PROCESS FOR THE PREPARATION OF METHYL TERT-BUTYL ETHER

Abstract: A process for producing high yields of methyl-tert-butyl ether by the reaction of isobutylene and methanol compris­ ing using a fixed bed of acid ion exchange resin, effluent recycle, and specific temperature conditions, and preferably a second fixed bed of acid ion exchange resin with specific temperature conditions.

Description: EROCESS z so FOR SEE PREPARATION OF METHYL TERT-BUTYL ETHER Field of the Invention The present invention relates to the production of methyl-tertbutyl ether from isobutylene. Background of Invention In view of the growing need to limit the use of lead-containing additives as octane improvers for gasoline, there is an incre2síne need for more environmentally safe octane-improving addities. One of the more promising additives is methyl tert-butyl ether (MTBE). It has long been known that MTBE can be produced from the reaction of isobutylene and methanol. See Leum et al, U. S. patent 2,480,940. In a commercial scale MTBE plant, it is obviously desirable to maximize the production of substantially pure MTBE without the need for numerous or expensive separation steps. It has previously been suggested that the MTBE yield could be increased b using excess amounts of either the isobutene or the methanol. Such techniques have, hovever, led to separation problems or undesirable by-products which adversely affect catalyst life An object of the present invention is to provide a method for producing MTBE In a for that is readily separated into a substantially pure MTBE product. Still another object of the present invention is to provide a process in which the catalyst activity can be maintained over long periods of time. Other aspects objects and advantages of the present invention will be apparent from the following disclosure and the attached Figures. Summary of the Invention In accordance with the present invention, a fresh feedstream comprising isobutylene and methanol is passed through a first reaction zone comprising a fizzed bed of acid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain 2 liquid phase reaction. Effluent from this first reaction zone is recycled through the reaction zone along with the fresh feedstream. The fresh feedstream and the recycle feedstream are passed into said first reaction zone at a temperature of about 120 K to about I4OF and the rates of addition of said recycle stream and said res feed stream are such that the conversion of isobutene is at least about 90 weight percent and at least as great as the conversion would be under adiabatic conditions at the inlet temperature and fresh feed LHSV if no recycle streams were passed through the first reaction zone. In a preferred embodiment of the present invention, effluent from said first reaction zone still containing substantially all its MTBE is passed through a second reaction zone comprising a fixed bed of acrid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain a liquid phase reaction under conditions which maximize the overall conversion of isobutene obtained from the two reaction steps The term "substantially adiabatic conditions" is used herein to indicate that no cooling of the reactor is employed other than the small amount that would normally occur under the ambient conditions. Brief Description of the Figures r.IG' 1 is a graphical illustration of the effect of recycle ratio and fresh feedrate on isobutene conversion in the first reaction # zone. FIGURE 2 is a graphical illustration of the effect 0 inlet temperature and recycle ratio on isobutene conversion reaction zone. FIGURE 3 is a graphical illustration of the effect of inlet temperature and space velocity on isobutene conversion in the second reaction zone. FIGURES 4 and 5 are graphical illustrations of the effect of temperature, recycle ratio, and fresh feed LHSV on isobutene conversion in the first reaction zone for a fresh feedstream containing 43 weight percent isobutene. FIGURE 6 is a graphical illustration of the effect of temperature, recycle ratio, and fresh feed SHSV on isobutene conversion in the first reaction zone for a fresh feed containing 60 weight percent isobutene. FIGURE 7 is a graphical illustration comprising the results obtained in the first reaction zone for fresh feeds having various levels of isobutene. FIGURES 8 and 9 are graphical illustrations comprising the results obtained in the first reaction zone for different methanol to isobutene ratios. FIGURE 10 is a schematic illustration of a process employing the present invention to obtain high yields of relatively pure MTBE products with minimal separation expenditure. Detailed Description of the Invention The catalyst employed in the present invention is a macroreticular acid ion exchange resin of the type known to be suitable for catalyzing the reaction of methanol and isobutene to ITBE. A typical example is Amberlyst 15 available from the Rohm and Haas Company. Any suitable isobutene-containing feed can be employed in the present invention. Typically, the isobutene feed is a C4 fraction from a steam or catalytic cracking operation. Preferably, the feed is subjected to a butadiene extraction step to remove any substantial amounts of butadiene prior to reaction with the methanol. Typically, the fresh feedstream on a methanol free basis contains at least about 10 weight percent isobutene no more than about 60 weight percent isobutene. Most preferably, the fresh feedstream contains no more than about 25 weight percent isobutene on a methanol-free basis. The use of fresh feedstream having more than 25 weight percent isobutene often results in final product streams containing more than about 1.5 weight percent methanol. If the amount of methanol in the final product stream is kept below 1.5 weight percent, it is possible to separate substantially all of the methanol from the MTBE by distilling the methanol overhead with the unreacted C41s. If product streams from the second reactor are obtained that have much more than 1.5 weight percent methanol, the methanol does not completely azeotrope overhead with the unreacted C41s and will contaminate the MTBE product which will necessitate the use of special additional separation techniques to obtain an TITLE product substantially free of methanol. As will be seen from the examples that follow, the I.HSV of the fresh.feed and the recycle rate that is employed in the first reaction zone can vary over a wide range depending upon the inlet temperature, the weight percent isobutene in the feed, the temperature conditions, and the level of isobutene conversion desired. The term LXSV as used herein refers to the volumes of the particular stream that is passed through the reactor per volume of catalyst per hour wherein the volume of the catalyst refers to the dry volume of the catalyst. The recycle ratio refers to the volumes of recycle stream per volume of fresh feed. Typically, the SHSV for the fresh feed to the first reaction zone is no greater than about 5. The recycle ratio is generally no greater than about 14, more normally no greater than about 5. Obviously, the best conditions are those which result in isobutene conversion that is greater than the conversion that would be obtained at the same conditions of temperature and fresh feed LHSV but without the recycle. It is typically desired that the recycle be employed at such a rate that the maximum hot spot in the catalyst bed is at a temperature no greater than about 25F above the inlet temperature, with lower hot spot temperatures being more desirable for the higher inlet temperatures. The molar ratio of methanol to isobutene in the stream resulting from the combination of the fresh feed and the recycle should be about 1/1. Methanol to isobutene ratios in the range of about 0.99 to about 1.02 have been found quite suitable. Since occasionally some of the isobutene in the fresh feed may dimerize or react with small amounts of water present to form tert-butyl alcohol, it is generally preferred that the molar ratio of methanol to isobutene in the fresh feed be not greater than l/l, so that the methanol to isobutene ratio in the combined streams will be maintained to about 1/1. The recycled effluent from the first reaction zone can be passed through the second reaction zone at any LHSV that will provide at least about 50 weight percent conversion of the remaining isobutene. Generally, it is desirable to employ a LllSV in the second reaction zone which results in a catalyst hot spot no more than about 10F hotter than the inlet temperature, more preferably no more than about 5 hotter than the inlet temperature. Typically, the LHSV of the unrecycled effluent passed into the second reaction zone will be in the range of about 3 to about 7. A A further understanding of the present invention and its advantages will be provided by the following examples which summarize the results obtained using pilot plant scale etherization reactions. The evaluations were made using a two inch 1.1). carbon steel reactor insulated to provide substantially adiabatic conditions. The reactor was filled with 780 cc of dry Amberlyst 15 ion exchange resin available from Rohm and Haas. The Amberlyst 15 was a strongly acidic macroreticular cation exchange resin comprising particles over 90 percent of which were 20-50 mesh. The bulk density of the dry catalyst was 38 pounds/cubic foot. In as much as the dry catalyst swells when wetted, it is noted that the LHSV used herein (i.e., the volumes of liquid feed per volume of catalyst per hour) are based on the dry weight of the catalyst. Example I A typical hydrocarbon feed was mixed with enough ethanol to give a fresh feed having a methanol/isobutene feed ratio of 1/1. The composition of the fresh feed was: Weight, ' Propane 0.28 Propene 0.20 Isobutane 23.25 n-Butane 19.S5 Butene-1 11.S7 Isobutene 13.10 t-Butene-2 13.64 c-Butene-2 9.86 1,3-Butadiene 0.22 isopentane 0.25 Methanol 7.48 The feedstrcam was then used to evaluate the effect of recycle on the conversion of isobutene. An automatic level control scheme was used to purge inert gases and insure a liquid-full reactor. Reactor effluent was cooled, metered, and then reheated along with fresh feed in an electric furnace, controlling heat input to the furnace to obtain the desired inlet temperature. The pressure was maintained in the range of about 150 to about 170 psig to insure liquid phase reaction. The effect of varying the LHSV of fresh feed and the recycle - ratio, i.e., volumes of reactor effluent recycle per volumes of fresh feed, is shown in FIGURE 1. Under the noted conditions, the temperature buildup in the reactor decreased with increased recycle ratio. More importantly the data shows that the use of recycle can result in higher isobutene conversion than can be obtained without recycle. The term isobutene conversion as used herein refers to the isobutene conversion based on the isobutene. The effect of varying the inlet temperature is shown in FIGURE 2. Again the reactor "hot spot" was lower at higher recycle ratios. It further shows that at an inlet temperature of 120P some improvement in isobutene conversion is obtained at recycle ratios lower than 1. At inlet temperatures of 130 and 14?F high conversions of isobutene were obtained over a broad range of recycle ratios. Optimum conversion was obtained using an inlet temperature of 1300F and recycle ratios in the range of about 1.0 to about 3.5. Example II Effluent from a reaction carried out in a first reactor as set forth in Example I was passed through a second reaction zone comprising a bed of Amberlyst 15 to determine the effect of the inlet temperature on the total isobutene conversion. The fresh feed supplied to the first reactor was as indicated in Example I. NTo recycle was employed in the second reactor and the second reactor was operated under substantial1; adiabatic conditions. The operating conditions and results are suamar- ized in FIGURE 3. The results show that when the LHSV is in the range of 3 to 7, the best overall isobutene conversion is obtained when the inlet temperature to the second reactor is in the range of about 100OF to about liO F. Example III Using the recycle pilot plant reactor as in Example I, a series of runs were made using fresh feeds containing either 43 weight percent or 60 weight percent isobutylene. The conditions employed and the results obtained are summarized in FIGURES 4 to 6. A comparison of these results to those obtained with a 14 weight percent isobutylene feed is provided in FIGURE 7. The results in FIGURE 7 that under the given operating conditions increasing the isobutene feed concentration from 14.0 to 60 weight percent (methanol free basis) reduces the isobutene conversion by no more than about 2 weight percent. Example IV Again using the recycle pilot plant reactor as in Example I, a series of runs were made using a fresh feed having a methanol/isobutylene of 1.5/1. As indicated earlier such a technique has often been suggested as a means of increasing the isobutene conversion. The results are summarized in FIGURES 8 and 9. The data indicates that while it is true that when no effluent recycle is employed, the excess methanol results in greater isobutylene conversion. However, when recycle is used, greater isobutylene conversion can be obtained using a 1/1 molar ratio. An even more important feature is illustrated by FIGURE 9 where it is demonstrated that although isobutylene conversion is greater with excess methanol, the weight percent MTBE obtained is much less than when a 1/1 molar ratio is employed. In addition, the use of excess methanol results in an effluent having much higher levels of methanol. The higher levels of methanol are quite significant since high levels of methanol in the effluent can make it impossible to obtain a relatively clean separation of methanol and MTBE by distillation. FIGURES 8 and 9 thus demonstrate that there is a distinct advantage to carrying out the etherization reaction in the first reaction zone in the manner set forth in this disclosure. Example V Again using the recycle pilot plant reactor as in Example I, a series of runs were made using fresh feeds having methanol to isobutene ratios of 0.4/1 or 0.7/1. The results are summarized in Tables I and II. TABLE I EFFECT OF SPACE VELOCITY AND INLET TEMPERATURE AT A METHANOL/ISOBUTENE MOLAR FEED RADIO OF 0.7/1 Run No. 111 112 105 106 103 104 109 113 110 107 108 Conditions Fresh Feed LHSV, hr-1 3 5 3 5 3 5 3 3 5 3 5 Recycle Ratio 0 0 0 0 0 0 2.1 4.0 2.0 2.2 2.0 Total LHSV, hr-1 3 5 3 5 3 5 9.4 15.0 15.0 9.4 15.0 Reactor Inlet Temp., F 110 110 120 120 130 130 120 120 120 130 130 Reactor Pressure, psig 159 160 160 160 160 160 157 157 157 157 157 Results iC4 = Conversion, Wt % 78.3 75.4 77.8 75.0 77.8 75.5 76.7 79.2 74.7 76.9 75.5 MeOH Conversion, Wt % 88.3 86.8 86.4 83.3 85.0 84.8 88.3 89.8 89.1 86.2 88.9 MTBE in Reactor Eff., Wt % 12.8 13.0 12.6 13.1 12.1 12.3 12.9 14.2 12.9 13.1 13.1 DIB & MSBE(Ú) in Reactor Eff., Wt % -- -- -- -- -- -- -- -- -- -- - (1) Diisobutene and methyl secondary butyl ether. TABLE II EFFECT OF SPACE VELOCITY AND INLET TEMPERATURE AT A METHANOL/ISOBUTENE MOLAR FEED RADIO OF 0.4/1(Ú) Run No. 117 116 120 121 115 114 118 119 Conditions Fresh Feed LHSV, hr-1 3 5 3 5 3 5 3 5 Recycle Ratio 0 0 2.1 2.0 0 0 2.1 2.0 Total LHSV, hr-1 3 5 9.4 15.0 3 5 9.40 15.0 Reactor Inlet Temp., F 121 121 121 120 131 130 130 130 Reactor Pressure, psig 162 162 158 158 162 160 157 158 Results iC4 = Conversion, Wt % 85.1 84.0 61.3 51.8 86.9 82.8 73.5 63.7 MeOH Conversion, Wt % 80.3 82.9 87.0 87.3 79.4 77.5 86.3 85.7 MTBE in Reactor Eff., Wt % 5.6 4.8 6.4 6.6 2.8 4.6 6.4 6.3 DIB & MSBE(ê) in Reactor Eff., Wt % 6.3 7.3 2.7 1.6 8.8 4.2 4.1 3.5 (1) Using single-stage reactor. (2) Diisobutene and methyl secondary butyl ether. This data indicates that the lower mole ratios of methanol to isobutylene did not result in sobutylene conversions of 90 weight percent. Further, surprisingly, the lower levels of methanol did not result in a greater weight percent of methanol conversion than the runs using a ratio of about 1/1. Still further, it was noted that as the molar ratio of methanol of isobutylene is decreased, there is an increasing tendency for the formnation of undesired diisobutene and methyl secondary butyl ether by-products. The lower molar ratios were also found to affect the activity of the catalyst probably as a result of catalyst fouling by polymer or other undesirable by-products formation. the ¯The schematic process flow diagram presented in FIGURE 10 illustrates a plant designed to produceftiTBE using the beneficial results provided by the present invention. A C4 olefinic stream containing isobutene is combined with methanol and passed through line l to a first reactor 2 containing a fixed bed of an acid ion exchange resin such as Amberlyst 15. A portion of the effluent from the reactor 2 is cooled and recycled via line 3 to the inlet of reactor 2. The cooling of the recycled effluent is used to control the temperature of the combined streams at the inlet of reactor 2. The unrecycied effluent is cooled and passed via line 4 to a reactor 5 also containing a fixed bed-of acid ion exchange resin. The effluent from reactor 5 is heated and passed via line 6 to a fractionation column 7 wherein NTBE is separated from methanol and unreacted portions of the C4 feed. The overhead from fractionator 7 is cooled and passed via line 8 to a water wash column 9 wherein methanol is washed out of the unreacted portions of the C4 feed. The bottoms from the wash column 9 comprising methanol and water is then heated and passed via line 10 to a fractionation column 11 wherein water and methanol are separated. Generally, the fractionation in column II can be carried out so as to result in methanol suitable for reuse as the methanol reactant stream that is passed into reactor 2. In a typical operation, a C4 hydrocarbon cut from a catalytic cracking operation containing about 15 to about 20 weight percent isobutene is combined with methanol to result in a fresh feedstream having a methanol to isobutene ratio of about 1/1. This feedstream is passed via line 1 along with recycle effluent from line 3 through reactor 2. The inlet temperature of the combined streams would typically be about 130OF. The pressure in reactor 2 under these conditions would typically be about 180 to 235 psia. The effluent is recycled via line 3 at such a rate that the temperature of the effluent at the outlet of reactor 2 is in the range of about 155 to 160n e. Such a fresh feed would be passed through the first reactor at a LHSV of about 3 to 5. The recycle ratio would be in the range of about 2 to about 6. Unrecycled effluent would be passed via line 4 into the second reactor 5. The unrecycled effluent would be cooled to a temperature in the range of about 100 to about llOF and the LESV of the unrecycled effluent supplied to reactor 5 would be such as to assure that the temperature of effluent of reactor 5 at the outlet has a temperature in the range of about 5 to 10F greater than that of the inlet temperature of the feed to said reactor 5. The pressure would typically be about 170 to about 210 psia. The effluent from the second reactor is then heated and passed via line 6 to a distillation column 7. The distillation column is operated under conditions such that methanol and unreacted hydrocarbons are distilled overhead and MTBE is recovered from the bottom in a form substantially free of methanol. Typically, the pressure in the column 7 would be in the range of about 85 to about 125 psia. Typically, the recovered TRIBE product will contain essentially no methanol and will be at least about 98 weight percent MTBE, the remainder generally comprising higher boiling hydrocarbons such as pentanes and l-peatene present in the fresh feed stream. The overhead from the fractionator 7 is then passed to a methanol extractor 9 wherein countercurrent contact with water separates the methanol and the hydrocarbons. Typical operating conditions for extractor 9 are a temperature of about 1000F and a pressure of about 210 psia. The C4 raffinate can be recovered and processed as desired for further use. The methanol-water mixture is passed to fractionator 11 wherein the methanol and water are fractionated. Typically, this fractionator is operated at pressures in the range of about 30 to about 50 psia. Generally, under such conditions, the methanol that is recovered is sufficiently free of water that it can be used as make-up for the methanol supplied to etherization reactor 2. The following part of the description are preferred embodiments 1 to 16 presented in the form of claims. 1. In a process for preparing methyl tert-butyl ether by reacting isobutylene and methanol, the improvement comprising carrying out said reaction in two stages by feeding a fresh feedstream comprising isobutylene and methanol through a first reaction zone comprising a fixed bed of acid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain the reactants in the liquid phase and recycling effluent from said first reaction zone through said first reaction zone along with said fresh feedstream wherein the molar ratio of methanol to isobutylene in the combined feeds entering said first reaction zone is about 1/1 and said fresh feedstream and said recycle stream are passed into said catalyst bed of said first reaction zone at a temperature in the range of about 120n e and 1400F and the rates of addition of said fresh feedstream and said recycle stream are such that the conversion of isobutene is at least 90 weight percent and at least as great as it would be under the same inlet temperature, substantially adiabatic conditions, and fresh feed LHSV if no effluent recycle were passed through said first reaction zone; and passing unrecycled effluent from said first reaction zone through a second reaction zone comprising a fixed bed of acid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain the reactants in the liquid phase, wherein said unrecycled effluent is passed into said catalyst bed of said second reaction zone at a temperature in the range of about 100F to about 110?F and at a LHSV such that the isobutylene conversion is at least about 50 weight percent. 2. A process according to claim 1 wherein the LHSV of effluent passed through said second reaction zone is such that the hottest spot in the catalyst bed is no greater than about 10n e above the inlet temperature of said effluent into said second reaction zone. 3. A process according to claim 2 wherein the LHSV of effluent passed through said second reaction zone is in the range of about 3 to about 7. 4. A process according to claim 3 wherein said fresh feedstream contains about 10 to about 60 weight percent isobutylene on a methanol free basis. 5. A process according to claim 4 wherein said fresh feedstream contains no more than about 25 weight percent isobutylene on a methanol free basis. 6. A process according to claim 5 wherein said fresh feedstream comprises the fraction of the hydrocarbons from a steam or catalytic cracking process that boils in the range of C4 hydrocarbons. 7. A process according to claim 6 wherein the recycle ratio of effluent from said first reaction zone is no greater than about 14. 8. A process according to claim 7 wherein the recycle ratio of effluent from said first reaction zone is.no greater than about 5. 9. A process according to claim 8 wherein the LHSV of the fresh feedstream through said first reaction zone is in the range of about 2 to about 5. 10. A process according to claim 9 wherein the SHSV of the fresh feedstream is about 5, the recycle ratio is in the range of about 1.5 to about 3, and the inlet temperature to said first reaction zone is about 130 oF. A A process according to claim 10 wherein the methanol to isobutene ratio in the total feed to said first reaction zone is in the range of about 0.99 to about 1.02. 12. A process according to claim ii wherein said fresh feedstream contains about 10 to about 20 weight percent isobutylene on a methanol free basis. 13. A process according to claim 13 wherein the effluent from said second reaction zone is subjected to distillation to obtain an hITBE product substantially free of methanol. 14. A process according to any one of claims 1-13 wherein the conversion of isobutene is greater than it would be under the same inlet temperature, substantially adiabatic conditions, and fresh feed LHSV if no effluent recycle were passed through said first reaction zone. 1-5. In a process for preparing methyl tert-butyl ether by reacting isobutylene and methanol, the improvement comprising carrying out said reaction in two stages by feeding a fresh feedstream comprising isobutylene and methanol through a first reaction zone comprising a fixed bed of acid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain the reactants in the liquid phase and recycling effluent from said first reaction zone through said first reaction zone along with said fresh feedstream wherein the fresh feedstream contains no more than about 25 weight percent isobutylene on a methanol free basis, the molar ratio of methanol to isobutylene entering said first reactor is about 1/1, said fresh feedstream and said recycle stream are passed into said first reaction zone at a temperature of about 120 to about 140n e, the LHSV of said fresh feedstream is in the range of about 3 to about 5, the recycle ratio is about 2 to about 6; and passing unrecycled effluent from said first reaction zone through a second reaction zone comprising a fixed bed of acid ion exchange resin under substantially adiabatic conditions and a pressure sufficient to maintain the reactants in the liquid phase wherein said unrecycled effluent is passed into said catalyst bed of said second reaction zone at a temperature of about 100F to about llOF and a IMSV of about 3 to 7. 16. A process according to claim 15 wherein said fresh feedstream contains isobutylene in the range of about 15 to about 20 weight percent on a methanol free basis.

Claims: Claims 1. A process for preparing methyl tert. butyl ether by reacting isobutylene and methanol, c h a r a c t e r i z e d b y carrying out said reaction in two stages in a first and a second reaction zone each comprising a fixed bed of acid ion exchange resin and keptunder substantially adiabatic conditions and a pres sure sufficient to maintain the reactants in the liquid phase, and feeding a fresh feedstream comprising isobutylene and methanol through said first reaction zone and recycling effluent from and through said first reaction zone along with said fresh feedstream wherein the molar ratio of methanol to isobutylene in the combined feeds entering said first reaction zone is about 1/1, the inlet temperature of the feeds is in the range of 49 to 600C and the rates of addition are such that the conversion of isobutylene is at least 90.weight percent and at least as great as it would be under the same inlet temperature, adiabatic and fresh feed LHSV conditions without effluent recycling; and passing unrecycled effluent from said first reaction zone through said second reac tion zone with an inlet temperature in the range of 38 to 430C and at a LHSV yielding an isobutylene conversion of at least 50 weight percent. 2. A process according to claim 1 characterized in that the LHSV of effluent passed through said second reaction zone is such that the hottest spot in the catalyst bed is no greater than about 60C above the inlet temperature of said effluent into said second reaction zone; in parti cular wherein the LHSV of effluent passed through said second reaction zone is in the range of 3 to 7. 7. 3. A process according to claim 1 or 2 characterized in that said fresh feedstream contains from 10 to 60 weight per cent isobutylene on a methanol free basis; in particular wherein said fresh feedstream contains no more than about 25 weight percent isobutylene on a methanol free basis; in particular wherein said fresh feedstream contains from 10 to 20 weight percent isobutylene on a methanol free basis; in particular wherein said fresh feedstream con tains isobutylene in the range of 15 to 20 weight percent on a methanol free basis. 4. A process according to at least one of the preceding claims characterized in that said fresh feedstream com prises the fraction of the hydrocarbons from a stream or catalytic cracking process that boils in the range of C4 hydrocarbons. 5. A process according to at least one of the preceding claims characterized in that the recycle ratio of effluent from said first reaction zone is no greater than about 14; in particular wherein the recycle ratio of effluent from said first reaction zone is from 2 to 6; in particular wherein the recycle ratio of effluent from said first reaction zone is no greater than about 5. 6. A process according to at least one of the preceding claims characterized in that theLHSV of the fresh feed stream through said first reaction zone is in the range of 2 to 5 or 3 to 5. 7. A process according to at least one of the preceding claims characterized in that the LHSV of the fresh feedstream is about 5, the recycle ratio is in the range of 1.5 to 3, and the inlet temperature to said first reaction zone is about 540C. 8. A process according to at least one of the preceding claims characterized in that the methanol to isobutene ratio in the total feed to said first reaction zone is in the range of 0.99 to 1.02. 9. A process according to at least one of the preceding claims characterized in that the effluent from said se cond reaction zone is subjected to distillation to ob tain an MTBE product substantially free of methanol.

Inventors: MAKOVEC, DONALD JOHN
Applicants: PHILLIPS PETROLEUM COMPANY
Application year: 1982
Main classification: C07C43
IPC codes: C07C41, C07C43, B01J31, C07C67