Abstract:
Alkenes, such as normal butenes in a mixed C 4  stream are oligomerized, preferably to dimers, which are dimerized in a distillation column reactor over ZSM-57 zeolite catalyst at high conversions and high selectivity to octenes. Prior to oligomerization the mixed C 4  stream is pretreated to remove dimethyl ether, butadienes and sulfur compounds.

Description:
This application claims the benefit of provisional application 60/489,977 filed Jul. 25, 2003. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to the oligomerization of alkenes, e.g., the oligomerization of normal butenes to produce primarily octenes. More particularly the invention relates to the oligomerization of 1-butene and 2-butene contained in a mixed C 4  stream which has been depleted of isobutenes such as from an MTBE unit or isobutene purification units. More particularly the invention relates to the oligomerization of butenes over ZSM-57 zeolite catalyst in a distillation column reactor. 
     2. Related Art 
     The mixed C 4  stream from an MTBE unit or an isobutene purification unit, often called a raffinate stream, contains diluted normal butenes, especially butene-1 and butene-2. These streams have been dimerized in the past in tubular reactors containing catalysts such as supported phosphoric acid (SPA) and the zeolites ZSM-22 and ZSM-57. However the reaction conditions have been severe, e.g., temperatures of between 330° F. to 482° F. and pressures of between 1,000 psig to 1,215 psig. 
     Besides the reaction conditions the catalysts have previously had short lives. The SPA catalyst produces only about 333 tons of oligomers per ton of catalyst and has a useful lifetime of 2–3 weeks on stream, after which the catalyst must be discarded. The zeolite catalysts have longer lifetimes (3–4 months), but lose activity and must be regenerated off-line at considerable expense. 
     The selectivity of the above-mentioned catalysts is lower than ideal. The desired product from butenes is octenes, which can be converted to isononyl alcohols. Higher oligomers, such as C 12  olefins are useful to the extent that profitable outlets, e.g., tridecyl alcohol or isopar solvents, can be found. 
     Typical results of the selectivity of the above catalysts in the tubular reactors are shown below in TABLE I: 
     
       
         
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE I 
               
             
             
               
                   
                   
               
               
                   
                 Catalyst 
               
             
          
           
               
                   
                   
                 ZSM-22 
                 ZSM-22 
                 ZSM-57 
                 ZSM-57 
               
               
                   
                 SPA 
                 @ 94%* 
                 @ 50%* 
                 @ 94%* 
                 @ 50%* 
               
               
                   
               
             
          
           
               
                 Selectivity, 
                   
                   
                   
                   
                   
               
               
                 Mol % 
               
               
                 Paraffin 
                 &lt;1 
                 6 
                 6 
                 &lt;1 
                 &lt;1 
               
               
                 C 6  Olefin 
                 1 
                 &lt;1 
                 &lt;1 
                 &lt;1 
                 &lt;1 
               
               
                 C 7  Olefin 
                 4 
                 &lt;1 
                 &lt;1 
                 &lt;1 
                 &lt;1 
               
               
                 C 8  Olefin 
                 45 
                 50 
                 70 
                 78 
                 88 
               
               
                 C 9  Olefin 
                 9 
                 1.5 
                 &lt;1 
                 3 
                 &lt;1 
               
               
                 C 10 –C 11   
                 13 
                 2 
                 &lt;1 
                 1 
                 &lt;1 
               
               
                 Olefin 
               
               
                 C 12  Olefin 
                 22 
                 27 
                 18 
                 10 
                 7 
               
               
                 C 12 + Olefin 
                 4 
                 13 
                 5 
                 7 
                 2 
               
               
                   
               
               
                 *Olefin conversion per pass 
               
             
          
         
       
     
     Finally, it should be noted that isobutenes have been oligomerized over acid cation exchange resin catalysts in distillation column reactors in combination with boiling point reactors as disclosed in U.S. Pat. Nos. 4,242,530 and 5,003,124. 
     The present invention provides higher conversion per pass than in other processes with higher selectivity. A further advantage is that the present process operates under less severe conditions of temperature and pressure than prior commercial oligomerization processes using ZSM-57 catalyst. Still another advantage is a much longer online time before turnaround to regenerate the catalyst and potentially longer catalyst life. It is a feature of the present invention that the catalyst can be regenerated and enhanced in situ, thus providing even greater efficiency and cost savings. 
     SUMMARY OF THE INVENTION 
     Briefly, the present invention is a process for the oligomerization of alkenes comprising feeding alkenes to a distillation column reactor containing a bed of ZSM-57 zeolite catalyst, contacting said alkenes with said ZSM-57 zeolite catalyst under conditions of oligomerization, thereby catalytically reacting said alkenes to form oligomers and concurrently separating and recovering said oligomers. Preferably the alkenes comprise linear alkenes having from 3 to 8 carbon atoms, such as C 4  alkenes, preferably n-butenes. 
     In a preferred embodiment the mixed butenes, such as raffinate, may be readily oligomerized over the zeolite catalyst ZSM-57 in a distillation column reactor at very high selectivity to octenes (&gt;90 mol %). The oligomerization is preferably carried out under conditions which favor dimerization as opposed to longer chain oligomers, preferably at pressures of between 300 and 400 psig and temperatures in the range of 240 to 320° F. at conversions of up to about 97 mol %. 
     To obtain the advantages of the present process the mixed butenes must be free of certain components that poison the ZSM-57 catalyst such as dimethyl ether (DME), and some sulfur compounds, e.g., dimethyl sulfide, and butadiene. This is also required for the prior non catalytic distillation processes using ZSM-57. All of the undesirable materials can be removed conventionally by distillation, sulfur chemisorption and butadiene hydrogenation. 
     In cases where the sulfur guard bed has failed and sulfur compounds have poisoned the ZSM-57 catalyst, the catalyst may be regenerated in situ by washing with normal heptane. The regeneration has been found to have increased the catalyst activity. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWING 
       The FIGURE is a simplified flow diagram of the preferred embodiment of the invention. 
     
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The feed to the present process is preferably pretreated to remove contaminants such as DME, butadiene and sulfur compounds. Acceptable levels of these impurities are: DME&lt;1 wppm; total sulfur&lt;1 wppm; and 1–3 butadiene&lt;10 wppm. The DME can be removed by distillation which may be conveniently combined with the selective hydrogenation of the 1–3 butadiene in a distillation column reactor. A hydrogenation catalyst, such as palladium or nickel, is used in a distillation column reactor at mild conditions. The DME is taken as overheads and the remainder is taken as bottoms. The sulfur compounds may be removed by chemisorption on reduced massive nickel catalysts, such as Sud-Chemie C46 or Engelhard D-4130. 
     A typical feed to the process of the present invention comprises dilute normal butenes in a mixed C 4  stream which has typically been depleted of isobutene. Table II below lists the components of such a typical stream. 
     
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE II 
               
               
                   
                   
               
               
                   
                 Hydrocarbons, wt. % 
                 Sulfur Compound, wppm 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Ethane 
                 00.09 
                 H 2 S 
                 0.000 
               
               
                   
                 Ethylene 
                 00.00 
                 Carbonyl Sulfide 
                 0.401 
               
               
                   
                 Propane 
                 00.87 
                 Methyl Mercaptan 
                 0.756 
               
               
                   
                 Propylene 
                 00.17 
                 Ethyl Mercaptan 
                 1.835 
               
               
                   
                 Isobutane 
                 24.00 
                 Dimethyl Sulfide 
                 1.178 
               
               
                   
                 n-butane 
                 22.73 
                 Dimethyl Disulfide 
                 1.057 
               
               
                   
                 propadiene 
                 00.00 
                 Methylethyl Disulfide 
                 1.925 
               
               
                   
                 Butene-1 
                 20.08 
                 Diethyl Disulfide 
                 1.386 
               
               
                   
                 Isobutene 
                 01.07 
                 Total Sulfur 
                 8.538 
               
               
                   
                 t-Butene-2 
                 17.96 
               
               
                   
                 c-Butene-2 
                 11.71 
               
               
                   
                 Butadiene 1–3 
                 0.04 
               
               
                   
                 Isopentane 
                 01.16 
               
               
                   
                 Pentene-1 
                 00.06 
               
               
                   
                 DME 
                 00.07 
               
               
                   
                 Total Butenes 
                 50.81 
               
               
                   
                   
               
             
          
         
       
     
     The use of the distillation column reactor is known. Catalyst is placed on trays or combined into a distillation structure and placed into a distillation column. The selective hydrogenation of diolefins such as propadiene and 1–3 butadiene in a distillation column reactor is disclosed in U.S. Pat. No. 6,169,218 which is hereby incorporated by reference. In the present invention a fractional distillation is made simultaneously with the selective hydrogenation of the 1–3 butadiene to remove the DME contaminant as overheads. 
     The catalyst, to be effective, must be in the form so as to provide gas liquid contact. There are many forms of catalyst structures available for this purpose and these are disclosed variously in U.S. Pat. Nos. 5,266,546; 4,731,229; and 5,073,236. The most preferred catalyst structure is disclosed in U.S. Pat. No. 5,730,843 which is hereby incorporated by reference. 
     It is believed that in the present reactions catalytic distillation is a benefit first, because the reaction is occurring concurrently with distillation, the initial reaction products and other stream components are removed from the reaction zone as quickly as possible reducing the likelihood of side reactions. Second, because all the components are boiling the temperature of reaction is controlled by the boiling point of the mixture at the system pressure. The heat of reaction simply creates more boil up, but no increase in temperature at a given pressure. As a result, a great deal of control over the rate of reaction and distribution of products can be achieved by regulating the system pressure. Also, adjusting the throughput (residence time=liquid hourly space velocity −1 ) gives further control of product distribution and to a degree control of the side reactions such as oligomerization. A further benefit that this reaction may gain from catalytic distillation is the washing effect that the internal reflux provides to the catalyst thereby reducing polymer build up and coking. Internal reflux may be varied over the range of 0.2 to 20 L/D (wt. liquid just below the catalyst bed/wt. distillate) and gives excellent results. 
     Referring now to the FIGURE a simplified flow diagram of the preferred embodiment of the invention is shown. The mixed C 4  stream is fed along with hydrogen via flow line  101  to a first distillation column reactor  10  containing a bed  12  of hydrogenation catalyst. In the distillation column reactor  10  the butadienes are selectively hydrogenated to butenes and at the same time the DME is separated by fractional distillation and removed as overheads via flowline  102 . The bottoms containing the butenes and less than 10 wppm butadiene are removed via flow line  103  and fed to reactor  20  containing a bed  22  of catalyst that chemisorbs the sulfur compounds. 
     The effluent from the reactor  20  containing less than 1 wppm total sulfur compounds is removed via flow line  104  and fed, along with recycle from flow line  108 , via flow line  105  to a second distillation column reactor  30  containing a bed  32  of ZSM-57 zeolite catalyst. A portion of the butenes in the stream are oligomerized to higher olefins, preferably octenes, in the catalyst bed. The higher boiling oligomers and some butenes are removed as bottoms via flow line  107 . Some butenes may be taken as overheads and recycled as reflux (not shown) with a purge of lighter material taken via flow line  106  to prevent buildup of the lighter material. 
     The bottoms in flow line  107  are fed to a debutanizer column  40  where any C 4 &#39;s are removed as overheads and recycled to the second distillation column reactor  30  for further conversion. Product oligomers are removed from the debutanizer as bottoms via flow line  109  for further separation. 
     EXAMPLE 1 
     Twenty-one pounds of ZSM-57 zeolite catalyst were loaded in a distillation column reactor utilizing the catalyst structure shown in U.S. Pat. No. 5,730,843. A typical feed, as shown in TABLE II above, after treatment to remove the DME, butadiene and sulfur to acceptable levels was fed to the reactor. The reactor conditions and results are shown in TABLE III below. 
     
       
         
               
               
               
               
               
               
             
           
               
                 TABLE III 
               
               
                   
               
             
             
               
                 Hrs. on line 
                 392 
                 640 
                 742 
                 804 
                 888 
               
               
                 Feed, lbs/hr 
                 20 
                 20 
                 20 
                 20 
                 30 
               
               
                 Reflux, 
                 30 
                 30 
                 30 
                 30 
                 45 
               
               
                 lbs/hr 
               
               
                 Pressure, 
                 300 
                 350 
                 375 
                 400 
                 350 
               
               
                 psig 
               
               
                 Temp. ° F. 
                 245–255 
                 271–286 
                 274–289 
                 293–313 
                 299–317 
               
               
                 Upflow 
                 66.68 
                 93.88 
                 97.03 
                 98.23 
                 86.88 
               
               
                 Conv. % 
               
               
                 Select., 
               
               
                 wt. % 
               
               
                 C 6  olefins 
                 0.1286 
                 0.2083 
                 0.1612 
                 0.2108 
                 0.0912 
               
               
                 C 8  olefins 
                 96.6607 
                 90.8567 
                 92.8994 
                 92.8113 
                 93.3147 
               
               
                 C 10  olefins 
                 0.2383 
                 0.5438 
                 0.2862 
                 0.2564 
                 0.2371 
               
               
                 C 12  olefins 
                 2.9724 
                 7.7808 
                 6.4369 
                 6.4651 
                 6.2268 
               
               
                 C 12 + olefins 
                 0.000 
                 0.6104 
                 0.2164 
                 0.2564 
                 0.1302 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 2 
     The catalyst was regenerated in situ by washing with normal heptane under the following conditions: 
     
       
         
               
               
               
             
           
               
                   
                 TABLE IV 
               
               
                   
                   
               
             
             
               
                   
                 Pressure, psig 
                 250 
               
               
                   
                 Temperature, ° F. 
                 460 
               
               
                   
                 n-heptane feed, lbs/hr 
                 15 
               
               
                   
                 n-heptane overhead, lbs/hr 
                 10 
               
               
                   
                 n-heptane bottoms, lbs · hr 
                 10 
               
               
                   
                 catalyst, lbs 
                 21 
               
               
                   
                 WHSV 
                 1.4 
               
               
                   
                 Treatment time, hrs 
                 50 
               
               
                   
                   
               
             
          
         
       
     
     The mixed C 4  feed was restarted to the reactor and a comparison of the regenerated and fresh catalyst is shown in TABLE V below. 
     
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE V 
               
               
                   
                   
               
               
                   
                 Catalyst 
                 Fresh 
                 Regenerated 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Feed, lbs/hr 
                 20 
                 20 
               
               
                   
                 Reflux, lbs/hr 
                 30 
                 30 
               
               
                   
                 Pressure, psig 
                 400 
                 300 
               
               
                   
                 Temp. ° F. 
                 293–313 
                 220–230 
               
               
                   
                 Upflow Conv. % 
                 98.23 
                 99.95 
               
               
                   
                 Select., wt. % 
               
               
                   
                 C 6  olefins 
                 0.2108 
                 0.1931 
               
               
                   
                 C 8  olefins 
                 92.8113 
                 93.4661 
               
               
                   
                 C 10  olefins 
                 0.2564 
                 0.5570 
               
               
                   
                 C 12  olefins 
                 6.4651 
                 5.6407 
               
               
                   
                 C 12 + olefins 
                 0.2564 
                 0.1481 
               
               
                   
                 Activity constant, k 
                 0.4696 
                 2.7807 
               
               
                   
                 Cat. Prod., g-mole/hr-lb cat 
                 2.5342 
                 3.5278 
               
               
                   
                   
               
             
          
         
       
     
     Unexpectedly the regenerated catalyst performed better than the fresh catalyst.