CA1048062A - Process for the production of methyl tert-butyl ether - Google Patents
Process for the production of methyl tert-butyl etherInfo
- Publication number
- CA1048062A CA1048062A CA228,655A CA228655A CA1048062A CA 1048062 A CA1048062 A CA 1048062A CA 228655 A CA228655 A CA 228655A CA 1048062 A CA1048062 A CA 1048062A
- Authority
- CA
- Canada
- Prior art keywords
- isobutylene
- methanol
- mixture
- parts
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
ABSTRACT OF THE DISCLOSURE:
Methyl tert-butyl ether of high purity is prepared by reacting methanol with isobutylene in the presence of an acid ion exchange resin in two stages by feeding methanol and isobutylene mixed with other hydrocarbons to the respective members of a pair of interconnected reactors so that the quantity of alcohol present in one of the reactors is in excess of the stoichiometric equivalent of the quantity of isobutylene therein, while the quantity of isobutylene present in the other reactor is in excess of the stoichiometric equivalent of the quantity of methanol therein. The methyl tert-butyl ether so formed is recovered through distillation.
Methyl tert-butyl ether of high purity is prepared by reacting methanol with isobutylene in the presence of an acid ion exchange resin in two stages by feeding methanol and isobutylene mixed with other hydrocarbons to the respective members of a pair of interconnected reactors so that the quantity of alcohol present in one of the reactors is in excess of the stoichiometric equivalent of the quantity of isobutylene therein, while the quantity of isobutylene present in the other reactor is in excess of the stoichiometric equivalent of the quantity of methanol therein. The methyl tert-butyl ether so formed is recovered through distillation.
Description
rrhe present invention relates to a process for the production of methyl tert-bu-tyl ether.
Tert alkyl ethers are prepared by reacting a primary alcohol with olefines having a double bond on a tertiary carbon atom~ ~or instance methanol reac-ts with isobutylene or iso-amylenes (2-methyl 1- or 2-pentene)to ~orm respectively methyl tert-butyl ether (MT~E) or methyl ter-amyl ether. (MTAE).
Since the reaction is selective with respect to tertiary olefins, it can thus be utilized for removing such olefins from olefinic streams wherein linear unreactive olefins are also present. The reaction has an equilibrium which is shifted towards the synthesis of the ether when the reaction temperature is lowered, in accordance with its negative enthalpy.
The reaction is catalyzed by Lewis acids (alumini~n trichloride, boron trifluoride), mQneral acids (sulphuric acid) or organic acids ~alk~l and aryl sulphonic acids~ ion-exchange resins). Ion exchange resins in their acid form have been found -to be particularly suitable to this end, and the best results are obtained in fact with macroreticular resins of the "Amberlyst*15" -type. ~y means o~ such catalysts, it is possible to reach the therm~dynamic equilibrium with industrially acceptable contact times, at temperatures of 50-60C. At lower temperatures, which thermodynamically are more favourable, the kinetics is not sufficiently high to permit in practice to reach equilibrium. This fact thus limits the conversions; in the particular case of isobutylene and methanol used in eguimole-cular ratios, the conversions reached are not higher -than 92%~
The conversion of a reagent can of course be increased by increasing in the feed the content oL the other reagent but this involves a lowering of the conversion of -the reagent in excess. This can cause some dra~backs as, for instance, occurs in the synthesis of llTBE starting from methanol and isobutylene * Trademark r -j !
~4~B~iZ
contained in an olefinic stream. The use of an excess of isobutylene involves as consequence that the olefinic stream, after separation of the MTBE, still contains 5-10% isobutylene and this constitutes a drawback when such stream is utilized for the production of maleic anhydride or butadiene; vice-versa, an excess of methanol renders the purification of MTBE very difficult because of the formation of azeotropes.
The present invention proposes to provide a process by means of which a high conversion for both reagents can be obtained, even when these are maintained globally in stoichio-metric ratios.
According to the subject invention, there is provided a process for the production of methyl tert-butyl ether by reacting isobutylene with methanol at a pressure sufficient to maintain the liquid phase in the presence of a catalyst consisting of an acid ion exchange resin, which comprises the steps of:
(a) reacting in a first reactor in the presence of the catalyst at a temperature of from 60-70C (i) methanol.and (ii) a mixture comprising isobutylene, linear olefins and methanol, the total quantity of methanol being in stoichiometric excess of the quantity of isobutylene;
~ b) subjecting the product of step (a) to distillation to obtain an off gas comprising linear olefins and less than 2 percent of isobutylene and a bottoms product comprising methanol and tert-butyl ether;
(c) reacting in a second reactor in the presence of thecatalyst at a temperature of from 60 to 70C the bottoms product of step ~b) with a mixture comprising isobutylene and linear olefins, the space velocity of the mixture being in the range of 20 to 50 LHSV and the respective total quantities of methanol and isobutylene reacted in steps (a) and (c) being stoichiometrically equivalent; and
Tert alkyl ethers are prepared by reacting a primary alcohol with olefines having a double bond on a tertiary carbon atom~ ~or instance methanol reac-ts with isobutylene or iso-amylenes (2-methyl 1- or 2-pentene)to ~orm respectively methyl tert-butyl ether (MT~E) or methyl ter-amyl ether. (MTAE).
Since the reaction is selective with respect to tertiary olefins, it can thus be utilized for removing such olefins from olefinic streams wherein linear unreactive olefins are also present. The reaction has an equilibrium which is shifted towards the synthesis of the ether when the reaction temperature is lowered, in accordance with its negative enthalpy.
The reaction is catalyzed by Lewis acids (alumini~n trichloride, boron trifluoride), mQneral acids (sulphuric acid) or organic acids ~alk~l and aryl sulphonic acids~ ion-exchange resins). Ion exchange resins in their acid form have been found -to be particularly suitable to this end, and the best results are obtained in fact with macroreticular resins of the "Amberlyst*15" -type. ~y means o~ such catalysts, it is possible to reach the therm~dynamic equilibrium with industrially acceptable contact times, at temperatures of 50-60C. At lower temperatures, which thermodynamically are more favourable, the kinetics is not sufficiently high to permit in practice to reach equilibrium. This fact thus limits the conversions; in the particular case of isobutylene and methanol used in eguimole-cular ratios, the conversions reached are not higher -than 92%~
The conversion of a reagent can of course be increased by increasing in the feed the content oL the other reagent but this involves a lowering of the conversion of -the reagent in excess. This can cause some dra~backs as, for instance, occurs in the synthesis of llTBE starting from methanol and isobutylene * Trademark r -j !
~4~B~iZ
contained in an olefinic stream. The use of an excess of isobutylene involves as consequence that the olefinic stream, after separation of the MTBE, still contains 5-10% isobutylene and this constitutes a drawback when such stream is utilized for the production of maleic anhydride or butadiene; vice-versa, an excess of methanol renders the purification of MTBE very difficult because of the formation of azeotropes.
The present invention proposes to provide a process by means of which a high conversion for both reagents can be obtained, even when these are maintained globally in stoichio-metric ratios.
According to the subject invention, there is provided a process for the production of methyl tert-butyl ether by reacting isobutylene with methanol at a pressure sufficient to maintain the liquid phase in the presence of a catalyst consisting of an acid ion exchange resin, which comprises the steps of:
(a) reacting in a first reactor in the presence of the catalyst at a temperature of from 60-70C (i) methanol.and (ii) a mixture comprising isobutylene, linear olefins and methanol, the total quantity of methanol being in stoichiometric excess of the quantity of isobutylene;
~ b) subjecting the product of step (a) to distillation to obtain an off gas comprising linear olefins and less than 2 percent of isobutylene and a bottoms product comprising methanol and tert-butyl ether;
(c) reacting in a second reactor in the presence of thecatalyst at a temperature of from 60 to 70C the bottoms product of step ~b) with a mixture comprising isobutylene and linear olefins, the space velocity of the mixture being in the range of 20 to 50 LHSV and the respective total quantities of methanol and isobutylene reacted in steps (a) and (c) being stoichiometrically equivalent; and
- 2 -,''' ` .~
48~6Z
(d) subjecting the product of step (c) to distillation to produce an off gas comprising isobutylene, linear olefins and methanol, and a bottoms product comprising methyl tert-butyl ether, the off gas being recycled as feed to the reactor in step (a).
In a preferred embodiment of the invention, the mixture comprising isobutylene, linear olefins and methanol in step (a) consists essentially of the off gas from step (d) and a portion of a mixture comprising isobutylene and linear olefins, the remainder of this mixture being introduced in step (c).
The ratio by weight of isobutylene to methanol in step (a) is preferably from about 0.62 to 0.72 while that in step (c) is preferably from about 2.35 to 2.8.
According to a furtheradvantageous embodiment, the space velocity of the mixture in step (a) is 5 LHSV.
The present invention will now be better understood by means of the following description of embodiments, followed by non-restrictive working examples, reference being made to the appended drawings, wherein:
Fig. 1 is a flow diagram illustrating the synthesis of methyl tert-butyl ether in accordance with an embodiment of the invention; and - 2a -A
~ ig- 2 i3 a flow diagram illus-tra-ting the synthesis of methyl -tert-butyl ~her in accordance with another embodiment of the invention.
Methanol 1 is fed to a reactor R-1 together with the effluent stream 3 coming from the top of column C-2, constituted by an olefinic stream free of isobutylene. The reaction mixture contains an excess of metha~ol such that the isobutylene converslon will be very high.
~ he e~fluent stream 4 discharged from R-1 is sent to the distillation column C-1, from the top of which an olefinic fraction 6 is recovered having an isobutylene content lower than 2~ and from the botto~ of which a mixture 5 of methanol and MTBE is obtained. ~he bottom stream 5 together with an olefinic feed 2 are introcluced into reactor R-2. The reaction mixture in R-2 contains an excess of isobutylene so that the methanol conversion is high.
'~he product 7 leaYing reactor R-2 is sent to the distillation column C2, from the bottom of which MT~æ 8 having a high degree o~ purity is discharged and from the top of which an olefinic stream 3 free of isobutylene is discharged ana is recycled to R-1.
I~ reactor R-2, a strong excess of isobutylene is present and it is possible to have secondary oligomerization reactions of isobu-tylene; this effectively occurs when working at 60-70C and space velocities of 5-10. ~he phenomenon can be minimized by distributing the olefin ~eed both to reactor R-1 and to reactor R-29 as best shown in fig. 2. It has been moreover found that it is possible to obtain high selectivities also in presence of an e~cess of isobutylene, by working at a
48~6Z
(d) subjecting the product of step (c) to distillation to produce an off gas comprising isobutylene, linear olefins and methanol, and a bottoms product comprising methyl tert-butyl ether, the off gas being recycled as feed to the reactor in step (a).
In a preferred embodiment of the invention, the mixture comprising isobutylene, linear olefins and methanol in step (a) consists essentially of the off gas from step (d) and a portion of a mixture comprising isobutylene and linear olefins, the remainder of this mixture being introduced in step (c).
The ratio by weight of isobutylene to methanol in step (a) is preferably from about 0.62 to 0.72 while that in step (c) is preferably from about 2.35 to 2.8.
According to a furtheradvantageous embodiment, the space velocity of the mixture in step (a) is 5 LHSV.
The present invention will now be better understood by means of the following description of embodiments, followed by non-restrictive working examples, reference being made to the appended drawings, wherein:
Fig. 1 is a flow diagram illustrating the synthesis of methyl tert-butyl ether in accordance with an embodiment of the invention; and - 2a -A
~ ig- 2 i3 a flow diagram illus-tra-ting the synthesis of methyl -tert-butyl ~her in accordance with another embodiment of the invention.
Methanol 1 is fed to a reactor R-1 together with the effluent stream 3 coming from the top of column C-2, constituted by an olefinic stream free of isobutylene. The reaction mixture contains an excess of metha~ol such that the isobutylene converslon will be very high.
~ he e~fluent stream 4 discharged from R-1 is sent to the distillation column C-1, from the top of which an olefinic fraction 6 is recovered having an isobutylene content lower than 2~ and from the botto~ of which a mixture 5 of methanol and MTBE is obtained. ~he bottom stream 5 together with an olefinic feed 2 are introcluced into reactor R-2. The reaction mixture in R-2 contains an excess of isobutylene so that the methanol conversion is high.
'~he product 7 leaYing reactor R-2 is sent to the distillation column C2, from the bottom of which MT~æ 8 having a high degree o~ purity is discharged and from the top of which an olefinic stream 3 free of isobutylene is discharged ana is recycled to R-1.
I~ reactor R-2, a strong excess of isobutylene is present and it is possible to have secondary oligomerization reactions of isobu-tylene; this effectively occurs when working at 60-70C and space velocities of 5-10. ~he phenomenon can be minimized by distributing the olefin ~eed both to reactor R-1 and to reactor R-29 as best shown in fig. 2. It has been moreover found that it is possible to obtain high selectivities also in presence of an e~cess of isobutylene, by working at a
3 temperature of 60C and a space velocity of 40, without lowe~ing the conversion to M~æ.
~ ~ _ E3~
r~he operation was carried out in accordance with figure 1. 21.11 parts by weight of methanol 1 were joi~ed to the stream 3 leaving the top of column C-2, constituted by 23~38 parts of isobutylene, 43.43 parts of linear olefines and 0.35 parts of methanol. '~he mixture, in which the isobutylene-methanol molar ratio - was 0. 62, was fed to reactor R-1 in which it was reacted in presence of Amberlyst*15 at a temperature of 60c with a space velocity of 5 volumes per hour and per volume f catalyst and at a pressure sufficient to maintain the system in liquid phase.
'~he effluent stream 4 from reactor R-1, which contained 8.46 parts of methanol, 35.76 parts of MTEE, 0.62 parts of isobutylene and 43.43 parts of linear butenes was then fed to the distillation column C-1; from the top o~ column C-1 (line 6) were obtained 44.95 parts of a fraction having the following composition:
isobutylene (~0 by weight) - 1.4 methanol (% by weight) - 2.0 linear olefines (% by weight) = 96.6 - ~rom the bot-tom of column C-1 (line 5), 35.76 parts of M~B~ and 7.56 parts of methanol were discharged and, together with 37.00 parts of isobutylene and 43~.43 parts of linear butenes 2, were fed to reactor R-2 in which the reaction was effected in thepresence of Amberlyst*159 at a temperature of 60C and a space velocity of 40. '~he isobutylene-methanol molar ratio was 2.8 in the reactor R-2.
'l'he effluent stream 7 from reactor R-2 which was constituted by 55. 60 parts of M~EE, O.35 parts of methanol, 23.38 parts of isobutylene, 53.43 parts of linear butenes and 0.99 parts of diisobutylene was fed to the distillation column C-2~ from the top of which (line 3) 23.38 parts of isobutylene, * Trademark
~ ~ _ E3~
r~he operation was carried out in accordance with figure 1. 21.11 parts by weight of methanol 1 were joi~ed to the stream 3 leaving the top of column C-2, constituted by 23~38 parts of isobutylene, 43.43 parts of linear olefines and 0.35 parts of methanol. '~he mixture, in which the isobutylene-methanol molar ratio - was 0. 62, was fed to reactor R-1 in which it was reacted in presence of Amberlyst*15 at a temperature of 60c with a space velocity of 5 volumes per hour and per volume f catalyst and at a pressure sufficient to maintain the system in liquid phase.
'~he effluent stream 4 from reactor R-1, which contained 8.46 parts of methanol, 35.76 parts of MTEE, 0.62 parts of isobutylene and 43.43 parts of linear butenes was then fed to the distillation column C-1; from the top o~ column C-1 (line 6) were obtained 44.95 parts of a fraction having the following composition:
isobutylene (~0 by weight) - 1.4 methanol (% by weight) - 2.0 linear olefines (% by weight) = 96.6 - ~rom the bot-tom of column C-1 (line 5), 35.76 parts of M~B~ and 7.56 parts of methanol were discharged and, together with 37.00 parts of isobutylene and 43~.43 parts of linear butenes 2, were fed to reactor R-2 in which the reaction was effected in thepresence of Amberlyst*159 at a temperature of 60C and a space velocity of 40. '~he isobutylene-methanol molar ratio was 2.8 in the reactor R-2.
'l'he effluent stream 7 from reactor R-2 which was constituted by 55. 60 parts of M~EE, O.35 parts of methanol, 23.38 parts of isobutylene, 53.43 parts of linear butenes and 0.99 parts of diisobutylene was fed to the distillation column C-2~ from the top of which (line 3) 23.38 parts of isobutylene, * Trademark
4 -,.c~
3L0~ 2 43.43 parts OI linear butenes and 0.~5 ~par-ts of me-thanol were discharged a~d recycled to reactor R 1, and from l;he bottom of which (line 8) 56.59 parts of MTEE having a purity of 98.25%
were withdrawn.
The total conversion of methanol was 960to ~vith a selectivity of 100%' while the isobutylene conversion was 98 with a selectivity of 97%~
This example ~as carried out in accorda~ce with figure 2.
32.12 parts by weight o methanol 1 were joined with the effluent stream 3 from the top o~ colwnn C-2, constituted by 0.98 parts of methanol, 40.73 parts o:~ linear butenes and 23.94 parts of isobu-tylene, ~d with a portion 4 ofi the feed olefines 2. This portion was constituted by 16.44 parts of isobutylene and 16.77 parts of linear butenes.
The reaction mixture in which the isobutylene-methanol ratio was 0.72 was fed to reactor R-1 at a space ~elocity of 5, ' wherein the reaction was effected in the presence of Amberlyst*
15, at a temperature of 60C and a pressure sufficient to maintain the system in the liquid state.
The reaction product 6 which was constituted by 10.67 parts of methanol9 1.11 parts of isobutylene, 57.50 parts of linear butenes and 61.70 parts of MT~ was fed to the distillation column C-1" from the top of which (line 10) were obtained 59.67 parts of a fraction having the following composition:
isobutylene (% by weight) ~ 1.9 methanol (% by weight) = 1.8 linear butenes (% by weight) =96.3 ~rom the bottom of column C 1 were obtained 9.61 parts of methanol and 61.70 parts of MT~E. The bottom product 7, together with 39.66 parts of isobutylene and 40.73 parts of linear butenes constituting the remaining portion of the olefinic * Trademark -- 5 ~
,, c(, ,~,.
-~4~6~
~eed 2, were reacted in reactor R-2 at 60~ and a space velocity of 40. ln this reactor, the isobu-~lene/methanol ratio was 2.35. The reaction product 8 which ~s cons-tituted by 0.98 parts of methanol, 85.45 parts of M~E 9 23.94 parts of iso-butylene, 40.73 parts of linear butenes and 0.88 parts of diisobutylene was sent to the distillation column C-2; 0.98 parts of methanol, 23.94 parts o~ isobutylene and 40.73 parts of llnear butenes were obtained as overhead products 3 which were recycled to reactor R~ rom the bottom of column C-2 (line 9) were recovered 86.33 parts of I~Eæ having a purity of 99%-The total conversion o~ methanol was 96.7~ with a selec-tivity of 100%; the isobutylene conversion was 98% with a selectivity of 98%.
The feed to reactor ~o2 of the preceding example was reacted at t~ dif~erent tempexatures and at three different ~pace velocities; the results obtained were the following:
Temperature 60 C 70 C
~HSV . 3 8.5 40 3 8.5 40 .
~otal conversion of isobutylene 61 55 44 63 55 45.5 Conversion o~ isobuty-lene to M~BE 41.5 46.5 41 43 42-5 37 Selectivity 68 83 93 68 77-5 82 IHSV - space veloci-ty expressed as volumes of liquid ~eed per volume o~ catalyst per hour.
3L0~ 2 43.43 parts OI linear butenes and 0.~5 ~par-ts of me-thanol were discharged a~d recycled to reactor R 1, and from l;he bottom of which (line 8) 56.59 parts of MTEE having a purity of 98.25%
were withdrawn.
The total conversion of methanol was 960to ~vith a selectivity of 100%' while the isobutylene conversion was 98 with a selectivity of 97%~
This example ~as carried out in accorda~ce with figure 2.
32.12 parts by weight o methanol 1 were joined with the effluent stream 3 from the top o~ colwnn C-2, constituted by 0.98 parts of methanol, 40.73 parts o:~ linear butenes and 23.94 parts of isobu-tylene, ~d with a portion 4 ofi the feed olefines 2. This portion was constituted by 16.44 parts of isobutylene and 16.77 parts of linear butenes.
The reaction mixture in which the isobutylene-methanol ratio was 0.72 was fed to reactor R-1 at a space ~elocity of 5, ' wherein the reaction was effected in the presence of Amberlyst*
15, at a temperature of 60C and a pressure sufficient to maintain the system in the liquid state.
The reaction product 6 which was constituted by 10.67 parts of methanol9 1.11 parts of isobutylene, 57.50 parts of linear butenes and 61.70 parts of MT~ was fed to the distillation column C-1" from the top of which (line 10) were obtained 59.67 parts of a fraction having the following composition:
isobutylene (% by weight) ~ 1.9 methanol (% by weight) = 1.8 linear butenes (% by weight) =96.3 ~rom the bottom of column C 1 were obtained 9.61 parts of methanol and 61.70 parts of MT~E. The bottom product 7, together with 39.66 parts of isobutylene and 40.73 parts of linear butenes constituting the remaining portion of the olefinic * Trademark -- 5 ~
,, c(, ,~,.
-~4~6~
~eed 2, were reacted in reactor R-2 at 60~ and a space velocity of 40. ln this reactor, the isobu-~lene/methanol ratio was 2.35. The reaction product 8 which ~s cons-tituted by 0.98 parts of methanol, 85.45 parts of M~E 9 23.94 parts of iso-butylene, 40.73 parts of linear butenes and 0.88 parts of diisobutylene was sent to the distillation column C-2; 0.98 parts of methanol, 23.94 parts o~ isobutylene and 40.73 parts of llnear butenes were obtained as overhead products 3 which were recycled to reactor R~ rom the bottom of column C-2 (line 9) were recovered 86.33 parts of I~Eæ having a purity of 99%-The total conversion o~ methanol was 96.7~ with a selec-tivity of 100%; the isobutylene conversion was 98% with a selectivity of 98%.
The feed to reactor ~o2 of the preceding example was reacted at t~ dif~erent tempexatures and at three different ~pace velocities; the results obtained were the following:
Temperature 60 C 70 C
~HSV . 3 8.5 40 3 8.5 40 .
~otal conversion of isobutylene 61 55 44 63 55 45.5 Conversion o~ isobuty-lene to M~BE 41.5 46.5 41 43 42-5 37 Selectivity 68 83 93 68 77-5 82 IHSV - space veloci-ty expressed as volumes of liquid ~eed per volume o~ catalyst per hour.
Claims (6)
1. In a process for the production of methyl tert-butyl ether by reacting isobutylene with methanol at a pressure sufficient to maintain the liquid phase in the presence of a catalyst consisting of an acid ion exchange resin, the improvement which comprises the steps of:
(a) reacting in a first reactor in the presence of the catalyst at a temperature of from 60°-70°C (i) methanol and (ii) a mixture comprising isobutylene, linear olefins and methanol, the total quantity of methanol being in stoichiometric excess of the quantity of isobutylene;
(b) subjecting the product of step (a) to distillation to obtain an off gas comprising linear olefins and less than 2 percent of isobutylene and a bottoms product comprising methanol and tert-butyl ether;
(c) reacting in a second reactor in the presence of the catalyst at a temperature of from 60° to 70°C the bottoms product of step (b) with a mixture comprising isobutylene and linear olefins, the space velocity of the mixture being in the range of 20 to 50 LHSV and the respective total quantities of methanol and isobutylene reacted in steps (a) and (c) being stoichiometrically equivalent; and (d) subjecting the product of step (c) to distillation to produce an off gas comprising isobutylene, linear olefins and methanol, and a bottoms product comprising methyl tert-butyl ether, the off gas being recycled as feed to the reactor in step (a).
(a) reacting in a first reactor in the presence of the catalyst at a temperature of from 60°-70°C (i) methanol and (ii) a mixture comprising isobutylene, linear olefins and methanol, the total quantity of methanol being in stoichiometric excess of the quantity of isobutylene;
(b) subjecting the product of step (a) to distillation to obtain an off gas comprising linear olefins and less than 2 percent of isobutylene and a bottoms product comprising methanol and tert-butyl ether;
(c) reacting in a second reactor in the presence of the catalyst at a temperature of from 60° to 70°C the bottoms product of step (b) with a mixture comprising isobutylene and linear olefins, the space velocity of the mixture being in the range of 20 to 50 LHSV and the respective total quantities of methanol and isobutylene reacted in steps (a) and (c) being stoichiometrically equivalent; and (d) subjecting the product of step (c) to distillation to produce an off gas comprising isobutylene, linear olefins and methanol, and a bottoms product comprising methyl tert-butyl ether, the off gas being recycled as feed to the reactor in step (a).
2. The process of claim 1, wherein the mixture comprising isobutylene, linear olefins and methanol in step (a) consists essentially of the off gas from step (d).
3. The process of claim 1, wherein the mixture comprising isobutylene, linear olefins and methanol in step (a) consists essentially of the off gas from step (d) and a portion of a mixture comprising isobutylene and linear olefins, the remainder of said mixture being introduced in step (c).
4. The process of claim 1, wherein the ratio by weight of isobutylene to methanol in step (a) is from about 0.62 to 0.72.
5. The process of claim 1, wherein the ratio by weight of isobutylene to methanol in step (c) is from about 2.35 to 2.8.
6. The process of claim 1, wherein the space velocity of the mixture in step (a) is 5 LHSV.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23013/74A IT1012690B (en) | 1974-05-21 | 1974-05-21 | PROCEDURE FOR THE PRODUCTION OF TER-ALKYL ETHERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048062A true CA1048062A (en) | 1979-02-06 |
Family
ID=11202877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA228,655A Expired CA1048062A (en) | 1974-05-21 | 1975-05-21 | Process for the production of methyl tert-butyl ether |
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| JP (1) | JPS516914A (en) |
| AR (1) | AR226992A1 (en) |
| AT (1) | AT338223B (en) |
| BE (1) | BE829303A (en) |
| BG (1) | BG26514A3 (en) |
| BR (1) | BR7503196A (en) |
| CA (1) | CA1048062A (en) |
| CH (1) | CH605509A5 (en) |
| CS (1) | CS219316B2 (en) |
| DD (1) | DD118067A5 (en) |
| DE (1) | DE2521963B2 (en) |
| DK (1) | DK135796B (en) |
| EG (1) | EG12653A (en) |
| ES (1) | ES438189A1 (en) |
| FR (1) | FR2272065B1 (en) |
| GB (1) | GB1506312A (en) |
| HU (1) | HU176319B (en) |
| IE (1) | IE43301B1 (en) |
| IN (1) | IN143295B (en) |
| IT (1) | IT1012690B (en) |
| LU (1) | LU72542A1 (en) |
| MW (1) | MW3075A1 (en) |
| NL (1) | NL183886C (en) |
| NO (1) | NO144524C (en) |
| PH (1) | PH13250A (en) |
| PL (1) | PL103015B1 (en) |
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| SE (1) | SE425482B (en) |
| SU (1) | SU858557A3 (en) |
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| 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 |
| JPS5342698U (en) * | 1976-09-17 | 1978-04-12 | ||
| DE2706465C3 (en) * | 1977-02-16 | 1980-10-02 | Deutsche Texaco Ag, 2000 Hamburg | Process for the production of butadiene or n-butenes from hydrocarbon mixtures containing them with separation of isobutene |
| JPS54130679U (en) * | 1978-03-03 | 1979-09-11 | ||
| DE2853769B2 (en) * | 1978-12-13 | 1980-10-09 | Chemische Werke Huels Ag, 4370 Marl | Process for the simultaneous production of pure MTB and largely isobutene-free C4 hydrocarbon mixture |
| DE2928509A1 (en) * | 1979-07-14 | 1981-01-29 | Basf Ag | METHOD FOR THE SIMULTANEOUS PRODUCTION OF METHYL-TERT.-BUTYL ETHER AND PRODUCTION OF ISOBUTEN |
| EP0075838A1 (en) * | 1981-09-24 | 1983-04-06 | Phillips Petroleum Company | Process for the preparation of methyl tert-butyl ether |
| JPS5921206U (en) * | 1982-07-31 | 1984-02-09 | 武田 精 | Fitting member for snap fasteners |
| DE3322753A1 (en) * | 1983-06-24 | 1985-01-10 | Deutsche Texaco Ag, 2000 Hamburg | METHOD FOR THE PRODUCTION OF METHYL-TERT.-BUTYLAETHER |
| JPS6013010U (en) * | 1983-07-05 | 1985-01-29 | カラ−フアスナ−工業株式会社 | hook device |
| JPH0641833Y2 (en) * | 1989-05-11 | 1994-11-02 | 三菱製紙株式会社 | Lower blade shaft of shear cut method |
| IT1247108B (en) | 1991-02-28 | 1994-12-12 | Snam Progetti | INTEGRATED PROCEDURE FOR THE PRODUCTION OF ISO-BUTENE AND ALCHIL-TER-BUTYL ETHERS. |
| EP3919468A1 (en) * | 2020-06-03 | 2021-12-08 | SABIC Global Technologies B.V. | Systems and processes for producing methyl tertiary butyl ether |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1968601A (en) * | 1934-02-14 | 1934-07-31 | Shell Dev | Preparation of olefine derivatives |
| US2480940A (en) * | 1946-09-20 | 1949-09-06 | Atlantic Refining Co | Production of aliphatic ethers |
| AT230345B (en) * | 1961-01-09 | 1963-12-10 | Bayer Ag | Process for the production of tert-butyl alkyl ethers |
| DE1224294B (en) * | 1961-01-09 | 1966-09-08 | Bayer Ag | Process for the production of tertiary butyl alkyl ethers |
| GB1173128A (en) * | 1968-09-20 | 1969-12-03 | Shell Int Research | Process for the preparation of Olefins |
-
1974
- 1974-05-21 IT IT23013/74A patent/IT1012690B/en active
-
1975
- 1975-05-06 ZA ZA00752914A patent/ZA752914B/en unknown
- 1975-05-12 MW MW30/75A patent/MW3075A1/en unknown
- 1975-05-13 GB GB20209/75A patent/GB1506312A/en not_active Expired
- 1975-05-13 TR TR18546A patent/TR18546A/en unknown
- 1975-05-15 IE IE1094/75A patent/IE43301B1/en unknown
- 1975-05-15 PL PL1975180405A patent/PL103015B1/en unknown
- 1975-05-16 DE DE2521963A patent/DE2521963B2/en active Granted
- 1975-05-16 YU YU1263/75A patent/YU37301B/en unknown
- 1975-05-18 EG EG297/75A patent/EG12653A/en active
- 1975-05-19 IN IN999/CAL/1975A patent/IN143295B/en unknown
- 1975-05-20 ES ES438189A patent/ES438189A1/en not_active Expired
- 1975-05-20 DK DK222275AA patent/DK135796B/en unknown
- 1975-05-20 BG BG7530034A patent/BG26514A3/xx unknown
- 1975-05-20 AT AT381375A patent/AT338223B/en not_active IP Right Cessation
- 1975-05-20 CS CS753520A patent/CS219316B2/en unknown
- 1975-05-20 NO NO751787A patent/NO144524C/en unknown
- 1975-05-20 FR FR7515722A patent/FR2272065B1/fr not_active Expired
- 1975-05-20 HU HU75SA2797A patent/HU176319B/en not_active IP Right Cessation
- 1975-05-20 LU LU72542A patent/LU72542A1/xx unknown
- 1975-05-21 BE BE156545A patent/BE829303A/en not_active IP Right Cessation
- 1975-05-21 SE SE7505804A patent/SE425482B/en not_active IP Right Cessation
- 1975-05-21 DD DD186165A patent/DD118067A5/xx unknown
- 1975-05-21 RO RO7582288A patent/RO72850A/en unknown
- 1975-05-21 ZM ZM64/75A patent/ZM6475A1/en unknown
- 1975-05-21 PH PH17183A patent/PH13250A/en unknown
- 1975-05-21 NL NLAANVRAGE7505998,A patent/NL183886C/en not_active IP Right Cessation
- 1975-05-21 AR AR258895A patent/AR226992A1/en active
- 1975-05-21 JP JP50059793A patent/JPS516914A/en active Granted
- 1975-05-21 CH CH649575A patent/CH605509A5/xx not_active IP Right Cessation
- 1975-05-21 SU SU752136591A patent/SU858557A3/en active
- 1975-05-21 CA CA228,655A patent/CA1048062A/en not_active Expired
- 1975-05-22 BR BR4088/75D patent/BR7503196A/en unknown
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