427A1 (en) | 1981-11-13 |
| FR2479186A1 (en) | 1981-10-02 |
| IE810602L (en) | 1981-09-30 |
| ES8202776A1 (en) | 1982-02-16 |
| DK137281A (en) | 1981-10-01 |
| ES501396A0 (en) | 1982-02-16 |
| FR2479186B1 (en) | 1982-11-26 |
| SE8101977L (en) | 1981-10-01 |
| NZ196606A (en) | 1984-03-16 |
| NO811022L (en) | 1981-10-01 |
| AU550088B2 (en) | 1986-03-06 |
| IT1140794B (en) | 1986-10-10 |
| YU41038B (en) | 1986-10-31 |
| GB2072668B (en) | 1984-03-28 |
| DE3112277C2 (en) | 1985-05-02 |
| RO84498B (en) | 1984-08-30 |
| DE3112277A1 (en) | 1982-03-18 |
| DD157700A5 (en) | 1982-12-01 |
| CS221292B2 (en) | 1983-04-29 |
| AU6890381A (en) | 1981-10-08 |
| RO84498A (en) | 1984-06-21 |
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