CA1267645A

CA1267645A - Process and catalyst for the oligomerization of olefins

Info

Publication number: CA1267645A
Application number: CA000509427A
Authority: CA
Inventors: Robert R. Frame
Original assignee: UOP LLC
Current assignee: Honeywell UOP LLC
Priority date: 1985-05-23
Filing date: 1986-05-16
Publication date: 1990-04-10
Anticipated expiration: 2007-04-10
Also published as: JPS61278355A; FI862163A; US4613580A; KR890002861B1; EP0202670A3; FI862163A0; AU5781386A; ATE55279T1; DE3673238D1; ZA863716B; KR860008799A; CN86103976A; BR8602344A; AU577695B2; AR241478A1; EG18249A; EP0202670A2; EP0202670B1; CN1003912B

Abstract

"PROCESS AND CATALYST FOR THE
OLIGOMERIZATION OF OLEFINS"

ABSTRACT
Olefins are oligomerized to a desired oligomer by utilizing a catalyst which comrpises a porous support containing a catalytically effective amount of an iron group metal hydrate in which the mole ratio of water of hydration to iron group metal is greater than 0.5:1 in combination with a catalytically effective amount of an alkyl aluminum compound and and aluminum halide.

Description

~L~6~6~

; "PROCFSS AND CQTALYST FOR THE
;- OLIGOMERIZATION OF OLEFINS' BACKGROUND OF _HE INVENTION

The oligomerizat.on of olefins is known in the art, such oligo-merization processes being effected by treating olefinic hydrocarbons with certain catalysts to obtain various oligomers which will find a useful function in the chemical art. One type of catalyst which may be employed for this particular type of reaction comprises a supported metal compound.
For example, U.S. Patent 3,562,351 discloses a method for dimerizing ole-fins utilizing a supported catalyst which has been prepared by impregna-ting a suitable support with a salt solution of a Group VIII metal followed by a heat treatment in an inert atmosphere at a temperature less than that which is required to form a metal oxide but which will form a complex on the surface of the solid support. Following this, the catalyst is acti-vated by treatment with an organometallic compound. U.S. Patent 3,483,269 describes a catalyst useful for oligomerizing lower olefins which com-prises a ~r-allyl nickel halide supported on an acidic inorganic oxide support. If so desired, the support may have been optionally treated with an alkyl aluminum compound. U.S. Patent 3,592,869 also describes a cata-lyst which is useful for the oligomerization of olefins. A divalent nickel compound and an alkyl aluminum compound are contacted with an olefinic compound. The resulting mixture is then used to impregnate an inorganic refractory oxide support. Another patent, namely U.S. Patent 3,644,56~, describes a catalyst for the oligomerization of ethylene which comprises an organo aluminum-free reaction product of a nickel compound which is an atom of nickel in complex with an olefinically unsaturated compound and a fluorine-containing ligand. The catalysts are typically formed in situ.
U.S. Patent 3,679,772 describes a process for reacting monoolefins with diolefins, the catalyst for such a reaction comprising a complex of ~1) nickel, ~2) a Group VA electron donor ligand such as an organophosphine, (3) a nonprotonic Lewis acid and (4) a reducing agent which itself may be :

a Lewis acid, all of which are composited on an acidic silica-based sup-port.
U.S. Patent 3,697,617 describes an oligomerization process in-volving the use of a catalyst ~omprising a complex of nickel with a chlo-ro-containing electron donor ligand such as chlorodiphenylphosphine com-bined with a nonprotonic Lewis acid which is capable of forming a coordin-ation bond with nickel and a reducing agent capable of reducing nickel acetylacetonate to an oxidation state less than 2. This complex may be composited on a solid support comprising an acidic silica-based material such as silica alumina. The Lewis acid and the reducing agent may com-prise the same compound as, for example, ethyl aluminum sesqui chloride.
U.S. Patent 3,663,451 describes a catalyst which is obtained by reacting a transition metal halide such as nickel halide with a carrier to give a carrier-metal bond. This product is then reacted with a ligand such as a phosphine or ~ ketone and finally activated by treatment with an aluminum alkyl or chloro alkyl.
U.S. Patent 3,755,490 describes the polymerization of an olefin utilizing a catalyst comprising nickel, a Group VA electron donor ligand, a Lewis acid, and a reducing agent on a solid acidic silica-based support.
U.S. Patent 3,954,668 is drawn to an oligomerization catalyst comprising a nickel compound, a chloro-containing electron donor ligand, or a phos-phorous compound, a nonprotonic Lewis acid reducing agent which is capable of reducing nickel acetylacetonate to an oxidation s~ate of less than 2 and which is also capable of forming a coordination bond with a nickel.
U.S. Patent 3,170,904 speaks to a catalyst which is useful for polymeriza-tion comprising a large surface area metal of Groups VIIA or VIII of the Periodic Table, boron trifluoride etherate, an organometallic compound of Groups I, II, III or IV or a halo derivative of an organometallic compound of Groups II, III or IV or a hydride of a metal of Groups I, II or III.
The large surface area metal which comprises one component of this cata-lyst is in metallic form as, for example, Raney nickel. If so desired, the catalyst may be composited on a diatomaceous earth carrier. In like manner, U.S. Patent 3,170,904 discloses a catalyst which compr;ses (A) a ~6~

carrier-supported nickel or cobalt oxide which has been prepared by impreg-nating th~ carrier with the hydroxide, organic acid salt, inorganic acid salt, followed by oxidation in the presence of oxygen or a combination of nitrogen and oxygen; (B) a boron, titanium, zirconium, or vanadium ha-lide; and (C) an alkyl metal or alkyl metal halide. In addition to these patents, British Patent 1,390,530 describes an oligomerization catalyst which has been prepared by thermally pretreating a metal oxide carrier material followed by reacting with a halogen-containing organo-aluminum compound and thereafter in a step-wise fashion, impregnating this product -with a divalent nickel or cobalt complex at temperatures ranging from -50 to 150C.
As will hereinafter be shown in greater de~ail, the oligomeriza-tion of olefinic hydrocarbons may be accomplished by treating said olefins in the presence of a catalyst which has been prepared in a manner such ~5 that the catalyst will remain active and stable for a relatively long period of time and, in addition, will provide products which possess a de-sired configuration with respect to the branching or minimal branching oF
the chain.
BRIEF SUMMARY OF T~E INVENTION
This invention relates to a catalytic composite which is useful for the oligomerization of olefinic hydrocarbons. More specifically9 the invention is concerned with a catalyst composite and a process for the oligomerization of olefinic compounds, particularly olefinic hydrocarbons, whereby the use of the catalytic composite will result in the obtention of selective oligomers of the olefinic feed stock.
The term "polymerization" has a relatively broad meaning in the chemical art. Although it is generally referred to as the preparation of relatively high molecular weight polymers, that is polymers possessing molecular weights of greater than 50,000 or more, it may also refer ~o low molecular weight polymers9 that is, polymers possessing molecular weights lower than 50,000. In contradistinction to this, the term "oligomeriza-.

67~

tion" refers to polymeric compounds in which the molecules consist of only a r-elatively few monomeric units and thus would include dimerization, trimerization or tetramerization.
Many olefinic hydrocarbons which contain from 4 to about 12 car-bon atoms in the chain are utilized in various industries in many ways.
For example, dimers of propylene regardless of the amount of branching may be used to improve the octane number of motor fuels which are utilized in internal combustion engines utilizing gasoline as the fuel thereof. The presence of these compounds in a motor fuel such as gasoline will improve the octane number of the fuel to a high level, thus enabling the gasoline to be utilized in combustion engines in an unleaded state. Other uses For dimers containing 6 carbon atoms would be in the synthesis of flavors, per-fumes, medicines, dyes and resins. Another use of an oligomer would be found in the d;merization product of butene in which the dimer which pos-sesses a relatively straight chain configuration with a minimum of branch-ing such as one methyl substituent on the chain would be as an intermediate in the production of a plastici2er. The plasticizer, when added to a plastic will facilitate compounding and improve the flexibility as well as other properties of the finished product. Likewise, a trimer of butene or a dimer of hexene in which the olefin contains 12 carbon atoms may be used as an intermediate in various organic syntheses such as in the prep-aration of detergents, lubricants, additives, plasticizers, flavors, per-fumes, medicines, oils, dyes, etc. In addition, linearized oligomers con-taining 12 or more carbon atoms, upon hydrogenation, provide excellent diesel fuels.
It is therefore an object of this invention to provide a cata-lyst for the oligomerization of olefinic hydrocarbons.
A further object of this invention is to provide a specific cata-lyst system which may be used in a process for the oligomerization of olefinic hydrocarbons whereby selective oligomers may be obtained thereby.
In one aspect an embodiment of this invention resides in a cata-lytic composite comprising a combination of a catalytically effective ~ ~6 7~

amount o~ an alkyl aluminum compound on a porous support containing a cata-lytically effective amount of an iron group metal hydrate in which the mole ratio of water of hydration to iron group metal is greater than 0.5:1.
Another embodiment of this invention is found in a process for the oligomerization of an olefinic hydrocarbon which comprises treating said hydrocarbon in the presence of a catalyst comprising a combination of a catalytically effective amount of an alkyl aluminum compound composited on a porous support containing a catalytically effective amount of an iron group metal hydrate in which the mole ratio of water of hydration to iron group metal is greater than 0.5:1, at oligomerization conditions, and re-covering the resultant ol;gomer.
A specific embodiment of this invention is found in a catalytic composite comprising a combination of a catalytically effective amount of diethyl aluminum chloride on an alumina support which contains a catalyti-cally effective amount of nickel hydrate, the mole ratio of water of hy-dration to iron group metal being in a range o`f from about 0.5:1 to about 6:1 prior to reaction with said diethyl aluminum chloride, said diethyl aluminum chloride being present in a mole ratio in the range of from about 0.05:1 to about 6:1 moles of diethyl aluminum chloride per mole of nickel.
Another specific embodiment of this invention is found in the process for the oligomerization of an olefinic hydrocarbon which comprises treating propylene in the presence oFa catalyst comprising a combination of a catalytically effective amount of diethyl aluminum chloride on an alumina support wh;ch contains a catalytically effective amount of nickel hydrate, the mole ratio of water of hydration to iron group metal being in a range of from about 0.5:1 to about &:1 prior to reaction with said di-ethyl aluminum chloride, said diethyl aluminum chloride being present in a mole ratio in the range of from about 0.05:1 to about 6:1 moles of di-ethyl aluminum chloride per mole of nickel at a temperature in the range of from about -20 to about 120C and a pressure in the range of from about 350 to about ~O`O`Opsig t2410 to 6895 kPag), and recovering the resul-tant oligomer comprising a mixture of hexene, methylpentene and dimethyl-butene.

-pther objects and embodiments will be found in the following de-tailed description of the invention.
DETAILED D~SCRIPTION OF THE INVENTION
.
; As hereinbefore set forth, the present invention is concerned with a catalyst composite which may be utilized for the oligomerization of olefins and to a process which employs the catalyst. HeretofQre, the preparation of a catalytic composite which may be used for the polymeriza-tion or oligomerization of olefinic compounds was relatively difficult in-asmuch as several relatively expensive compounds were required as compo-nents of the composite. In contradistinction to this, the catalytic com-posite of the present invention is relatively easy to prepare and, in addi-tion, employs compounds which are less expensive than the components of the other catalyst. The final catalytic composite of the present invention will possess a high activity and will be stable over a relatively long period of time. In addition to these desired attributes, the catalyst will also produce a high yield of dimer products9 especially from C3 and C4 ole-fins as compared to trimer and tetramer products. The dimer products pro-duced by the oligomerization of propylene or the n-butenes will possess a high percentage of linear compounds, that is, n-hexenes and n-octenes and also a high percentage of dimers which contain only one methyl substituent;
more highly branched oligomers being minority products. The propylene di-mers which are produced by the process of the present invention all possess high octane numbers regardless of the branching, and thus are excellent octane blending components. In addition, the n-butene dimers are excellent as intermediates in the preparation of plasticizers.

2~ The catalytic composite of the present invention will comprise a combination of a catalytically effective amount of an alkyl aluminum com-pound on a porous support which contains a catalytically effective amount of an iron group metal hydrate. In addition, if so desired, the catalytic composite can also contain, in combination therewith, a catalytically ef-3n fective amount of an aluminum halide. In the preferred embodiment of the ~67~

invention, the iron group metal hydrate will be obtained from a soluble salt of nic;~el or cobalt such as, for example, nickel nitrate, nickel hydroxi~e, nickel bromide, nickel chloride, nickel fluoride, nickel ace-tate, cobaltic chloride, cobaltous acetate, cobaltous ammoni~m chloride, co-baltous bromide, cobaltous fluoride, cobaltous perchlorate, cobaltous sulfate,etc. The porous support upon which the iron group metal hydrate is im-pregnated will include inorganic metal oxides such as alumina, silica9 mix-tures of oxides such as alumina-silica, alumina-zirconia-magnesia, etc. or crystalline aluminosilicates which are commonly known as zeolites.
The other components of the catalytic composite will comprise alkyl aluminum compounds such as dimethyl aluminum chloride, diethyl alu-minum chloride, dipropyl aluminum chloride, dimethyl a1uminum bromidè, diethyl aluminum bromide, dipropyl aluminum bromide, dimethyl aluminum iodide, diethyl aluminum iodide, dipropyl aluminum iodide, etc. In addition, the aluminum halide which may be used to form a component of the catalytic composite in conjunction with the alkyl aluminum compound will include aluminum chloride, aluminum bromide, aluminum iodide, etc. It is to be understood that the aforementioned list of iron group metal compounds, porous supports, alkyl aluminum com-pounds and aluminum halides are only representative of the class of com-pounds which may be employed to form the catalytic composite of the pres-ent invention, and that said in~ention is not necessarily limited thereto.
The oligomerization catalyst of the present invention may be pre-pared in such a manner so as to provide the finished catalyst with certain characteristics with regard to the selectivity of olefins obtained by the reaction of an olefin in the presence of sa;d catalyst as well as a speci~
ficity of the product so obtained. The catalyst composite is prepared by impregnating a porous support of the type hereinbefore set forth with a simple divalent iron group metal salt such as, for example, nickel nitrate, ~2~;76~5 preferably from an aqueous solution. After impregnation of the porous sup-port such~as alumina, which is effected at ambient temperature and atmo-spheric pressure, the impregnated support is then subjected to a thermal treatment. By varying the temperature of the thermal treatment, it is pos-sible to obtain a catalyst composite which will provide a greater selec-tivity to dimer products resulting from the oligomerization of the olefin in contrast to trimer and tetramer products than are obtained when using other conventional oligomerization catalys~s. The thermal treatment of the impregnated support is preferably effected in a range of from about 350~ to about 450C, the preferred thermal treatment temperature being in a range of from about 340 to about 360C. The thermal treatment of the catalyst base containing the impregnated iron group metal salt in hydrate form will result in a weight loss due to a loss of water of hydration from the metal salt. In the preferred embodiment of the invention, the mole ratio of water of hydration to iron group metal following the thermal treatment will be greater than 0.5:1 and preferably in a range of from about 0.5:1 to about 6:1.
Following the thermal treatment, the iron group metal impreg-nated catalyst base is then treated with an alkyl aluminum compound where-in the activated solution will produce a catalyst of maximum activity.The treatment of the base with the activating agent is also effected at ambient temperature and atmospheric pressure utilizing a solution of the alkyl aluminum compound dissolved in an organic solvent such as benzene, toluene, the xylenes, etc. In the preferred embodiment of the invention, in addition to the alkyl aluminum compound which may be of the type herein-before set forth in greater detail, an aluminum halide compound may also be used in this step. The addition of the impregnated base to the organic solution will result in an exothermic reaction and after thorough admix-ture, the solution is allowed to return to room temperature. The solvent may then be removed by conventional means such as decantation~ evaporation7 etc. and the catalyst thereafter washed with an organic solvent to remove residue or trace portions of unwanted compounds. Thereafter, the catalyst ~L267~

may then he dried by purging with nitrogenl and recovered. In the fin-ished composite, the alkyl aluminum compound ia present in the composite in a mole ratio in the range of from about 0.05:1 to about 6:1, prefer-ably in a range of from about 0.1:1 to about 1:1, moles of alkyl aluminum compound per mole of iron group metal, the latter being present in said composite, on an elemental basis, in an amount in the range of from about 1% to about 20% by weight of the composite, and preferably in an amount in a range of from about 1% to about 10%.
As will hereinafter be shown in greater detail, by preparing a lo catalyst which possesses the various components in the finished composite in mole ratios or weight percent within the ranges hereinbefore set forth, it is possible to selectively oligomeri~e olefin compounds containing from about 2 to about 6 carbon atoms with a concurrent obtention of de-sirable isomers ~n each of the ol~gomer products. In addition, by ut;l-izing an aluminum halide as a component of the catalyst composite in addi-tion to the alkyl aluminum compound, it is possible to obtain a catalyst composite which will be more stable and more active in the conversion of olefins to oligomers than are catalysts which do not contain this com-POund .
As an example of how the catalyst composite of the present in-vention may be prepared, a predetermined amount of a porous base such as alumina, silica, silica-alumina, aluminosilicate, e~c. which may be in the form of spheres, pellets, rods, etc. may be prepared in an appropriate apparatus such as an evaporator along with an aqueous solution of a hy-drated salt of an iron group metal. The mixture may be thoroughly admixed and following this~ the apparatus heated to form the desired iron group metal impregnated base. The impregnated base may then be placed in a heating apparatus such as a tube furnace and treated with air while bring-ing the catalyst to a temperature of about 250~C. The heating is accom-plished at a relatively slow rate and after the determined temperature has been reached, it is maintained thereat for an additional period of time which may range from about 2 to about 4 hours or more in duration. The - `
~2~i7~

calcination of the catalyst base is then effected by increasing the tem-perature to a predetermined level and maintaining thereat for a period of time su fficient to bring the mole ratio of water of hydration present in the iron group metal salt to a determined level which is preFerably in an excess of about 5:1 moles of water of hydration per mole of iron group metal.
After allo~ing the calcination to pro~eed for this predetermined period of time, heating is discontinued and the catalyst base which con-tains from about 1% to about 20% by weight of iron group metal is allowed to cool. The cooled base may then be admixed with a solution of an alkyl aluminum compound and an aluminum halide dissolved in an organic solvent.
As previously discussed, the resulting reaction is exothermic in nature and after allowing the heat to dissipate, the resulting admixture is thor-oughly stirred and allowed to stand for a period of time which may range from about 1 to about 100 hours or more in duration. At the end of this period, the organic solvent is removed by decantation, filtration, cen-trifugation, etc. and the solid catalyst is washed to remove any unreacted material. After washing, the catalyst is then dried in an inert atmo-sphere such as that provided for by the presence of nitrogen, and recovered.
The oligomerization of olefins containing from 2 to about 6 car-bon atoms such as ethylene, propylene, butene-l, butene-2, pentene-1, pentene-2, pentene-3 may then be effected by treating the ole~in in the presence of the catalyst at oligomerization conditions which will include a temperature in the range of from about -20C to about 120C, the pre-ferred range being from about 30 to about 80C, and a pressure in the range of from about 350 to about 1000 psig (2410 to 6895 kPag).
The pressure which is utilized may be the autogenous pressure provided for by the feedstock, if in gaseous phase, or, the feedstock may supply only a partial pressure, the remainder of said pressure being provided by the introduction of an inert gas such as nitrogen, helium, argon, etc. into the reaction zone.
It is conte~plated within the scope of this invention that the oligomerization process may be effected in either a batch or continuous type operation. For example, when a batch type operation is employed, a quantity; of the novel catalyst composite of the present invention mav be placed in an appropriate apparatus such as, for example, an autoclave of the rotating, mixing or stirring type. If the olefinic feedstock is in gaseous form, the autDclave is sealed and the feedstock comprising the olefinic hydrocarbon or a mixture of olefinic and paraffinic hydrocarbon or similar carbon atom length are charged to the reactor until the de-sired operating pressure has been attained. The apparatus is then heated to the desired operating temperature and maintained thereat for a prede-termined period of time which may range from about 1 to about 6 hours or~ore in duration. At the end of this period of time, heating is discon-tinued and after the apparatus and contents thereof have returned to room temperature, the excess pressure is discharged and the autoclave is opened. The reaction product is recovered, separated from the catalyst by conventional means such as decantationl filtratlon, centrifugation, etc.
and, if so desired, subjected to fract;onal distillation whereby the vari-ous isomers may be separated, one from another, and stored. Conversely, if so desired, the reaction product comprising a mixture of isomers may ; be recovered and stored per se without separating the various isomeric fractions which are present in the product mixture.
In the event that the olefinic charge stock is in liquid form, it may be charged to the reactor which is thereafter sealed and pressured to the desired operating pressure by the introduction of an inert gas of the type hereinbefore set forth. The remainder of the operating pressure to obtain the desired oligomer product is carried out in a manner similar to that previously described.
When utilizing a continuous method of operation to obtain the desired oligomer products, a quantity of the catalyst composite is placed in an appropriate apparatus. The feedstock comprising the olefinic com-pound is continuously charged to this reactor which is maintained at theproper operating conditions of temperature and pressure. As in the case of the batch type operation, the desired operating pressure may be pro-~2~i7~

vided for by the olefinic hydrocarbon itself or by the addition of a heated ine~t gas. After passage through the reactor for a predetermined period of time, the reactor effluent is continuously discharged and the reaction product may be recovered and passed to storage or it may be passed to a distillation apparatus whereby separation of the various iso-mers and oligomers may be effected. Any unreacted olefinic hydrocarbon which is recovered from the reactor effluent may be recycled back to the reactor to form a portion of the feed charge.
Inasmuch as the catalyst composite of the present invention is in solid form, the continuous method of operation for obtaining the de-sired oligomers of the olefinic hydrocarbons may be effected in various types of operations. For example, in one type of operation, the catalyst is positioned as a fixed bed in the reaction zone and the olefinic feed-stock is charged so that it passes over the catalyst bed in either an up-ward or downward flow. Another type of continuous operation which may be employed comprises the moving bed type of operation in which the catalyst bed and the feedstock are passed through the reaction zone either concur-rently or countercurrently to each other. In addition to the fixed or moving bed type of operation, it is also contemplated that the slurry type of operation may be employed, especially when the olefinic hydrocar-bon feedstock is in liquid form. When this type of operation is employed, the catalyst is charged to the reactor as a slurry in the olefinic feed-stock.
Examples of oligomers of olefinic compounds which may be ob-tained when utilizing the catalyst composite of the present invention will include n-butene, isobutene, n-hexene, methyl pentene, dimethyl butene, _-octene, the isomeric heptenes, dimethyl hexenes, n-dodecene, the isomeric methyl undecenes, dimethyl decenes, etc. As was previously stated, the oligomer products which are obtained in the process of this invention will comprise, in the main, the dimers of the particular olefinic compound which was employed as the feedstock, thus, for example, when employing ethylene as the feed, the reaction product will comprise mostly ~4 olefins;
when employing propylene as the feedstock, the reaction product will com-~2~7Ç~

prise mostly C6 olefins; and when employing butene as the feedstock, the reaction ~roduct will comprise mostly C8 olefins. Thus, the catalyst composite of the present invention will result in products which find particular uses in the finished product.
The following examples are given for purposes of illustrating the novel catalyst composites of the present invention9 methods for pre-paring these composites and a process for utilizing these composites.
However, it is to be understood that these examples are merely illustra-tive in nature and that the present invention is not necessarily limited thereto.
EXAMPLE I
A catalyst was prepared by impregnating 250 cc of alumina spheres with an aqueous solution of 250 cc of water containing 34.6 grams of nickel nitrate hexahydrate. The impregnation was effected in a rotary evaporator in which the mixture was rolled for a period of 0.5 hours with no heat.
The evaporator was then heated with steam for a period of two hours at which time the water phase was evaporated. The catalyst base was then loaded into a tube furnace and air was passed through the catalyst bed at a rate of 600 cc per minute. Following this, the temperature of the bed was raised to 2~0C during a period of two hours and thereafter the bed was maintained at this temperature for an additional period of three hours.
At the end of this time, the bed was allowed to cool to room temperature and thereafter the bed was calcined by raising the temperature to 400C
during a two-hour period. The 400C calcination temperature was maintained for an additional period of three hours following which heating was dis-2~ continued and the impregnated base was recovered.
An activating solution was prepared by adding 3.91 grams of an-hydrous aluminum chloride to 174 cc of toluene in a 500 cc flask along with 18 grams of diethyl aluminum chloride as a S0 weight percent solution in toluene. The addition ~f the solutions was accomplished in a glove box while maintaining a nitrogen atmosphere for the addition. After thorough admixture, 67~

the solution was allowed to stand for a period of 3.5 hours with intermit-tent swirl;ing thereof.
The impregnated base was placed in a 500 cc flask along with 240 cc of toluene. The activating solution containing the aluminum chlo-~ 5 ride and diethyl aluminum chloride was slowly added during a period of 15 ; minutes to avoid overheating of the catalyst due to the exothermic nature of the reaction. After addition of the activating solution to the sup-port, the resulting solution was slightly warm with a concurrent emission of some gas bubbles. The solution was allowed to stand for a period of 18.5 hours at the end of which time thP impregnated liquors were decanted and the catalyst was washed with six portions of isopentane utilizing 100 to 115 cc per wash. The resulting catalyst compos;te was then allowed to dry in a glove box under nitrogen atmosphere until it became free-flowing.
This catalyst was designated as "A."
EXAMPLE II
A second catalyst composite was prepared in a manner similar to that set forth in Example I above. The catalyst base comprised 250 cc of alumina containing 5% by weight of nickel, said impregnated base again be-ing calcined at a temperature of 400C. The catalyst support was placed in a ~00 cc ftask along with 250 cc of toluene. A solution prepared in a manner similar to that set forth in Example I above from 18 grams of diethyl aluminum chloride as a 50 weight percent solution in toluene and 174 cc of toluene (no aluminum chloride being present) was slowly added during a period of 15 minutes to prevent overheating of the catalyst.
Again, it was noted that the solution was slightly warm following the addi-tion with the evolution of some gas bubbles. The solution was again al-lowed to stand for a period of 18.5 hours following which the impregnation liquors were decanted and the solid catalyst washed with six portions of isopentane using 115 to 120 cc per wash. This catalyst was then allowed to dry in a glove box under nitrogen until it was free-flowing in nature.
The catalyst was designated as "B."

~ Z~ t~3 EXAMPLE III
;- ~he catalysts prepared according to the methods set forth in Ex-amples I and II above were utilized in the oligomerization of butene-l.
The oligomerization was effected by placing 100 cc of l;he catalysts in a tubular reactor having an outside diameter of 0.5". A feedstock compris-ing a mixture of 60% butene-l and 40% n-butane was charged to the reac-tor at a LHSV of 1.0 hours 1 based upon the otefin. Reaction conditions which were employed for the oligomerization included a reactor inlet tem-perature of 35C and a pressure of 700 psig ~4827 kPag). The oligomerization was allowed to proceed for a period of 100 hours, samples being taken and analyzed at various points during the react;on period. The results of these analyses are set forth in Table 1 below:
Table 1 -Catalyst A Catalyst B
Unreacted Olefin %
Hours - ~8 11.5 12.5 31.5 12.0 - 32.5 100 13.0 37.5 Butene Conversion %

EXAMPLE IV
To illustrate the difference in selectivity factors which may be obtained by calcining the impregnated catalyst base at various tempera-tures, three different catalysts were prepared. The calcination of the alumina base was effected in a manner similar to that set forth in Example

3~;2676`'~

I above utilizing a nickel nitrate hydrate solution which resulted in a base containin~ 5~0 by weight of nickel. After drying the impregnated base at a tempe~ature of 250C for a period of three hours, the base was then cal-cined by raising the temperature at which each base was calcined to dif-ferent levels. After calcining the bases at the different temperatures, the bases were then treated with an activating solution of diethyl alu-minum chloride and aluminum chloride in a manner also similar in nature to that set forth in Example I above to prepare the three ~inished catalyst composites.
The three catalyst bases were calcined at temperatures of 350, lD 400, and 450C respectively, the finished catalyst composites which re-sulted from the use of these bases being labeled C, D and E respectively.
The finished catalyst composites were then utilized in an oligomerization reaction involving a feedstock comprising 60% butene-2 and 400~ n-butane, said reaction being effected at a reactant inlet temDerature of 70C, a pressure of 700 psig (4827 kPag) and an olefin LHSV of 0.6 for C and 1.0 for D
and E hrs. 1.
The weight loss which each catalyst base underwent during the calcination period as well as the selectivity to isomeric octenes at a conversion rate of 50% of the butene-2 are set forth in Table 2 below:
Table 2 2D Catalyst C D E
Calcination Temp. C 350 400 450 Wt. Loss % 2.9 1.5 0.8 C8 = Selectivity 88 76 54 It is apparent from the above Table that the temperature at which the impregnated catalyst base is calcined will have an effect upon the se-lectivity of the olefin oligomerization process, the lower calcination temperature providing the greatest percentage of selectivity.
In like manner, it is also evident from the results obtained 3~ when using two catalysts, one of which did not contain an aluminum halide as one component thereof, that a catalyst co~posite comprising a combina-tion of a catalytically effective amount of an alkyl aluminum compound and an aluminum halide on a porous support which contains a catalytically effective amount of an iron group metal hydrate will result in obtaining a greater amount of oligomer than will be obtained when ut;lizing a cata-lyst which does not contain the aforesaid aluminum halide.
EXAMPLE V
An oligomerization catalyst was prepared by impregnating 250 cc of alumina spheres with an aqueous solution of 250 cc of water containing 34.6 grams of nickel nitrate hexahydrate. The impregnation was effected 1~ in a rotary evaporator in which the mixture was rolled for a period of 0.5 hours without heating, followed by heating with steam for a period of two hours at which time the water was evaporated. The catalyst base was then calcined in a manner set forth in the above example by loading into a tube furnace, heating to 250C for a period of two hours, cooling to room tem-perature followed by raising the temperature to 400DC and maintaining the temperature for a period of three hours.
An activating solution was prepared by adding 1.5 grams of an-hydrous aluminum chloride to 62 grams of toluene in a S00 cc flask along with 5.45 grams of diethyl aluminum chloride in 33 cc of hexane. The addi-tion of the solutions was effected in a glove box wh;le maintaining a nitrogen atmosphere and after thorough admixture, the solution was allowed to stand for a period of 3.5 hours.
To prepare the desired catalyst, 125 cc of the catalyst base was placed in a 500 cc flask along with 125 cc of toluene. The act;vator solution was then slowly added to the catalyst base over a period of 30 minutes in order to avoid overheating. The solution was warm and in addi-tion, gas bubbles were formed after the addition. After allowing the sol-ution to stand for a period of 18 hours, the solvents were decanted and the catalyst was washed with six 80 cc portions o~ isopentane. The cata-lyst composite was allowed to dry in a glo~e box under a nitrogen atmo-~z~

sphere and designated as "F."
EXAMPLE VI
In this example, 250 cc of alumina spheres were impregnated with an aqueous solution of 250 cc of water containing 34.6 grams of nickel ni-trate hexahydrate in a manner similar to that set forth in Example V above.
The catalyst base was then divided into six separate portions, loaded into a tube furnace, and treated in a manner similar to that set forth in the above example by calcining at a temperature of 400C for a period of three hours.
Six batches of activating solution were prepared by adding 3.9 grams of anhydrous aluminum chloride and 16.9 grams of diethyl aluminum chloride as a 50 wt. % solution and 39 cc of toluene to 174 cc of toluene.
The mixing was effected in a glove box under a nitrogen atmosphere and after 3.5 hours all of the solid had dissolved. Each batch of the solu-tion was used to activate the six 250 cc catalyst bases prepared accord-ing to the above paragraph. Each portion of the catalyst base was placed in a 500 cc flask along with 250 cc of toluene, the addition of the acti-~ator solution being accomplished over a 15 minute period. After allo~-ing the solution to stand for a period of 18.5 hours, the solvent was decanted and each catalyst was washed with six 100-115 cc portions of iso-pentane. Thereafter, the catalyst portions were allowed to dry in a glove box under nitrogen and combined, this catalyst being designated "G."
EXAMPLE VII
To vary the ratio of nickel to aluminum halide, a catalyst was prepared by impregnating 250 cc of alumina spheres with an aqueous solu-tion comprising 250 cc of water containing 71.3 grams o~ nickel nitrate hexahydrate. After impregnation, the catalyst base was treated in a man-ner similar to that hereinbefore set ~orth and loaded into a tube furnace during which air was passed through the catalyst bed at a rate of 600 cc per minute. Following this, the temperature of the bed was raised to ~2676~5 250~C du~ing a period of two hours and maintained thereat for an addi-tional period of three hours. At the end of this time, the bed was al-lowed to cool to room temperature and thereafter, the catalyst was cal-cined by raising the temperature of the furnace to 350~C during a two-hour period. The 350C calcination temperature was maintained for an addi-tional period of two hours following which heating was discontinued and the impregnated base was recovered.
An activating solution was prepared by adding 5.87 grams of an-hydrous aluminum chloride to 80 cc of toluene in a 500 cc flask along with 58.1 cc of a 50 wt. % diethyl aluminum chloride in a toluene solution ~27.0 grams of diethyl aluminum chloride). A portion (125 cc) of the im-pregnated catalyst base was then placed in a 500 cc flask along with 120 cc of toluene. The activating solution was slowly added during a period of 15 minutes and allowed to stand for 18.5 hours. At the end of th;s time, the impregnating liquors were decanted and the catalyst was washed with six portions of isopentane utilizing 100 to 115 cc per wash. The catalyst com-posite was allowed to dry in a glove box under a nitrogen atmosphere until it became free-flowing, this catalyst being designated ~F.
EXAMPLE VIII
Catalysts F, G and H which were prepared according to the above examples were used in a propylene oligomerizatiDn test. Each catalyst in an amount of 50 cc was placed in a tube reactor and a charge comprising 90% by weight of propylene and 10% by weight of propane was charged to each reactor at olefin Liquid Hourly Space Velocities ranging from 2.0 to 3.0 hours 1. The reactors were maintained at a pressure of 700 psig (4827 kPag) while the bath temperatures were maintained at from 35D to 50~C. A fract;onation column was used to separate unreacted C3's from the oligomers and a portion of the unreacted C3's (both propylene and propane) was recycled to the reactor inlet. The results of the runs are set forth in Table 3 below:

~2~i7~

Table 3 ;
Catalyst "F''Catalyst "G" Catal~st l'H"
Run Length (hrs.) 1385 1042 36 Overall Propylene 88.7 - 99.8 92.6 - 99.9 61.3 - 91.7 Conversion (wt.%) 5 C - selectivity 70.7 - 81.5 77.4 - 92.6 6 (wt. %) Research Octane No. 95 - 96 95 - 96 Motor Octane No. 80 - 81 80 - 81

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A catalytic composite comprising d combination of a cata-lytically effective amount of an alkyl aluminum compound on a porous sup-port containing a catalytically effective amount of an iron group metal hydrate in which the mole ratio of water of hydration to iron group metal is greater than 0.5:1.

2. The catalytic composite as set forth in Claim 1 further characterized in that said composite contains in combination therewith a catalytically effective amount of an aluminum halide.

3. The catalytic composite as set forth in Claim 1 in which said iron group metal is present in said composite, on an elemental basis, in an amount in the range of from about 1% to about 20% by weight of said composite.

4. The catalytic composite as set forth in Claim 1 in which said alkyl aluminum compound is present in said composite in a mole ratio in the range of from about 0.05:1 to about 6:1 moles of alkyl aluminum compound per mole of iron group metal.

5. The catalytic composite as set forth in Claim 1 in which the mole ratio of water of hydration to iron group metal in said iron group metal hydrate is in a range of from about 0.5:1 to about 6:1 prior to reaction with said alkyl aluminum compound.

6. The catalytic composite as set forth in Claim 3 in which said iron group metal is nickel or cobalt.

7. The catalytic composite as set forth in Claim 1 in which said alkyl aluminum compound comprises an alkyl aluminum halide.

8. A process for the oligomerization of an olefinic hydrocar-bon which comprises treating said hydrocarbon in the presence of the cata-lyst of Claim 1 at oligomerization conditions and recovering the resultant oligomer.

9. The process as set forth in Claim 8 in which said oligo-merization conditions include a temperature in the range of from about -20° to about 120°C and a pressure in the range of from about 350 to about 1000 psig (2410 to 6895 kPag).

10. The process as set forth in Claim 8 in which said ole-finic hydrocarbon contains from 2 to about 6 carbon atoms.

11. The process as set forth in Claim 8 in which said ole-finic hydrocarbon is propylene and said oligomer is a mixture of hexene, methyl hentene and dimethyl butene.

12. The process as set forth in Claim 8 in which said ole-finic hydrocarbon is butylene and said oligomer is a mixture of octene, methyl heptene and dimethyl hexene.

13. A process for the oligomerization of an olefinic hydrocarbon which comprises treating said hydrocarbon in the presence of the catalyst of Claim 2, 3 or 4 at oligomerization conditions and recovering the resultant oligomer.

14. A process for the oligomerization of an olefinic hydrocarbon which comprises treating said hydrocarbon in the presence of the catalyst of Claim 5, 6 or 7 at oligomerization conditions and recovering the resultant oligomer.