ETHER PRODUCTION WITH STAGED REACTION OF OLEFINS

Abstract: A process for upgrading olefin feedstock containing a mixture of iso-olefin and linear olefin to produce tertiary-alkyl ether and high octane gasoline components comprising dimerized iso-olefin. Product recovery is integrated between primary and secondary reaction stages. In a preferred embodiment, a two stage etherification process employs a secondary solid acid regenerable catalyst bed to dimerize unconverted iso-butene in the debutanizer overhead stream of a conventional MTBE primary reactor stage. Both stages can utilize a regenerable acid catalyst such as ZSM-5 or Zeolite Beta for etherification and to upgrade unconverted alkenes and methanol from the primary stage.

Description: ETHER PRODUCTION WITH STAGED REACTION OF OLEFINS The present invention relates to a multi-stage process and apparatus for preparing al yl ethers in high yield. In particular, it relates to catalytic conversion of a mixture of alkene isomers by reaction with alkanol under etherification conditions, followed by selective oligomerization of unreacted iso-alkene from the primary stage. Recent efforts have been made in the field of gasoline blending to increase gasoline octane performance without the addition of deleterious components such as tetraethyl lead and benzene. It has been found that lower molecular weight unsymmetrical ethers such as MTBE and TAME can be added to Cb_-C1, Λ 0 hydrocarbon-containing gasoline products in order to increase octane number. The research octane number (RON) of MTBE has been listed at 115 (Lander, E.P.. et al, "National Petroleum Refiners Association Annual Meeting", San Francisco, Calif., March 20-24, 1983). The blending octane number of MTBE has been calculated over various concentrations and some of the readings are: RON, 115-135; MON (motor octane number), 98-110; and (RON & M0N)/2, 106-122.5 (Pecci, G. et al, Hydrocarbon Processinσ. 1977, 56, 98). Blending octane number rises when MTBE concentration is decreased and saturates concentration of the base fuel is increased. Conventional etherification processing uses as catalyst a macroreticular cation exchange resin in the hydrogen form. An example of such a catalyst is "Amberlyst 15". A resin catalyst gives a high conversion rate but is unstable at elevated temperatures (above 90°C) . When overheated, the resin catalyst releases sulfonic and sulfuric acids. In addition leaching of acid substances from the resin catalyst even at normal operating temperatures causes a reverse reaction - decomposition of ether products to starting materials - to occur upon distillation of ether product. Overall yield is thereby significantly decreased (see U.S. Patent No. 4,182,913). Etherification reactions conducted over a resin catalyst such as "Amberlyst 15" are usually conducted in the liquid phase below a temperature of about 90"C and at a pressure of about 1480 kPa (200 psig) . Equilibrium is more favorable at lower temperatures but the reaction rate decreases significantly. Also excess methanol appears to be required to achieve acceptable selectivity over "Amberlyst 15" (see Chu et al, Industrial Engineering and Chemical Research, Vol. 26, No. 2, 1987, 365-369). Some recent efforts in the field of etherification reactions have focused on the use of acid medium-pore zeolite catalyst for highly selective conversion of n-alkene and iso-alkene with lower aliphatic alcohol starting materials. Examples of such zeolite catalysts are ZSM-4, ZSM-5. ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-50 and zeolite Beta. Due to lower acidity as compared to resin catalysts, the zeolites need to be employed at higher reaction temperature to achieve the desired conversion rates. These solid acid catalyst particles are much more thermally stable than resin catalyst f are less sensitive to methanol-to-alkene ratio, give no acid effluent, and are easily and quickly regenerated (see Chu et al, "Preparation of Methyl Tert-Butyl Ether (MTBE) over Zeolite Catalysts", Industrial Engineering and Chemical Research , op cit.). Etherification of isoalkenes and n-alkenes with medium pore zeolites is disclosed in U.S. Patent Nos. 4,605,787 and 4,714,787. Co-conversion of etherification effluent from MTBE production is described in U.S. Patent Nos. 4,788,365; 4,826,507; and 4,854,939 wherein unreacted oxygenates and olefins are upgraded in a second zeolite catalyst stage under high temperature reaction conditions to obtain aromatics-rich C_+ hydrocarbon components suitable for use in blending high octane gasoline. This technique is advantageous for eliminating costly methanol and other oxygenates recovery and converting the unconverted butene to higher molecular weight products. It has been discovered that 2-stage ether and gasoline production can be enhanced by upgrading etherification effluent under controlled moderate severity reaction conditions to oligomerize and etherify isoalkene, thereby producing a second stage effluent rich in high octane C_+ branched hydrocarbons and additional t-alkyl ether products. Under selected reaction conditions, it is possible to effect the isoalkene oligomerization, etherification and alkylation of olefins with alkanol without forming aromatic or a large amount of low octane linear olefins products. One important aspect of this invention is its ability to remove iso-olefins from linear aliphatics, which typically are blended into gasoline. Iso-olefins are highly reactive gasoline components in the atmosphere, and their removal from gasoline pool hydrocarbons is important in production of clean fuels. A multistage process has been found for etherifying a mixed C.+ olefinic hydrocarbon feedstock containing isoalkene and n-alkene. The novel process includes the steps of: contacting the olefinic feedstock and aliphatic alcohol in a first reaction stage reaction zone under partial etherification. conditions with acid etherification catalyst to convert a major amount of the isoalkene to C_+ tertiary-alkyl ether; recovering a reactant effluent from the first stage containing tertiary-alkyl ether product, unreacted alcohol and unreacted olefin including n-alkene; separating an ether-rich C + liquid product stream from the first stage effluent; reacting the first stage effluent under low severity di erization conditions at moderate temperature in a secondary stage catalytic reaction zone containing porous solid acid oligomerization catalyst to dimerize at least a portion of iso-alkene; recovering a C g + liquid hydrocarbon stream rich in C_ branched alkene from secondary stage effluent; and recovering n-alkene substantially free of iso-alkenes from secondary stage effluent. In the preferred embodiment the alcohol consists essentially of methanol, the secondary stage catalyst comprises medium pore zeolite and the primary stage catalyst comprises polymeric sulfonic acid resin, and the mixed olefin feedstock consists predominantly of C. hydrocarbons containing isobutene and n-butene. Figure 1 is a schematic diagram of a preferred embodiment of the present process, showing major operating units and flow of reactants and chemical products; and Figure 2 is a detailed equipment diagram for a referred fixed bed reactor arrangement. While the invention can be employed with various C 3 -C_. olefins, primary attention is directed to C 4 streams containing isobutene, 1-butene and/or 2-butene. In a preferred embodiment, the present inventive process relates to the preparation of MTBE. Two reaction stages are maintained in series. The first reaction stage contains solid acid etherification catalyst particles. The second reaction zone contains medium pore zeolite solid acid catalyst, such as a fluidized bed of zeolite beta, ZSM-5 or the like. Mixed feedstock containing methanol and C. hydrocarbons, including n-butenes and isobutene, is contacted with solid catalyst particles in the first stage reaction zone under etherification conditions to obtain an intermediate product comprising MTBE and unreacted feedstock, including 10 to 55% of isobutene * in the fresh feedstock and excess methanol. The intermediate product is then withdrawn from the first " 5 stage reaction zone, fractionated to recover MTBE, and added to the second stage catalyst zone for contact with acid catalyst under controlled severity reaction conditions. A product containing MTBE, isobutene oligomer and C_+ alkylate is then withdrawn from the 10 second reaction zone. The second stage product may be prefractionated to recover unreacted butenes and other C.- components. The preferred present process further comprises removing the second stage catalyst from on-line contact 15 with the feedstrea , replenishing or regenerating the solid catalyst particles in the second stage reaction zone, and resuming addition of feedstock to the second stage reaction zone. The preferred medium pore solid acid catalyst particles are aluminosilicate zeolites 20 selected from ZSM-5, ZSM-11, ZSM-50, zeolite Beta, MCM-22 and mixtures thereof, especially the finely divided particles useful as additives in cracking heavy petroleum (FCC) materials. Since the mixed olefinic feedstock obtained from 25 fluid catalytic cracking (FCC) light crackate gas contains many impurities, the solid acid zeolite catalyst from the second stage may also be employed in a guard chamber for pretreating etherification feed, whereby the zeolite becomes highly contaminated after a 30 period of on-line contact with etherification feedstock. Some of the impurities which may be absorbed on the zeolite particles in a guard chamber include nitrogen and oxygenated compounds; metals such as Al, Fe, Na and Mg; and oligomers of olefins and 35 diolefins, such as isoprene and cyclopentadiene. Diolefinic compounds and other related hydrocarbons are deposited as coke on the surface and interstices of the zeolite and/or resin catalytic particles. It is therefore an additional objective of the present process to remove feedstock impurities with second stage zeolite in a guard chamber contact zone concurrently with the preparation of ethers. The first stage etherification reaction zone preferably comprises a plurality of catalytic fixed bed reactors operatively connected in series for inter-reactor cooling. In an alternative embodiment, the second stage reaction zone comprises a moving bed, slurry, fluidized bed, or ebullated bed. The most preferred second stage reactor system is a fixed bed reactor containing zeolite Beta. It is within the scope of the present process and apparatus to adjust the number and types of reactors which contain acid zeolite catalyst in order to optimize both product yield and overall energy consumption as would be practiced by one skilled in the art. Optional catalyst regeneration can be achieved by contacting contaminated zeolite catalyst particles with oxygen or oxygen-containing gas in a regeneration zone under conditions of temperature and pressure sufficient to remove at least a major amount of impurities from the catalyst particles. Typical oxidative regeneration conditions are 371°-510°C (700°-950°F) and 103-1482 kPa (0-200 psig) . In an alternative embodiment zeolite catalyst particles can be regenerated by stripping with a hot stream of hydrogen gas at a temperature of about 371"-538 β C (700°-1000°F) . Hydrogen stripping avoids the problem of inactivating the catalyst by "steaming" which can occur under oxidative regeneration conditions due to water -formation. If the zeolite catalyst is not reused in the second stage conversion reactor or guard chamber contact zone, it may be passed without regeneration directly or indirectly to the associated FCC unit for cracking petroleum fractions. * The primary stage reaction zone contains an acid resin catalyst which is preferably a macroreticular 5 polystyrene sulfonic acid resin catalyst in one or more fixed bed catalytic reactor units, most preferably only in the last stage of the etherification reactor. The primary reactor section is preferably operated at a temperature of 40°-90 β C. Primary reactor configuration 10 can take many forms, for example, fixed bed or stirred slurry (see U.S. Patent No. 3,940,450), swing or ebullated bed. It is within the scope of the present process to employ for the primary stage reaction zone any reactor configuration for sequencing acceptable to 15 the skilled engineer. The secondary stage feed may be vapor, liquid or mixed phase fluid. The reaction is preferably operated in a vapor phase above 758 kPa (110 psia) for a feed containing more than 10% C.- components. The reaction 20 takes place at 70°-280 β C. In a preferred embodiment the olefinic feedstock comprises isobutene in an amount of at least about 10 wt %, preferably 25 to 40%. Although the preferred alcohol is methanol, 25 suitable lower aliphatic alkanols include ethanol and isopropanol (isopropyl alcohol) . Of course, use of these substitutes will yield different ether products. It is within the scope of the present process to employ , a mixture of lower molecular weight alcohols. Although 30 isomeric butenes are the preferred hydrocarbon feed, other iso-olefin such as C_ amylenes containing n-amylene and 3-methy1-2-butene can be etherified in. the present process. » The multi-stage reactor system includes a first 35 stage reactor containing acid etherification catalyst in a first reaction zone, including means for feeding and contacting the olefinic feedstock and aliphatic alcohol under partial etherification conditions to convert a major amount of the isoalkene to liquid tertiary-alkyl ether, and means for recovering a reaction effluent stream from the first stage containing tertiary-alkyl ether product, unreacted alcohol and unreacted olefin including n-alkene. Referring to Figure 1, a pre-washed C. hydrocarbon feedstock stream 10 is combined with a lower molecular weight aliphatic alcohol (methanol) feedstock 12. The combined reactants enter reaction zone 20. An acid etherification catalyst such as polysulfonic acid resin is contained in reaction section 20, which includes at least one primary etherification zone (I) . The mixed alcoholic C. hydrocarbon feedstream contacts the solid catalyst within the primary reaction section 20 at predetermined reaction zone conditions of temperature and pressure as described hereinbefore to convert at least a portion of the feedstream to MTBE. Stage I effluent may be separated in a first fractionator column operatively connected to receive the reaction effluent stream from the first stage including means for recovering an ether-rich liquid product bottom fractionator stream and an overhead fractionator stream containing unreacted alcohol and feedstock olefins. An intermediate primary reaction stream 21 containing MTBE and unreacted C hydrocarbons and alcohol is cooled in heat exchanger 22 before entering debutanizer fractionation tower 24 at a midstage thereof for recovering a product stream 25 rich in tertiary ether (MTBE) and gasoline range hydrocarbons. A liquid stream 26 containing iso-octene and other C_.+ components is introduced at an upper stage of debutanizer tower 24 to effect separation. Further upgrading of unreacted components takes place in a second stage reactor containing porous solid acid oligomerization catalyst in a secondary stage catalytic reaction zone, and including means for reacting at least a portion of the first stage effluent unconverted olefins and alcohol fraction under low severity dimerization conditions at moderate temperature to dimerize iso-alkene and form a normally liquid branched dimer hydrocarbon while leaving n-alkene recovered from the first stage effluent substantially unreacted. Overhead vapor stream 28, containing unreacted volatile C.- components (isobutene, n-butenes, methanol) are heated to moderate reaction temperature in heat exchanger 29 and passed to the secondary reaction zone (II) in reactor 30 for further conversion, as described herein. The C.+ olefins may be supplemented optionally with other light olefin feed 27. For instance, propene can co-dimerized with isobutene to produce a normally liquid branched aliphatic hydrocarbon components suitable for gasoline blending and recoverable by absorption/rectification in the second fractionation unit. Reactor 30 may contain a fluidized bed of solid metal oxide acid catalyst, such as ZSM-5 medium pore aluminosilicate zeolite, which is introduced as fresh or regenerated catalyst via line 31A and removed via line 3IB for conventional regeneration or passed for further use in a FCC unit as auxiliary catalyst. The vapor stream contacts solid catalyst under etherification conditions to obtain MTBE, and under moderate oligomerization conditions to convert isobutene to iso-octene dimer, while the n-butene component is substantially undimerized, i.e. less than 20%. Under the above reaction conditions, wherein substantially all (i.e. greater than 90%) of feedstock isobutene is converted, some alkylation of olefins by methanol may occur, depending on catalyst employed. In a preferred embodiment, an absorber column having distillation/rectification function is operatively connected to receive effluent from the second stage reactor. Advantageously, this includes overhead condenser means for cooling absorber overhead and recovering a n-alkene stream substantially free of iso-alkenes, and means for recycling condensed liquid from the condenser means for contact with second reactor effluent in the absorber column, thereby providing a hydrocarbon liquid rich in branched alkene dimer in an absorber column bottoms stream. This technique permits operative connection between effluent recovery sections of both stages and provides means for passing the absorber column bottoms stream to the first fractionator column for recovery of normally liquid branched dimer hydrocarbon with ether in the liquid product bottom fractionator stream. A second intermediate stream 32 containing MTBE, iso-octene, and other secondary effluent components, such as unreacted C. hydrocarbons and alcohol is withdrawn from reaction zone 30 and enters the second stage separation unit 36, such as distillation/ rectifying column 36. Temperature of second intermediate stream 32 may be reduced prior to entering column 36 or partially condensed therein by contact with cold liquid 37 refluxed by cooling means 38 and employing heat exchanger 40, separator 41 and pump 42. A light n-butene rich stream 39 is recovered substantially free of isobutene, and may be sent for further process (i.e. alkylation) or recycle via line 39A. A liquid stream 26 comprising MTBE and C8 dimer and other C_+ oligomers can be withdrawn from column 36 for recovery as product from first column 24 via line 25 along with C_+ components of the primary reactor effluent. The liquid stream 26 may be filtered from any fines leaving the fluid bed reactor upstream of the common fractionator 24. Regeneration of the solid acid catalyst from reaction zone 30 may be accomplished by procedures well known in the art. It is feasible to eliminate second stage catalyst regeneration by transporting inactivated fluidized catalyst particles to another process, such as the FCC unit, not shown. A preferred embodiment is depicted in Figure 2, employing multiple swing reactors for each stage. The first stage reactor and second stage reactor each comprise a plurality of alternately-connected swing reactor units RIA, RIB, RIIA, RUB, containing a fixed bed of regenerable solid catalyst particles. The regeneration loop RL provides means for treating inactivated catalyst employed in the first or second stage by contacting inactivated catalyst with regeneration gas under catalyst regeneration conditions. Conduits and valves provide fluid handling means for operatively connecting one of the swing reactor units from the first or second stage selectively with the regeneration means in a known manner. This reactor structure permits a single regeneration loop to be connected to any of the individual fixed bed process reactors, thus providing an efficient arrangement.

Claims: CLAIMS : 1. A process for the co-production of a high octane value C_+ hydrocarbon stream in tertiary alkyl ether and a high octane value C 5 + hydrocarbon stream rich in isoalkene, comprising: contacting a C.+ hydrocarbon feedstream containing isoalkene and n-alkene and alkanol feedstream with solid acid etherification catalyst in an etherification zone under isoalkene etherification conditions whereby an effluent stream is produced comprising alkyl tertiary alkyl ether, unconverted C + isoalkene, C 4.+ n-alkene and unreacted alkanol; distilling the etherification effluent stream in a debutanizer with a C_+ isoalkene stream and recovering a debutanizer bottom stream comprising a tertiary alkyl ether-rich C 5 + hydrocarbon stream and an overhead stream containing the unconverted isoalkene, n-alkene and unreacted alkanol; passing the overhead stream to an isoalkene oligomerization zone in contact with acidic medium pore metallosilicate catalyst particles under low severity isoalkene oligomerization and alkanol alkylation conditions at moderate temperature between 70° and 280 β C whereby the C.+ isoalkene is converted to a C_+ hydrocarbon stream rich in isoalkene; and recovering the C g + hydrocarbon stream rich in isoalkene. 2. The process of claim 1 wherein the alkanol comprises methanol whereby methyl tertiary butyl ether or methyl tertiary amyl ether or mixtures thereof is produced. 3. The process according to claim 1 wherein the metallosilicate catalyst particles comprise alumino- silicate zeolite having the structure of ZSM-5, ZSM-11, ZSM-50 or zeolite Beta. 4. The process according to claim 1 wherein the isoalkene oligomerization conditions comprise 0.5-50 weight hourly space velocity based on total olefins in the feed. 5. The process of claim 1 wherein the etherification catalyst comprises zeolite or polymeric sulfonic acid resin. 6. The process of claim 1 wherein the C_+ isoalkene-rich hydrocarbon stream is recovered as bottom stream by distillation of the effluent of the oligomerization zone and C.- n-alkene is recovered as an overhead stream. 7. The process of claim 6 wherein the bottom stream is recycled to the etherification effluent debutanizer whereby the debutanizer bottom stream comprises a high octane value C_+ hydrocarbon stream rich in tertiary alkyl ether and isoalkene. 8. A multi-stage process for etherifying a mixed C. olefinic hydrocarbon feedstock containing isobutene and n-butene and the production of a C 5 + ether-rich and isoalkene-rich hydrocarbon stream, comprising: contacting the olefinic feedstock and methanol in a first reaction zone under isobutene etherification conditions with solid acid etherification catalyst whereby an etherification effluent stream is produced comprising methyl tertiary butyl ether, unconverted isobutene, n-butene and unreacted methanol; distilling the etherification effluent stream in a first product recovery section debutanizer in contact with a C_+ isoalkene-rich stream and recovering a debutanizer bottom stream comprising the C_.+ ether-rich and iso-alkene-rich hydrocarbon stream and an overhead stream containing the unconverted isobutene, n-butene and unreacted methanol; reacting the debutanizer overhead stream under severity isoalkene dimerization conditions at moderate temperature between 70° and 280 C under olefin dimerization and methanol alkylation conditions in a secondary stage catalytic reaction zone containing acidic medium pore metallosilicate oligomerization catalyst particles to convert the unconverted iso-butene to a C-.+ isoalkene-rich hydrocarbon stream while reacting less than 20% of the n-butene; passing the effluent from the secondary stage reaction zone to a rectifying distillation tower for contact with a portion of the rectifying distillation tower overhead comprising condensed n-butene-rich liquid reflux, thereby condensing normally liquid hydrocarbons to recover a liquid hydrocarbon rectifier bottom stream comprising the C-.+ iso-alkene-rich recycle stream; passing the bottom stream from the rectifying distillation tower to the debutanizer in the first product recovery section along with the etherification effluent for recovery with the liquid product stream; and recovering n-butene from the rectifying distillation tower. 9. The process of claim 8 wherein the secondary stage catalyst comprises medium pore aluminosilicate zeolite and the primary stage catalyst comprises a zeolite or polymeric sulfonic acid resin. 10. The process of claim 8 wherein the secondary stage catalytic reactor zone is maintained at low severity oligomerization conditions, including reaction temperature of 50° to 250°C and space velocity of 0.5-50 WHSV based on total olefins present in the feed. 11. A process according to claim 8 wherein the secondary zone catalyst particles comprise aluminosili¬ cate zeolite having the structure of ZSM-5, ZSM-11, ZSM-50 or zeolite Beta.

Inventors: HARANDI MOHSEN NADIMI, OWEN HARTLEY, HARANDI, MOHSEN, NADIMI, OWEN, HARTLEY
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1991
Main classification: C07C41
IPC codes: C07C41, C10L1