Patent Publication Number: US-3878262-A

Title: Preparation of 1,9-decadiene and 1,5-hexadiene

Description:
United States Patent Vives et al.  
 [451 Apr. 15, 1975 2/1970 Zuech PREPARATION OF 1,9-DECADIENE AND ,493, 260/666 A 1 5 3,715,410 2/1973 Ray et al.... 260/680 R 3,786,111 1/1974 Vives 260/680 R [75] Inventors: Van C. Vives; Robert E. Reusser,  
  both of Bartlesvllle Okla- Primary Examiner-Paul M. Coughlan, Jr. [73] Assignee: Phillips Petroleum Company,  
 Bartlesville, Okla. [57] ABSTRACT [22] Filed; 2, 1973 The olefin disproportionation reaction of mixtures of acyclic and cyclic olefin hydrocarbons to produce di- [21] PP N05 412,335 enes is improved by using a consecutive bed catalyst Related Application Data arrangement wherein the first bed is a bed of magne- [62] Division of Ser No 213 928 Dec 30 1971 Pat No siumoxide and the second bed 15 a solld olefin dispro- 3 792 2 portionation catalyst. Subsequent to separation of the reaction effluent, the heavier olefin hydrocarbons pro- U.S. C I l l l I I n R, A duced in the consecutive bed reaction zone are re- [51] Int. Cl u C07c 3/62- C07c11/12 turned to the reaction zone at a point intermediate to [58] Field 2 R 6 A 666 B the two beds to provide conversion of the heavier materials to additional diene product. In addition, a combination process is provided wherein l 9-decadiene 56 Ref 5 Cit d 1 UNITED 22,3 PZTENTS and 1,5-hexadiene are produced from butadiene, ethylene, and hydrogen using dimerization, hydrogena- &#39;i grli g i 3 tion, and olefin disproportionation steps. 3I424Is11 1/1969 Mango 260/680 R 5 Claims, 1 Drawing Figure s ETHYIFENE H2 16 HYDROGENATION za 1 1 J&#39;\ ZONE J 1 I I7 19 l3- 68 z 5 u -72 v 5 -73 l,3-BUTAD|ENE g 2 g E 1,9-DECADIENE &#39;12 o 0 l 11 53 I E 2&#39;3 2 k a 2 5 E E l2 l4 28 2 L217 Z w 9 g &#39;2 1 S-HEXADIENE N g 1 I z 1: es- E g -71 29 PREPARATION OF 1,9-DECADIENE AND 1,5-HEXADIENE This application is a division of our copending application Ser. No. 213.928 filed Dec. 311. 1971. now U.S. Pat. No. 3.792.102.  
 BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to olefin disproportionation. In a further aspect. this invention relates to the reaction of acyclic olefins and cyclic olefins by means ofthe olefin disproportionation reaction to produce diene hydrocarbons. In a further aspect of this invention. 1.9- decadiene and 1.5-hexadiene are prepared from butadiene. ethylene. and hydrogen using dimerization. hydrogenation. and olefin disproportionation steps.  
 2. Description of the Prior Art The art has recently reported numerous catalytic materials which effect the olefin disproportionation reaction of unsaturated hydrocarbons. The olefin reaction can be visualized as the breaking of two existing double bonds between first and second carbon atoms. and between third and fourth carbon atoms. respectively. and the formation of two new double bonds. such as between the first and third carbon atoms and the second and fourth carbon atoms. respectively. wherein the new double bonds can be on the same or different molecules. The reaction can be visualized by using a mechanistic scheme involving a cyclobutane transition state wherein two pairs of carbon atoms each pair connected by a double bond combine to form a 4-center intermediate which then disassociates by breaking either set of opposing bonds. This reaction can be illustrated by the following formulas:  
  The above reaction has been described by various terms other than olefin disproportionation. Among those terms utilized are the olefin reaction.&#34; &#34;olefin dismutation.&#34; mutual cleavage. transalkylidenation.&#34; and olefin metathesis.&#34; Throughout this specification and claims. the term olefin disproportionation&#34; is used as a matter of choice and is deemed to be equivalent to the abovementioned terms. In addition. it has recently been discovered that the disproportionation reaction can be applied to materials other than olefinically unsaturated hydrocarbons. Accordingly. it has been reported that acetylenically unsaturated hydrocarbons and olefinic materials which contain functional groups such as nitrile groups or fluoro groups also undergo this type of reaction.  
  Among the numerous catalyst systems which have been reported to effect this disproportionation reaction are those of US. Pat. No. 3.261.879. Banks (1966). and U.S. Pat. No. 3.365.513. Heckelsberg 1968). The Heckelsberg patent discloses that tungsten oxide on silica is a suitable disproportionation catalyst.  
  The disproportionation reaction of any acyclic olefin and a cyclic polyene has been described in the prior art by Mango. US. Pat. No. 3.424.811 (1969). A problem in conducting the reactions described by Mango. wherein an acyclic olefin and a cyclic polyene are reacted to provide diene products. is that low initial conversion levels are often necessary in order to insure that the selectivity of the reaction to the primary products is very high. However, such a process is very expensive because it increases the size of subsequent separation units and recycle lines. An additional problem encountered with the hydrocarbon feedstocks utilizing the Mango process is that contaminants often associated with the feed have a deleterious effect on conversion levels. thereby reducing the activity to the olefin disproportionation catalyst. A solution to this latter problem has been suggested whereby a guard bed of activated magnesium oxide operated at low temperatures is used to purify the feed olefins prior to introduction into the olefin disproportionation catalyst zone. However. this solution has been only partially successful in that high conversions of the cyclic olefin material in the reaction zone have been difficult to obtain.  
 OBJECTS OF THE INVENTION It is an object of this invention to improve the initial conversion levels and ultimate yields of the acyclic diene products when disproportionating a mixture of acyclic olefins and cyclic olefin materials. It is a further object of this invention to provide 1.5-hexadiene and 1.9-decadiene from butadiene. hydrogen. and ethylene. Other objects and advantages of the present invention will be apparent to those skilled in the art from a reading of the following summary of the invention. detailed description of the invention. examples. and claims.  
 SUMMARY OF THE INVENTION The problems discussed above concerning the Mango process can be avoided by our discovery. Our process comprises disproportionating a mixture of acyclic olefins and cyclic olefins in an olefin disproportionation catalyst zone wherein the catalyst comprises consecutive beds of magnesium oxide and the olefin disproportionation catalyst. The use of magnesium oxide at the temperature of the olefin disproportionation reaction results in higher initial conversions than those obtainable without the presence of the magnesium oxide. Subsequent to separation of the reaction effluent. the heavy materials produced by the initial reaction are returned to the consecutive bed catalyst zone at a point between the two beds. Thus. the recycled heavy hydrocarbons are contacted only with the olefin disproportionation catalyst rather than the combination of the high temperature magnesium oxide bed over the solid olefin disproportionation catalyst bed.  
  In a further embodiment of our invention. we have provided a process whereby 1.5-hexadiene and 1.9- decadiene can be prepared by first dimerizing butadiene in the presence of a cyclodimerization catalyst to provide 1.5-cyclooctadiene and 1.5 .9- cyclododecatriene products. The two products of this reaction are then separated. and the cyclooctadiene is passed to a hydrogenation zone wherein the presence of hydrogen and a suitable hydrogenation catalyst the cyclooctadiene is converted to cyclooctene. The cycloocteneis then passed to an olefin disproportionation reaction zone in the presence of ethylene to provide 1.9-decadiene. The l.5.9-cyc1ododecantriene from the separation unit is passed to a second olefin disproportionation zone wherein it is reacted with ethylene to provide l,5-hexadiene.  
  In a further embodiment of our invention, this disproportionation reaction of ethylene and 1,5- cyclooctadiene and the disproportionation reaction of ethylene and l,5,9-cyclododecatriene is conducted in a single olefin disproportionation zone to provide 1,5- hexadiene, and 1,9-decadiene.  
 In our combination processes as discussed above, it  
 is preferred that the olefin disproportionation reaction of ethylene and acyclic olefin reactants be conducted in a manner as discussed above whereby consecutive bed arrangement of magnesium oxide and the solid disproportionation catalyst is employed and the heavy materials produced in this reaction are returned to the reactor(s) at a point between the two catalyst beds.  
 BRIEF DESCRIPTION OF THE DRAWING The sole FIGURE of the drawing presents a schematic flow diagram which illustrates the combination process of our invention wherein dimerization, hydrogenation, and olefin disproportionation steps are used to convert butadiene, hydrogen, and ethylene to 1,5- hexadiene, and l,9-decadiene.  
 DETAILED DESCRIPTION OF THE INVENTION The acyclic olefin and cyclic olefin reactant materials used in our process have been described by Mango. Accordingly, the disclosure of his patent, US. Pat. No. 3,424,81 l, of Jan. 28, 1969, at column 1. lines 6472, and column 2, lines l-50, are hereby incorporated by reference into this application.  
  The olefin disproportionation catalysts employed in our process are also known in the prior art. Any solid catalyst system which is capable of promoting or catalyzing the olefin disproportionation reaction of butene- 2 and ethylene to propylene is suitable for use in our process. Preferably, the disproportionation catalyst is one of molybdenum, tungsten, or rhenium oxide deposited on a support silica, alumina, silica-alumina, or aluminum phosphate. A molybdenum oxide-promoted catalyst is disclosed in the Banks patent mentioned supra. Tungsten oxide-promoted catalyst is discussed in the Heckelsberg patent mentioned supra. The rhenium oxide-promoted catalyst is disclosed in British Pat. Specification No. 1,054,864, Turner et al. As reported in the prior art, these solid catalysts can also contain minor amounts of various treating agents, such as trialkylaluminum compounds, dialkylaluminum halides, monoand polyvalent alcohols, and the like. It is also sometimes advantageous to treat the solid catalyst with suitable gases, such as CO, H and the like.  
  Disproportionation catalysts employed as the second bed in the catalyst zone of our invention can also be treated with alkaline earth and alkali metal compounds as reported in the prior art. Preferably, the alkaline earth or alkali metal compound is a compound of sodium or potassium.  
  The magnesia suitable for use in the invention can be any suitably activated material known in the art. The material normally has a surface area of at least 1 m /g. Magnesia can be naturally occurring, such as the mineral brucite, or can be synthetically prepared by suit able techniques. Minor amounts of other materials such as silica, alumina, and the like, can be present but the material is principally magnesium oxide. Depending upon the contacting technique used in the consecu- LII tive bed reaction zone, the activated magnesia can be in the form of pellets, extrudates, agglomerates, or even a fine powder. Before use in the process, the magnesium oxide is activated in a suitable manner such as by heating the flowing stream of oxygen-containing gas for about I to about 30 hours at 500 to l,500F. preferably 600 to about l,000F. After activation sometimes it is advisable to flush the catalyst with an inert gas to remove any absorbed oxygen or other gases from the magnesium oxide. The regeneration of the spent magnesium oxide catalyst is generally accomplished by a technique similar to the activation of this material.  
  The olefin disproportionation conversion of the mixture of acyclic olefins and cyclic olefin materials is accomplished in a reaction zone containing first a bed of the magnesium oxide and second a bed of the solid olefin disproportionation catalyst. Suitable techniques are well known in the art for suspending catalytic entities in a suitable reactor.  
  The reaction temperature of the conversion is dependent upon the particular olefin disproportionation catalyst employed, and will be selected for the temperature at which the catalyst gives the greatest amount of initial conversion of the reactant mixture to the primary products of the reaction. Generally, these temperatures range from about to 1,200F. In the process of the invention, pressures are not important but will be in the range of from 0 to 2,000 psig, and weight hourly space velocities (WI-ISV) of about 0.1 to about 1,000 w/w/hr.  
  The olefin disproportionation conversion reaction of the acyclic and cyclic olefins will generally produce a significant amount of heavier olefin materials having a greater molecular weight than the primary product of the reaction of the acyclic olefin with the cyclic olefin. For example, the reaction of ethylene and cyclooctene to produce l,9-decadiene will produce appreciable quantities of olefin materials having 10 or more carbon atoms. The effluent from the olefin reaction zone is then separated using conventional techniques to provide a stream of the heavier olefin products which is returned to the initial olefin reaction zone. Therein the heavy products are introduced into the reactor at a point between the consecutive beds of the magnesium oxide and olefin disproportionation catalyst. Using this aspect of our invention, it is possible to readily convert the heavier materials to additional primary product of the reaction. For example, in the case of the ethylene and cyclooctene reaction, the C material will be significantly converted to l,9-decadiene.  
  In that embodiment of our invention wherein the 1,9- decadiene and l,5-hexadiene are produced using a combination of dimerization, hydrogenation, and disproportionation steps, the dimerization catalyst can be any catalyst known in the art for the cyclooligomerization of butadiene to provide 1,5-cyclooctadiene and l,5,9-cyclododecatriene. For example, the catalysts disclosed in US. Pat. No. 3,250,817 (I966) can be used.  
  Hydrogenationcatalysts employed in our process can be any catalysts known in the art to promote the selective hydrogenation of 1,5-cyclooctadiene to cyclooctene. For example, the catalysts of US. Pat. No. 3,493,625 (1970) are suitable for this step of the process.  
  The combination process embodiment of our invention can best be understood by reference to the FIG- URE of our drawing. The FIGURE presents a schematic flow diagram of our process using separate olefin disproportionation reactors for the conversion of cyclooctene and the conversion of 1.5 .9- cyclod odecatriene. The process employs two disproportionation zones. 69 and 72. a dimerization zone 66. a hydrogenation zone 68 and three fractionation zones 67, 71 and 73. The disproportionation zone 72 uses a suitable catalytic reactor which contains a consecutive bed arrangement of magnesium oxide and a solid olefin disproportionation catalyst. Butadiene-l.3 enters in line 11 and is contacted with a suitable cyclodimeriza tion catalyst in zone 66. The cyclodimerization reaction produces a stream containing 1.5-cyclooctadiene and l.5.9-cyclododecatriene in line 12. If the catalyst in zone 66 is of the soluble or suspended type. it can be separated and recycled to zone 66 (separation and recycle means not shown). Disproportionation zone 69 comprises a suitable reactor containing a solid olefin disproportionation catalyst with no magnesium oxide.  
  The effluent in line 12 is passed to fractionation zone 67 wherein the 1.5-cyclooctadiene is removed overhead in line 13 and the 1.5.9-cyclododecatriene is removed as bottoms in line 14. Any unreacted butadiene can be recovered and returned to zone 66 if desired (recovery and return means not shown). The 1.5- cyclooctadiene is passed via line 13 into hydrogenation zone 68 along with H gas in line 16. Zone 68 contains a catalyst which is capable of selectively converting the cyclic diene to the cyclic monoene. cyclooctene. The conditions in the zone are maintained to minimize the formation of cyclic alkanes. The cyclooctene is removed from zone 68 via line 17 and passed into an olefin disproportionation zone 72. Ethylene is introduced into line 17 via lines 18 and 19. Recycle ethylene is present in line 19 from line 22.  
  Within zone 72 the ethylene&#39;cleavage of the cyclic monoolefin produces 1.9-decadiene. The 1.9- decadiene containing effluent stream 21 is passed to fractionation zone 73 wherein the ethylene is recovered and removed via line 22 to be returned to zone 72 via line 19. Heavier olefin hydrocarbons are removed via line 24 and returned to zone 72 at a point intermediate to the bed of magnesium oxide and the olefin disproportionation catalyst bed for further conversion therein. Product 1.9-decadiene is removed from the fractionation zone 73 via line 23 as a product of the process.  
  The bottoms stream 14 from fractionation zone 67 comprises l.5.9 cyclododecatriene which is passed to a second olefin disproportionation zone 69. Ethylene enters zone 69 via lines 18 and 26. The ethylene cleavage of l.5.9-cyclodedecatriene produces 1.5-hexadiene in the line 27 effluent which is passed to fractionation zone 71. Therein ethylene is separated and removed vialine 28 and returned to reactor 69 via line 28. Olefin hydrocarbons heavier than 1.5-hexadiene. including complished in a single olefin disproportionation zone.  
 The reaction occurs readily as long as sufficient ethylene is provided to the reaction zone to insure highconversions of the feed cyclic olefins. Moreover. in this embodiment of our invention. the l,5.9- cyclododecatriene is not contacted with the magnesium oxide catalyst bed which is maintained at high temperature. Thus. where separate reactors in the same conversion zone are used. the cyclooctene feed is passed through the hot magnesium oxide and the disproportionation reactor while the l.5.9- cyclododecatriene and the heavier recycle products are contacted only with the disproportionation catalyst. In a consecutive bed arrangement of the catalysts within a single reactor the same contacting order is also used. The acyclic olefin or the cyclic olefin. or both. can be pretreated by contact with a bed of activated magnesium oxide at mild temperatures prior to being introduced into the reaction zone. The purity of the cyclic olefin feed is an important factor in the process of our invention because it directly affects the efficiency and operability of the process. The olefin disproportionation reaction in general requires substantial absence of materials which cause difficulty as. for example. by poisoning of the catalyst. Some of these impurities such as oxygen and water are known; others are unknown. Activated magnesia is greatly superior to any other absorption agents in the purification of feed streams for the olefin disproportionation reaction. Thus the magnesia mentioned above and as described for use in combination with the olefin disproportionation catalysts can be employed at low temperature for pretreatment of the olefin feed. As opposed to the temperature of the activated magnesia in the olefin disproportionation zones. it is necessary that the pretreatment temperature be under mild temperature conditions. Accordingly. the temperature of treatment may be as low as the freezing point of the feed material. and may be as high as the point where significant isomerization of the single olefins such as butenes and pentenes is observed. Frequently. ambient temperatures such as room temperatures are satisfactory for pretreatment.  
 &#39; Any conventional contacting device can be used for the pretreatment. For example. the olefin can be treated by passing through a fixed or fluidized bed of activated magnesia or contact can be made by suspending the magnesia by suitable agitation in a vessel containing the olefin to be treated. Contact with the magnesia can be either in vapor or liquid phase. Time of contact. throughput rate in regard to the fixed bed of magnesia. or magnesia usage per unit weight of olefin can be varied over a wide range. However. a sufficient degree of treatment is allowed to bring the l.5- cyclooctadiene and 1.5.9-cyclododecatriene into condition for reaction. Generally. pretreatment tempera- .tures of from room temperature to about l50F are satisfactory.  
  lf desirable. magnesium oxide can be used in conjunction with other known absorptive materials in the pretreatment step. For example. magnesium oxide can be used either consecutively or in a mixture with alumina. silica gel. molecular sieve type materials. absorptive clays. and the like. When used in mixture. the regeneration procedure should be selected to be compatible with all components of the treated mixture.  
  Our invention can be further illustrated by the following examples. The examples are presented to illustrate the invention as described hereinabove. and  
  7 8 should not be construed as limiting that which has been Table 11 -Continued described heretofore.  
 Results Sample time. hrs. 1.5 6.5 10.5 EXAMPLE I Conversion. 92&#34; 92.6 90.3 87.8  
  Ultimate yield of 1.9-  
 \ z I 7 C yclooctene and ethylene were converted to 1.9- decadiene over a tungsten oxide on silica olefin dispropmduq cnmpusimm 5 portionation catalyst (6.871 WO;;.93.2/( SiO The cy- 51351 5 1 s clooctene feed was pur1f1e d by passage over a column Unknown A (m6 (m8 (m3 of MgO and a mol sieve prtor to bemg mtroduced to the i y y m 4 v @XSK 1611C reactor. Condltlons of the runs and results are summa cyclohemncm 2.18 L33 H5 r1zed below 1n Table l. Cy&#39;cloheptcne&#39; 5.49 3.84 3.41  
 Table 1 Conditions Temperature &#34;F 650 650 PS16 600 600 C HJcyclooctene 10/1 10/1 WHSV 50.8 81.7 100 Sample time. hrs. 0.75 1.33 0.5 2.35  
 Results Conversion&#34; 83.4 78.0 73.9 77.5 Ultimate yield of 1,9-decadiene, mol 7r 80.1 82.6 81.4 82.4 Wt. 7: Heavies&#34;&#34; 12.2 12.8 12.8 12.1 Product Composition (Wt/7r Propylene 0.33 0.29 0.13 0.13 Butenes 0.46 0.18 0.07 0.09 Unknown A 0.23 0.15 0.07 0.07 Unknown B 0.30 0.18 0.09 0.05 Cyclohexene 1 l 2 0.62 0.33 0.34 Cycloheptene 2.61 1.61 1.10 0.84 1,7-octadiene 5.08 3.51 3.44 2.77 1,9-decadiene 80.27 83.21 84.51 85.68 Heavier (C 9.74 10.25 10.61 10.03  
 &#34;&#34;Mol ratio &#34;Weight hourly space velocity &#34;Convcrsion and ultimate yield were calculated on a cyclooctene feed purity of 94.26% &#34;&#34;Expressed as weight percent of the cyclooctene converted Product composition was calculated on an ethylene and cyclooctene free basis &#34;The component was tentatively identified by GLC-mass spectroscopic analysis.  
  EXAMPLE 11 1.7-OLlzldlCne 9.11 7.119 6.41 1.9-dccadiene 72.48 77.411 79.60 In this example, 1,9-decad1ene was prepared from cy- Heavies (C,..+) 9.5-1 9.69 11.911  
 clooctene and ethylene. A reactor was partially filled with 1.20 g. tungsten oxide on silica (6.8% WO;,.93.2% silica). On top of this catalyst was placed a layer of asbestos fiber. On top of the fibers was placed a bed of 10.0 g. MgO.  
  The catalyst system was activated in place by passing air through the bed for about 3 hours at 1.000F. followed by treatment with CO for minutes at the same temperature. The feed cyclooctene was passed over a column ofMgO and a mol sieve to purify the feed prior to the reaction. The conditions of treatment and results are summarized in Table 11 below.  
 &#34;&#34;Weight hourly space velocity based on tungstate catalyst alone &#34;&#34;Mole ratio &#34;&#34;(onversions and ultimate yields were calculated on feed purity f 94.26&#39;1&#39; as It is readily apparent from the comparison of the results of Examples 1 and 11 that the addition of a bed of magnesium oxide over the tungstate disproportionation catalyst in the conversion reactor provides increased conversions of the cyclooctene feed.  
 EXAMPLE 111 A second run was made using an essentially identical catalyst and feed as employed in Example 11. In this run. the ethylene to cyclooctenemol ratio was varied. Conditions and results are summarized below in Table 111.  
 Table 111 I Conditions Temperature &#34;F 650 P G 600 WHSV 106 C,H /Cyclo C,.= 4/1 8/1 12.6/1 Sample time. hrs. 0.5 1.5 2.5  
 Results 7! Conversion 94.7 90.2 86.2 Ultimate yield of 1.9-decadiene 58.1 71.7 87.0 Wt. percent heavies 24.2 13.8 9.8 Product Composition (wtf/l Propylene 0.90 0.31 0.21 Butenes 0.41 0.14 nil Unknown A 0.19 0.09 nil Unknown B 0.16 0.10 nil 1,5-hexadiene 0.33 A 0.10 nil Cyclohexene 2,42. 0.99 0.59 Cycloheptene 5.37 3.11 1.83 1.7-octadiene 7.29 4.83 3.99 1.9-decadiene 62.20 78.29 86.40 Heavies (C..,+) 0.66 12.04 7.00  
  The above data demonstrate that at ethylene to cyclooctene mol ratios of 8/1 8/1 and 12.6/las compared I C. .H../c...+ feed&#34; 3.12 3.42 to 4/1. higher ultlmate yields are obta ned with concur- V 2t) 54 rent reduction in the .amountsof heavy materials pro- Results duccd I y &#34;/1 Conversion olC 37.5 59.0  
 &#39; 1.9-decadiene yield. wtf/l OnC +feed 1.0 28.7 EXAMPLE 1v On cIII+ consumed 2.6 48.7 Product Composition. wt./(&#34; Two runs were made to demonstrate the conversion Propylene 2.62 13.34 of the he; 1 n &#39;I I 1 811101183 10.10 1.51 m l l prepdrd m Example. ll UnknownA 17.70 0.33 above. Mass spectrographic analysis of the heavies Unknown B 2918 L34 showed the principal component of the C fi heavy ma- Unknown C 5.7 Nil t v C H l (s 99 {(7 y d 1.7-octadiene 12.46 9.03 etltt IL-l5 l. HOIICyC 1: 1 3 0 e In w f) an L1 L) decndiene noncycltc C,,.H;, olefin (84.59 wt.% The C,..H,, olefin was b li d t b 1 9 l7 t d i &#34;&#34;Wcight ratio based on the -1 content of the feed.  
  The heavy fructiolil of the run of Example was &#34;&#34;Wcighthuurl space \elocit of the l&#39;ced over the tungstate catalyst only, fl h d O -h d to remove y yg d p d 15 &#34;&#34;Net \ield. corrected for small amounts o1 1.9-tlccadienc in the feed.  
  h l i &#34;&#34;(alculated on an ethylene and -lheavies l&#39;rec h s. Slnce a hnnted amount of the flashed Overhead was &#34;(&#39;on\punent \vastentathely&#39; identified h \&#39;(il.(&#39;anal .isonl available, it was diluted with cyclohexane. The mixed feed was stored under nitrogen and repercolated over The above example demonstrates that in an operamagnesium oxide-mol sieve prior to being introduced tion in which the heavy C material is returned to the into the reactor. 0 process as a recycle stream, the yield of additional 1.9-  
  ln this example, one reactor was filled with the same decadiene is several fold larger when said stream is catalyst as used in Example 1. The other reactor was passed over only the WO .SiO catalyst as compared to filled with the catalyst used in Example 11. Conditions th yield Obtained by passing this stream over both the and results are summarized below in Table IV. g and az ly Table IV EXAMPLE V Conditions 1,5-Hexadiene was prepared by the conversion of RNA 1.5.9-cyclododecatriene and ethylene over an olefin (/1 MEOWOIJS&#39;O1 ml/S102 disproportionation catalyst of tungsten oxide on silica. cvciohe&#39;xune 51 7| 7110 The 1,5,9-cyclododecatriene feed was purified over a 1.9-de adi n 2 mol sieve prior to introduction into the reactor. Reacg g O :1 53 tion conditions and results are set forth below in Table PSlG 600 600 V.  
 Table V Conditions Sample No. 1 2 3 4 5 6 7 8 Temperature, F 600 600 680 650 675 700 700 700 PS10 400 400 400 400 400 400 400 400 C H /1.5,9-Cyclododecatriene (CDT) weight ratio 14/1 14/1 14/1 14/1 14/1 14/1 14/1 28/1 WHSV 10 l0 15 1O l0 10 20 10 Results Conversion (CDT) 98.6 99.3 99.6 99.9 99.8 99.9 99.9 99.7 Product Composition (Wt. 7r)  
 1,9-Decadiene 6.7 7.3 8.7 6.9 6.2 4.2 10.3 5.5 1.5-Hexadiene 85.1 87.8 85.2 85.9 87.3 89.0 81.6 88.0  
  This example demonstrates that l ,5 ,9- cyclododecatriene and ethylene can be converted to l.5-hexadiene in the presence of an olefin disproportionation catalyst.  
  Reasonable variations and modifications of the invention as described above will be apparent to those skilled in the art without departing from the spirit and scope thereof. Thus the description herein of a consecutive bed arrangement of the two catalyst entities in a single reaction zone is obviously equivalent to, and is intended to be synonymous with, an-arrangement of two separate catalytic reactors where the isomerization catalyst reactor is operated at isomerization conditions followed by the disproportionation reactor.  
 What is claimed is:  
  1. A process for the preparation of l,9-decadiene and 1.5-hexadiene from butadiene. ethylene and hydrogen which comprises the steps of a. dimerizing butadiene to provide a stream comprising l,5-cyclooctadiene and 1,59- cyclododecatriene;  
 b. separating the stream of step (a) to provide a stream of l.5-cyclooctadiene and a stream of 1,5,9- cyclododecatriene;  
 c. passing the stream of 1,5-cyclooctadiene from step (b) in the presence of hydrogen over a hydrogenation catalyst to produce a stream comprising cyclooctene;  
 d. disproportionating the cyclooctene of step (c) and the l,5,Q-cyclododecatriene of step (b) in the presence of ethylene to provide an effluent stream comprising unreacted cyclooctene, l,5,9-cyclododecatriene, ethylene, 1,9-decadiene and l,5-hexadiene;  
 unreacted.  
 e. separating the effluent stream of step (d) to provide an ethylene stream, a l,9-decadiene stream, a 1,5-hexadiene stream. and a heavier stream containing cyclooctene and 1,5,9-cyclododecatriene;  
 f. returning the ethylene stream and heavier stream of step (e) to step (d); and  
 g. recovering the l,9-decadiene stream, and 1,5-  
 hexadiene stream of step (e) as a product of the process.  
  2. The process of claim I wherein step (d) is accomplished in two olefin disproportionation zones wherein the cyclooctene of step (c) is converted in one zone, and the 1,5,9-cyclododecatriene is converted in the other zone.  
  3. The process of claim 1 wherein the olefin disproportionation catalyst is molybdenum oxide, tungsten oxide, or rhenium oxide on a support of silica, alumina, silica-alumina, or aluminum phosphate.  
  4. The process of claim 1 wherein step (d) is accomplished in a single olefin reaction zone wherein the cyclooctene and 1,5,9-cyclododecatriene first come into contact with magnesium oxide and then into contact with an olefin disproportionation catalyst and in step (f) the heavier stream is returned to step (d) and into the reaction zone at a point between the magnesium oxide catalyst and disproportionation catalyst.  
  5, The process of claim 1 wherein step (d) is accomplished in two separate olefin disproportionation zones wherein a first zone receives the cyclooctene stream of step (c) and the second zone receives the l,5,9- cyclododecatriene of step (b).