CA1131662A - Process for the preparation of tertiary alkyl ethers - Google Patents
Process for the preparation of tertiary alkyl ethersInfo
- Publication number
- CA1131662A CA1131662A CA321,866A CA321866A CA1131662A CA 1131662 A CA1131662 A CA 1131662A CA 321866 A CA321866 A CA 321866A CA 1131662 A CA1131662 A CA 1131662A
- Authority
- CA
- Canada
- Prior art keywords
- reactor
- reaction
- preparation
- alkyl ethers
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
Abstract
A B S T R A C T
A process for the preparation of tertiary alkyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor, characterized in that part of the reaction mixture from the reactor is directly recycled.
A process for the preparation of tertiary alkyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor, characterized in that part of the reaction mixture from the reactor is directly recycled.
Description
~3~6~
A PROCESS FOR TH~ PREPARATION OF TERTIARY ALKYL ETHERS
The invention relates to a process for the preparation of tertiary al]cyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor.
Such a process is known from United Kingdom Patents 957,000 and 1,506,596. For instance, in both applications the preparation is described of methyl tertiary butyl ether from isobutene and methanol at a temperature of about 60C over acidic cation exchange resins. It is known that the reaction has an equilibrium which is more favourable for the synthesis of the ether according as the reaction temperature is lower. A relative-ly low temperature will therefore be required for the synthesis of the ether, whilst the reaction rate has to be enhanced by a catalyst. However, since the reaction is exothermic, the steadily rising temperature causes the equilibrium to become increasingly unfavourable. This causes a considerable decrease in yield and conversion.
Th~ Applicant has now found that higher conversions can be obtained when part of the reaction mixture is directly recycled.
The invention therefore relates to a process for the preparation of tertiary alkyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor, characterized in that part of the reaction mixture from the reactor is directly recycled. The process according to the invention has been found to give a higher conversion at constant space velocities (LHSV) under otherwise identical circumstances, than when the .
~3~
process is carried out without recycling. The advantaye of the process according to the invention is that a smaller reactor will suffice, whilst as an additional advantage it may be mentioned that the relatively hot reactor effluent makes preheating of the feedstock superfluous during the reaction.
Examples of primary alcohols are methanol, ethanol, propanol, butanol, pentanol and, op-tionally, higher alkanols.
Methanol in particular is very suitable. The molar ratios of alcohol to tertiary mono-olefin may vary, but a molar ratio of 1:1 is very suitable.
Ter~ary mono-olefins with 4 to 7 carbon atoms, in par-ticular isobutene, are pre-eminently important for use in the process according to the invention.
The temperatures at which the reaction takes place are usually between 50 and 130C, preferably between 60C and 100C.
Suitable pressures at which the reaction may be effected are from 5 to 50 bar or higher.
The catalysts used are cation exchangers incorporating sulphonic acid groups and based on vinylaromatic polymers, as described in United Kingdom patent 957,000. Other sulphonated resins are also suitable, such as sulphona-ted coal obtained by treatment of bituminous coal with sulphuric acid, and sulphonated phenol-formaldehyde resins. Further suitable products are sulphonated resins of coumarone-indene with cyclopentadiene, sul-phonated resins of coumarone-indene with furfural and sulphonated resins of cyclopentadiene with furfural. It is preferred to use as the catalysts cation
A PROCESS FOR TH~ PREPARATION OF TERTIARY ALKYL ETHERS
The invention relates to a process for the preparation of tertiary al]cyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor.
Such a process is known from United Kingdom Patents 957,000 and 1,506,596. For instance, in both applications the preparation is described of methyl tertiary butyl ether from isobutene and methanol at a temperature of about 60C over acidic cation exchange resins. It is known that the reaction has an equilibrium which is more favourable for the synthesis of the ether according as the reaction temperature is lower. A relative-ly low temperature will therefore be required for the synthesis of the ether, whilst the reaction rate has to be enhanced by a catalyst. However, since the reaction is exothermic, the steadily rising temperature causes the equilibrium to become increasingly unfavourable. This causes a considerable decrease in yield and conversion.
Th~ Applicant has now found that higher conversions can be obtained when part of the reaction mixture is directly recycled.
The invention therefore relates to a process for the preparation of tertiary alkyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor, characterized in that part of the reaction mixture from the reactor is directly recycled. The process according to the invention has been found to give a higher conversion at constant space velocities (LHSV) under otherwise identical circumstances, than when the .
~3~
process is carried out without recycling. The advantaye of the process according to the invention is that a smaller reactor will suffice, whilst as an additional advantage it may be mentioned that the relatively hot reactor effluent makes preheating of the feedstock superfluous during the reaction.
Examples of primary alcohols are methanol, ethanol, propanol, butanol, pentanol and, op-tionally, higher alkanols.
Methanol in particular is very suitable. The molar ratios of alcohol to tertiary mono-olefin may vary, but a molar ratio of 1:1 is very suitable.
Ter~ary mono-olefins with 4 to 7 carbon atoms, in par-ticular isobutene, are pre-eminently important for use in the process according to the invention.
The temperatures at which the reaction takes place are usually between 50 and 130C, preferably between 60C and 100C.
Suitable pressures at which the reaction may be effected are from 5 to 50 bar or higher.
The catalysts used are cation exchangers incorporating sulphonic acid groups and based on vinylaromatic polymers, as described in United Kingdom patent 957,000. Other sulphonated resins are also suitable, such as sulphona-ted coal obtained by treatment of bituminous coal with sulphuric acid, and sulphonated phenol-formaldehyde resins. Further suitable products are sulphonated resins of coumarone-indene with cyclopentadiene, sul-phonated resins of coumarone-indene with furfural and sulphonated resins of cyclopentadiene with furfural. It is preferred to use as the catalysts cation
- 2 -.
6~
exchangers substantially consisting of sulphonated polystyrene resin, for instance a divinylbenzene-cross-linked poly-styrene matrix with 0.5~20% copolymerized divinylbenzene, having ionizable sulphonic acid groups. Other suitable catalysts are perfluorinated polymers or copolymers which contain sulphonic acid groups as well.
Examples of suitable resins are Amberlite IR-12 OH, Amberlite 200, Amberlyst 15 H ~, Dowex 50-X-4, Dowex ~5C-lH, Duoli-te C-26, Permutit ~1, Chempro-C-20 and Imac C8P/H`~--(registered trade marks). An especially suitable catalyst is Duolite C-26, giving a high reaction rate. In the preparation of the ethers the reaction rate is about 2 times higher with D~lite C-26 as a catalyst than with Amberlyst 15 H ~ as a catalyst. The exchange capacity of the acid resin is prefer-ably at least 2.0 meq. H /g dry resin, in particular 3.0 to 5.5 meq. H /g dry resin.
The recycling is performed preferably in such a way that the weight ratio of the recycle stream to the stream of mono-olefin and primary alcohol base materials is from 0.5:1 to 20 6:1. The preferred weight ratio is from 1:1 to 2:1. -Although a higher conversion is obtained by recycling the reaction mixture, the conversion into methyl tertiary butyl ether may amount to 95%, if a second reactor is mounted downstream of the reactor. After having left the first reactor system (with recycling), the reaction mixture is cooled to about 70 C and subsequently introduced into the second reactor in order to allow the isobutene and the alcohol to react further.
The reaction mixture may be purified further from iso-30 butene and alcohol, but it is also possible to top off only the isobutene and to use the methyl tertiary butyl ether, which still contains methanol, for instance as a component in low-lead or lead-free gasolines to increase the octane nuraber of these gasolines.
~Ll ~LV~
~ races of acid present in the reaction mixture, originating from the catalyst, can be removed, for instance, by treating with activated alumina. To th;s end the reaction mixture is passed through a vessel with activated alumina and thus neutralized. The alumina is regularly replenished or treated with a 2% sodium carbonate solution in water and used again.
EX~LE 1 A reactor (0.3 l) was partly filled with an aqueous slurry containing 90 g (dry) sulphonated styrene-divinyl benzene acid ion-exchange resin with an exchange capacity of 4.75 meq. ~ /g dry resin, and the resin was then washed with dry methanol to obtain a water-free resin bed.
A feed of methanol and isobutene (molar ratio 1.25:1) was continuously passed through the reactor at a pressure of 25 bar with a space velocity of 50 l.l catalyst .h 1, and the re-action mixture was continuously discharged. The initial temper-ature of the feed was 70 C and the temperature at the reactor outlet 130 C. The conversion of me-thsnol and isobutene into methyl tertiary butyl ether was determined in the effluent stream. The conversion into methyl tertiary butul ether was 73% (calculated on isobutene).
EXAMPEE 2 (according to the invention) Example 1 was repeated with this difference that the reaction mixture issuing from the reactor was separated into two streams. One stream was recycled via a line to the inlet of the reactor, the weight ratio of the recycle stream to the mixture of methanol and isobutene supplied being 1.5. Again, the space velocity of the feed was 50 l.l catalyst .h It was not necessary to pass the feed through a preheater -to bring it to 70 C. The temperature at the reactor outlet was 104 C. The second stream was discharged, and the conversion : into methyl tertiary butyl e-ther determined. The conversion was 84% (calculated on isobutene).
: .
':
.
6~
exchangers substantially consisting of sulphonated polystyrene resin, for instance a divinylbenzene-cross-linked poly-styrene matrix with 0.5~20% copolymerized divinylbenzene, having ionizable sulphonic acid groups. Other suitable catalysts are perfluorinated polymers or copolymers which contain sulphonic acid groups as well.
Examples of suitable resins are Amberlite IR-12 OH, Amberlite 200, Amberlyst 15 H ~, Dowex 50-X-4, Dowex ~5C-lH, Duoli-te C-26, Permutit ~1, Chempro-C-20 and Imac C8P/H`~--(registered trade marks). An especially suitable catalyst is Duolite C-26, giving a high reaction rate. In the preparation of the ethers the reaction rate is about 2 times higher with D~lite C-26 as a catalyst than with Amberlyst 15 H ~ as a catalyst. The exchange capacity of the acid resin is prefer-ably at least 2.0 meq. H /g dry resin, in particular 3.0 to 5.5 meq. H /g dry resin.
The recycling is performed preferably in such a way that the weight ratio of the recycle stream to the stream of mono-olefin and primary alcohol base materials is from 0.5:1 to 20 6:1. The preferred weight ratio is from 1:1 to 2:1. -Although a higher conversion is obtained by recycling the reaction mixture, the conversion into methyl tertiary butyl ether may amount to 95%, if a second reactor is mounted downstream of the reactor. After having left the first reactor system (with recycling), the reaction mixture is cooled to about 70 C and subsequently introduced into the second reactor in order to allow the isobutene and the alcohol to react further.
The reaction mixture may be purified further from iso-30 butene and alcohol, but it is also possible to top off only the isobutene and to use the methyl tertiary butyl ether, which still contains methanol, for instance as a component in low-lead or lead-free gasolines to increase the octane nuraber of these gasolines.
~Ll ~LV~
~ races of acid present in the reaction mixture, originating from the catalyst, can be removed, for instance, by treating with activated alumina. To th;s end the reaction mixture is passed through a vessel with activated alumina and thus neutralized. The alumina is regularly replenished or treated with a 2% sodium carbonate solution in water and used again.
EX~LE 1 A reactor (0.3 l) was partly filled with an aqueous slurry containing 90 g (dry) sulphonated styrene-divinyl benzene acid ion-exchange resin with an exchange capacity of 4.75 meq. ~ /g dry resin, and the resin was then washed with dry methanol to obtain a water-free resin bed.
A feed of methanol and isobutene (molar ratio 1.25:1) was continuously passed through the reactor at a pressure of 25 bar with a space velocity of 50 l.l catalyst .h 1, and the re-action mixture was continuously discharged. The initial temper-ature of the feed was 70 C and the temperature at the reactor outlet 130 C. The conversion of me-thsnol and isobutene into methyl tertiary butyl ether was determined in the effluent stream. The conversion into methyl tertiary butul ether was 73% (calculated on isobutene).
EXAMPEE 2 (according to the invention) Example 1 was repeated with this difference that the reaction mixture issuing from the reactor was separated into two streams. One stream was recycled via a line to the inlet of the reactor, the weight ratio of the recycle stream to the mixture of methanol and isobutene supplied being 1.5. Again, the space velocity of the feed was 50 l.l catalyst .h It was not necessary to pass the feed through a preheater -to bring it to 70 C. The temperature at the reactor outlet was 104 C. The second stream was discharged, and the conversion : into methyl tertiary butyl e-ther determined. The conversion was 84% (calculated on isobutene).
: .
':
.
Claims (3)
1. A process for the preparation of tertiary alkyl ethers by reaction of a tertiary mono-olefin with a primary alcohol in the presence of a catalyst, the reaction taking place in the liquid phase in a reactor, characterized in that part of the reaction mixture from the reactor is directly recycled.
2. A process according to claim 1, characterized in that the weight ratio of the recycle stream to the stream of base materials is from 0.5:1 to 6:1.
3. A process according to claim 2, characterized in that the ratio is from 1:1 to 2:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7803135A NL7803135A (en) | 1978-03-23 | 1978-03-23 | PROCESS FOR PREPARING TERTIARY ALKYL ETHERS. |
| NL7803135 | 1978-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131662A true CA1131662A (en) | 1982-09-14 |
Family
ID=19830543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA321,866A Expired CA1131662A (en) | 1978-03-23 | 1979-02-20 | Process for the preparation of tertiary alkyl ethers |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS54130508A (en) |
| CA (1) | CA1131662A (en) |
| CH (1) | CH638477A5 (en) |
| DE (1) | DE2911077A1 (en) |
| FR (1) | FR2420518A1 (en) |
| GB (1) | GB2017693B (en) |
| IT (1) | IT1112964B (en) |
| NL (1) | NL7803135A (en) |
| SE (1) | SE445995B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2440931A1 (en) | 1978-11-08 | 1980-06-06 | Inst Francais Du Petrole | PROCESS FOR PRODUCING ETHERS BY REACTION OF OLEFINS WITH ALCOHOLS |
| US4262146A (en) | 1980-01-15 | 1981-04-14 | Phillips Petroleum Company | Production of aliphatic ethers |
| FR2481269A1 (en) * | 1980-04-28 | 1981-10-30 | Inst Francais Du Petrole | PROCESS FOR PRODUCING ETHERS BY REACTING OLEFINS WITH ALCOHOLS |
| CA1254236A (en) * | 1981-07-27 | 1989-05-16 | Donald J. Makovec | Process for the preparation of methyl tert-butyl ether |
| WO2003002500A1 (en) | 2001-06-28 | 2003-01-09 | Zeon Corporation | Solvents containing cycloalkyl alkyl ethers and process for production of the ethers |
| FR2969147B1 (en) | 2010-12-21 | 2013-01-04 | Total Raffinage Marketing | PRODUCTION OF FUEL ADDITIVES BY DEHYDRATION AND SIMULTANEOUS SKELETAL ISOMERISATION OF ISOBUTANOL ON ACID CATALYSTS FOLLOWED BY ETHERIFICATION |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2629769B2 (en) * | 1976-07-02 | 1980-03-13 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of pure methyl tertiary butyl ether |
| JPS5938933B2 (en) * | 1976-11-22 | 1984-09-20 | 日石三菱株式会社 | Continuous production method of tertiary alkyl ether |
-
1978
- 1978-03-23 NL NL7803135A patent/NL7803135A/en not_active Application Discontinuation
-
1979
- 1979-02-20 CA CA321,866A patent/CA1131662A/en not_active Expired
- 1979-03-20 JP JP3185779A patent/JPS54130508A/en active Granted
- 1979-03-21 DE DE19792911077 patent/DE2911077A1/en active Granted
- 1979-03-21 IT IT21194/79A patent/IT1112964B/en active
- 1979-03-21 GB GB7909977A patent/GB2017693B/en not_active Expired
- 1979-03-21 SE SE7902561A patent/SE445995B/en not_active IP Right Cessation
- 1979-03-21 FR FR7907141A patent/FR2420518A1/en active Granted
- 1979-03-21 CH CH267079A patent/CH638477A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB2017693B (en) | 1982-08-11 |
| SE445995B (en) | 1986-08-04 |
| NL7803135A (en) | 1979-09-25 |
| FR2420518A1 (en) | 1979-10-19 |
| GB2017693A (en) | 1979-10-10 |
| JPS54130508A (en) | 1979-10-09 |
| DE2911077C2 (en) | 1988-10-06 |
| IT1112964B (en) | 1986-01-20 |
| SE7902561L (en) | 1979-09-24 |
| DE2911077A1 (en) | 1979-10-04 |
| JPS6339577B2 (en) | 1988-08-05 |
| FR2420518B1 (en) | 1984-06-29 |
| IT7921194A0 (en) | 1979-03-21 |
| CH638477A5 (en) | 1983-09-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |