GB1589457A - Method for purifying methyl tert butyl ether - Google Patents
Method for purifying methyl tert butyl ether Download PDFInfo
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- GB1589457A GB1589457A GB2120778A GB2120778A GB1589457A GB 1589457 A GB1589457 A GB 1589457A GB 2120778 A GB2120778 A GB 2120778A GB 2120778 A GB2120778 A GB 2120778A GB 1589457 A GB1589457 A GB 1589457A
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- methanol
- hydrocarbons
- mixture
- mtbe
- distillation
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Description
(54) METHOD FOR PURIFYING METHYL TERT-BUTYL ETHER
(71) We, SNAMPROGETTI S.p.A., an Italian company, of Corso Venezia, 16, Milan,
Italy, do herebv declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to a method for the separation of methyl tert-butyl ether and methanol from each other when both are admixed with a C4 hydrocarbon or a mixture of C4 hydrocarbons.
Methyl tert-butyl ether can be produced by reacting methanol with iso-butene. It is known that the reaction is conveniently conducted in the liquid phase on a catalyst comprising an ion-exchange resin, using the iso-butene contained in an olefin stream obtained by steam cracking or catalytic cracking. The reaction is exothermic and proceeds towards equilibrium when conducted in the presence of efficient catalysts. The result is that the reaction product will eventually contain, in addition to the desired ether, a portion of unreacted components and, if an olefin fraction has been used rather than pure iso-butene,
C4 hydrocarbons which are predominantly straight-chain butenes. The separation of the hydrocarbons is no special problem since it is possible to remove them by fractional distillation. Greater difficulties are experienced, however, in the separation of the methanol.
It has been suggested is to carry out a washing step with water to remove methanol selectively, but this procedure is cumbersome inasmuch as the ether becomes saturated with water and must be subjected to expensive dehydration steps.
According to the present invention there is provided a method for the separation of methyl tert-butyl ether and methanol from each other when both are present in a mixture comprising one or more C4 hydrocarbons, which method comprises subjecting the mixture to distillation, the amount of methanol present in the mixture and the pressure at the distillation head being related by the relationship: M # 1 + P
3 wherein M is the percentage by weight of methanol, relative to the total weight of C4 hydrocarbon(s) and methanol, and P is the pressure at the distillation head in atmospheres (absolute).
The percentage of methanol is generally less than 5% and is preferably less than or equal to 3%. The pressure is generally less than 20 atmospheres, preferably 6 atmospheres.
Preferably, the mixture subjected to distillation is one obtained by reacting a mixture of
C4 hydrocarbons, including iso-butene, with methanol.
As regards the operative conditions which are required in order that the reaction product may have the desired content of methanol, it is possible to adopt any means, such as an excess of iso-butene, the use of a number of reactors, or, when the final content of methanol is still somewhat high on completion of the reaction, dilution of the mixture to be distilled with an olefin fraction until the methanol content is within the desired range. In the latter case, a portion of the head distillate can be recycled to the mixtuure so that a partial recovery of methanol can be achieved.
The invention will now be illustrated by the following Examples, wherein all percentages are percentages by weight. Examples 3 to 8 are not in accordance with the invention, and are included for comparison purposes only.
The abbreviations "MTBE" and "TBA" used in the Examples mean "methyl tert-butyl ether" and " tert-butyl alcohol", respectively.
Example I
A distillation assembly consisting of a plate column having an efficiency of 15 theoretical plates and operating with a reflux ratio of 1:1 and at a head pressure of 6 atmospheres (absolute), was fed with a charge having the following composition:
C4 hydrocarbons . ................... . 59.54% MTBE ..... ....... ...... 39.75%
Methanol . ........ 0.52%
TBA ....... .. 0.08%
Di-isobutene . , ....... 0.11 No Thus the methanol content was 0.86% relative to the sum of the C4 hydrocarbons and the methanol.
At the column head, there was obtained a fraction which had the following composition:
C4 hydrocarbons . ........ . . 99.14%
Methanol . 0.86%
At the tail, there was obtained a fraction having the following composition; C4 hydrocarbons . ........ 0.22% MTBE . . 99.29% TBA . 0.21%
Di-isobutene . 0.28% Thus, all of the methanol had been removed.
Example 2
The same apparatus and the same conditions as in Example 1 were used. The apparatus was fed with a charge having the following composition:
C4 hydrocarbons . . 40.03% MTBE . . 58.31%
Methanol . 0.98%
TBA . 0.27%
Di-isobutene . 0.41%
Thus the methanol content was 2.39% relative to the sum of the C4 hydrocarbons and the methanol.
At the column head, there was obtained a fraction having the following composition:
C4 hydrocarbons .................. W 97.60%
Methanol . . 2.04%
At the column tail, there was obtained a fraction having the following composition;
C4 hydrocarbons . .... 0.24% MTBE ............... ........ 98.42%
TBA . .................... , 0.44%
Di-isobutene . .. ......... 0.90% Example 3 (Comparison)
The same apparatus and the same conditions as in Example 1 were used. The apparatus was fed with a charge having the following composition:
C4 hydrocarbons . ................ ....... . 39.55% MTBE ...... ........ ........... .. 57.96%
Methanol . ....... 2.15% TBA . ............. 0.16% Di-isobutene . ......... ................ ........ 0.18% Thus, the methanol content was 5.15% relative to the sum of the C4 hydrocarbons and the methanol.
At the head, there was obtained a fraction having the following composition:
C4 hydrocarbons . . . 97.25% Methanol . ............. 2.75% At the tail, there was obtained a fraction having the following composition;
C4 hydrocarbons . ....... 0.20%
MTBE .. . 97.48%
Methanol . 1.75%
TBA . 0.27%
Di-isobutene . 0.30%
Example 4 (comparison)
The same apparatus and the same conditions as Example 1 were used. The apparatus was fed with a charge having the following composition: C4 hydrocarbons . ........ . .................. . 39.26% MTBE . ....... . . 57.67% Methanol ....... .................. ...................... 2.80%
TBA . ............. ................. .............. 0.15% Di-isobutene ...... ....... 0.13%
Thus the methanol content was 6.66% relative to the sum of methanol and the C4 hydrocarbons.
At the head, there was obtained a fraction having the following composition:
C4 hydrocarbons .................. ...................... 97.50%
MTBE . ............ 0.03%
Methanol ........ ....... ....... 2.47%
At the bottom, there was obtained a fraction having the following composition; C4 hydrocarbons . ....... ....... ........... 0.06%
MTBE . . . 96.46%
Methanol . ....... ............. 3.00%
TBA . .......... 0.25%
Di-isobutene . ....... ....... ......... 0.24% Example 5 (Comparison)
The same apparatus and the same conditions as in Example 1 were used. The apparatus was fed with a charge having the following composition:
C4 hydrocarbons . . 39.48%
MTBE . . 56.67%
Methanol . 3.60%
TBA . 0.13%
Di-isobutene . 0.12% Thus the content of methanol was 8.36% relative to the sum of the methanol and the C, hydrocarbons.
At the column head there was obtained a fraction which had the following composition:
C4 hydrocarbons . . . 95.03% MTBE . 0.57% Methanol . 4.40%
At the tail, there was obtained a fraction having the following composition;
C4 hydrocarbons ........................................ 0.21%
MTBE .. ............... ....... ....... 96.41% Methanol . ....... ......... ....... ....... 3.00%
TBA . ............................ ....... 0.22% Di-isobutene .......... ........ ........ ......... 0.16%
Example 6 (Comparison)
The apparatus of Example 1 was fed with the charge described in Example 3. Distillation was carried out under conditions such that all of the methanol passed through the head of the column.
Under these conditions, there was obtained a head fraction having the following composition:
C4 hydrocarbons . ....... ........ . . 83.10% MTBE . ...... ........ ......................... 12.38% Methanol . ............. ............. 4.52%
There was also obtained a tail fraction having the following composition;
MTBE .. . . 99.35% TBA . 0.30%
Di-isobutene . ....... ....... ......... .............. 0.35% The recovery of MTBE was therefore 89.83%.
Example 7 (Comparison)
The apparatus described in Example 1 was fed with the charge described in Example 4.
Distillation was carried out under conditions such that all of the methanol was obtained at the head.
The head fraction which was thus obtained had the following composition:
C4 hydrocarbons . . 78.32% MTBE ....... ....... 16.74% Methanol . 4.94%
The tail fraction obtained had the following composition.
MTBE . . 99.36%
TBA . 0.32%
Di-isobutene . 0.32%
The recovery of MTBE was therefore 82.4%.
Example 8 (Comparison)
The apparatus described in Example 1 was fed with the charge described in Example 5.
Distillation was carried out under conditions such that all of the methanol was obtained at the head.
The head fraction obtained had the following composition: C4 hydrocarbons . ........ 74.08% MTBE . . 19.19% Methanol . 6.72%
The tail fraction obtained had the following composition;
MTBE . . 99.46% TBA 0.27% Di-isobutene . 0.27%
The recovery of MTBE dropped in this case to 71.3%.
Example 9
The apparatus of Example 1 was charged with the charge described in Example 3.
Distillation was carried out such that the reflux- ratio was 1:1 and the head pressure was 14 atmospheres (absolute).
At the head, the fraction obtained had the following composition:
C4 hydrocarbons 94.85%
Methanol 5.15%
The tail fraction obtained had the following composition;
C4 hydrocarbons . . trace
MTBE . . 99.42%
TBA 0.27%
Di-isobutene . 0.31%
Example 10
The apparatus of Example 1 was fed with the charge described in Example 4. Distillation was carried out such that the reflux ratio was 1:1 and the head pressure was 17 atmospheres (absolute).
The head fraction obtained had the following composition:
C4 hydrocarbons . . 93.34%
Methanol 6.66%
The tail fraction obtained had the following composition; C4 hydrocarbons . ........ .... trace MTBE . . 99.52% TBA . . 0.26%
Di-isobutene . 0.22%
WHAT WE CLAIM IS;
1. A method for the separation of methyl tert-butyl ether and methanol from each other when both are present in a mixture comprising one or more C4 hydrocarbons, which method comprises subjecting the mixture to distillation, the amount of methanol present in the mixture and the pressure at the distillation head being related by the relationship: M 1 P wherein M is the percentage by weight of methanol, relative to the total weight of C4 hydrocarbon(s) and methanol, and P is the pressure at the distillation head in atmospheres (absolute).
2. A method according to the claim 1, wherein M is less than 5.
3. A method according to claim 2, wherein M is 3 or less.
4. A method according to any of claims 1 to 3, wherein P is less than 20.
5. A method according to claim 4, wherein P is 6.
6. A method according to any of claims 1 to 5, wherein the mixture subjected to distillation is one obtained by reacting a mixture of C4 hydrocarbons, including iso-butene, with methanol.
7. A method according to claim 1, substantially as described in any of the foregoing
Examples 1, 2, 9 and 10.
8. Methyl tert-butyl ether whit. never obtained by a method according to any of claims 1 to 7.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (8)
1. A method for the separation of methyl tert-butyl ether and methanol from each other when both are present in a mixture comprising one or more C4 hydrocarbons, which method comprises subjecting the mixture to distillation, the amount of methanol present in the mixture and the pressure at the distillation head being related by the relationship: M 1 P wherein M is the percentage by weight of methanol, relative to the total weight of C4 hydrocarbon(s) and methanol, and P is the pressure at the distillation head in atmospheres (absolute).
2. A method according to the claim 1, wherein M is less than 5.
3. A method according to claim 2, wherein M is 3 or less.
4. A method according to any of claims 1 to 3, wherein P is less than 20.
5. A method according to claim 4, wherein P is 6.
6. A method according to any of claims 1 to 5, wherein the mixture subjected to distillation is one obtained by reacting a mixture of C4 hydrocarbons, including iso-butene, with methanol.
7. A method according to claim 1, substantially as described in any of the foregoing
Examples 1, 2, 9 and 10.
8. Methyl tert-butyl ether whit. never obtained by a method according to any of claims 1 to 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2523477A IT1081278B (en) | 1977-06-30 | 1977-06-30 | PROCESS FOR PURIFYING THE BUTYL TERTIARY ETHER METHY FROM METHANOL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589457A true GB1589457A (en) | 1981-05-13 |
Family
ID=11216080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2120778A Expired GB1589457A (en) | 1977-06-30 | 1978-05-22 | Method for purifying methyl tert butyl ether |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5412308A (en) |
| BE (1) | BE868636A (en) |
| CA (1) | CA1108553A (en) |
| DE (1) | DE2828664B2 (en) |
| FR (1) | FR2395978A1 (en) |
| GB (1) | GB1589457A (en) |
| IT (1) | IT1081278B (en) |
| LU (1) | LU79885A1 (en) |
| NL (1) | NL7807035A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2134905A (en) * | 1983-02-08 | 1984-08-22 | Phillips Petroleum Co | Processes for the production and recovery of methyl tertiary butyl ether |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322565A (en) * | 1979-08-23 | 1982-03-30 | Columbian Chemicals Company | Process for purifying ethers |
| US4262149A (en) * | 1980-04-21 | 1981-04-14 | Columbian Chemicals Company | Process for separating alkanols from aqueous calcium chloride |
-
1977
- 1977-06-30 IT IT2523477A patent/IT1081278B/en active
-
1978
- 1978-05-22 GB GB2120778A patent/GB1589457A/en not_active Expired
- 1978-05-30 CA CA304,387A patent/CA1108553A/en not_active Expired
- 1978-06-22 FR FR7818761A patent/FR2395978A1/en active Granted
- 1978-06-28 LU LU79885A patent/LU79885A1/xx unknown
- 1978-06-28 JP JP7757578A patent/JPS5412308A/en active Pending
- 1978-06-29 NL NL7807035A patent/NL7807035A/en active Search and Examination
- 1978-06-29 DE DE19782828664 patent/DE2828664B2/en not_active Withdrawn
- 1978-06-30 BE BE188986A patent/BE868636A/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2134905A (en) * | 1983-02-08 | 1984-08-22 | Phillips Petroleum Co | Processes for the production and recovery of methyl tertiary butyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2828664B2 (en) | 1979-09-06 |
| NL7807035A (en) | 1979-01-03 |
| LU79885A1 (en) | 1978-12-07 |
| CA1108553A (en) | 1981-09-08 |
| DE2828664A1 (en) | 1979-01-11 |
| IT1081278B (en) | 1985-05-16 |
| JPS5412308A (en) | 1979-01-30 |
| FR2395978A1 (en) | 1979-01-26 |
| BE868636A (en) | 1979-01-02 |
| FR2395978B1 (en) | 1981-02-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |