CA1258449A - Catalysts having alkoxide-modified supports - Google Patents

Abstract

ABSTRACT
A catalyst composition comprising a catalytic metal and a support, the support being prepared by depositing a metal alkoxide salt on a core support, then calcining the support.

Description

CATALYSTS H~VING ALKQXIDE-MODIFIED SUPPORTS

The present invention concerns supported metal catalyst compositions.

It is known to employ metal alkoxides in the preparation of solid catalysts. The reasons for employ-ing the metal alkoxides vary considera~ly, as can beseen from the use of alkoxides in the preparation of solid heterogeneous catalysts in the literature. For example, U.S. Patent 3,873,489 discloses the prepara-tion of metal catalysts for the purification of auto-mobile exhaust gases. The cakalysts are prepared byimpregnating a precious metal such as platinum, pal-ladium, rhodium, iridium, ruthenium or mixtures thereof onto a monolithic honeycomb structure. The honeycomb structure is composed of refractory compounds of low surface area. The shemically inert and refractory nature of this honeycomb is extremely important, as it should not undergo any drastic transformations during the extreme conditions encountered in typical auto-mobile exhaust systems. However, impregnation of precious metals onto such a support surface to obtain a 31,912D-F -1-~

1;25~

thermally stable catalyst having reasonably high metal dispersion is practically impossible. This difficulty is overcome in the teaching of the patent by employing a metal alkoxide to "wash coat" the low surface area honeycomb to obtain a honeycomb having higher surface area. The higher surface area support is suitable for catalyst preparation.

Similiarly, U.S. Patent 4,076,792 discloses the use of metal alkoxides to prepare layered support coatings on monolithic honeycombs to make catalysts having both platinum and rhodium deposited on a wash coated honeycomb. The wash coating method comprisès the impregnation of the selected support structure with the lower alkoxides of metals followed by the 1n situ hydrolysis of the metal alkoxides to form an adherent coating of hydrous metal oxides. The coated support structure may then be fired to convert the hydrous metal oxides to an oxide support coating of very high - surface area and good porosity.

The use of metal alkoxides to supply alkali metal ions in a nonaqueous form is described by R. Hombek, J. Kijenski, and S. Malinowski (Warsaw, Poland) in a paper presented at the Second International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts, held at Louvain-la-Neu~e, Belgium, on Septem-ber 4-7, 1978 (Proceedings published as Studies in Surace Science and Catalysis, Vol. 3, by Elsevier Scientific Publishing Company, Amsterdam/Oxford/New York, 1979; see pages 595-603). Many industrial cata-lysts, especially for dehydrogenation, and crackingprocesses, are modified by the controlled dosing of 31,912D-F -2-125~

alkali metal ions to suppress the unwanted strong aci-dity of the catalyst carrier or support. The new alkali impregnation procedure, using alkali metal alkoxides in alcoholic solutions, avoids the reaction of water with dehydrated alumina support surfaces; this is particularly important because the water causes considerable changes in the properties of catalysts prepared by the aqueous alkali-hydroxide addition method.

Still another development r~ported by M.
Glinski and J. Kijenski (same Polish group as above) is the method of impregnation with vanadyl tri-isobutoxide to prepare vanadium-alumina and vanadium-silica catalyst systems. This is described by the Polish au~hors in their paper presented at the Third International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysis, Vol. 16, 1983; see page 553-561). As in the case of impregnation with alkali-metal alkoxides, the application of vanadyl alkoxide in a non-aqueous medium avoids the secondary effects caused by the interaction of water with th~e dehydrated alumina or silica surface. Following the alkoxide impregnation, the resultant product was cal-cined in a stream of dry air at 573 K for 3 hours to obtain the respective vanadium-alumina or vanadium--silica catalysts, which can further be reduced if necessary.

- The principle of bringing the catalytically active material or materials in the form of an alkoxide precursor, followed by hydrolysis or thermal decom-position to obtain the final supported metal oxide or metal catalyst, is also the basis of the invention of 31,912D-F -3--4~ ~5~

U.S. Patent 4,400,306. This method of catalyst pre-paration comprises: impregnating a pre-formed catalyst support with a solution of an alkoxide of at least one metal selected from V, Mo, Sb, Nb, Ta, Zr, B and mix-tures thereof; contacting the impregnated supportwith a solution of at least one additional catalyst component to form the catalyst in situ; and drying or calcining the thus formed catalyst. The preformed catalyst support in such cases can be of different types and shapes, e.g. non-porous or microporous fluidizable powders, pellets or tablets, extrudates, monoliths and similar forms. U.S. Patent 4,400,306 (at column 3, lines 22-31) reads "the use of metal alkoxides in the impregnation step is advantageous because the alkoxide reagent represents an extremely pure source of the metal and metal oxide reagents, unlike water-soluble salts such as the alkali metal or sulfur-containing salts which carry possibly unwanted counter-ions into the support material for incorpor-ation into the catalyst. Upon heating or calcining,the alcohol adduct of the alkoxide is driven off or oxidized to form a metal oxide species." This use of the metal alkoxide as an extremely pure source of the metal is also one of the motives for using it for bringing a washcoat on monolith honeycombs, as des-cribed in U.S. Patent 3,873,469. Still another embodi-ment of the invention described in U.S. Patent 4,400,306 consists in `'choosing particular alkoxy derivatives of reducible metal ions", so that an ln situ reduction of the metal can be effected (column 3, lines 57-59).

The metal alkoxide impregantion step can also be repeated to increase the amount of metal (or metal oxide) deposited within the support. After the impreg-31,912D-F -4-~258~

nation of one metal alkoxide catalyst component, addi-tional catalyst components can be added in the form of metal alkoxide solutions or solutions of other catalyst component compounds. Catalysts prepared in this way are suitable for fixed-bed or fluid-bed catalytic processes, particularly for oxidation processes like the conversion of C4 hydrocarbons to maleic anhydride (see U.S. Patent 4,455,434).

` To summarize, metal alkoxides have been used in the prior art for the manufacture of solid catalysts for the following distinct purposes and with the follow-ing specific characteristics:

1. To wash-coat a monolithic honeycomb, to give the inert refractory substrate higher surface area and porosity for subsequent metal impre-gnation (U.S. Patent 3,873,469; U.S. Patent 4,076,792).

2. To bring alkali metal ions in a water-free system to catalysts to neutralize the unwanted strong acidity of the catalysts. (Paper of Hombek et al., 1978, supra. ).

3. To impregnate vanadium alkoxides on silica or alumina to prepare supported vanadium cata-lysts. The alkoxide is used as a water-free medium to prevent side effects to the cata-lyst support which would otherwise result from using an a~ueous solution of a vanadium salt. (Glinski and Kijenski, 1982, supra. ).

4. Use of the specific alkoxide of the cata-lytically active metal.

31,912D-F -5-125~

Motive: alkoxides are generally purer than the corresponding metal salts, hence trace impurities can be avoided if metal alkoxides are used instead of metal salt solutions (U.S. 4,400,306 and U.S. 4,4~5,~34).

Catalytic metals play an important role in heterogeneous catalysis. The catalytic metals typi-cally are employed on various support materials, as only the surface of a metal particle can participate in a catalytic process. Many people have proposed various solutions to the long-standing problem of how to dis-perse catalytic metals more efficiently on the surface of a support material. An improved solution to this problem is provided by the present invention.

In one aspect, the present invention concerns an improved catalyst composition which comprises a catalytic metal on an alkoxide-modified supportj which support has a core support material having a surface area of at least about 5 m2/g.

In another aspect, the invention is a process for increasing the catalytic activity of a catalytic metal ! which comprises supporting the catalytic metal on a support prepare~ by contacting a metal alkoxide with a core support material, then calcining the mix-ture of the metal alkoxide and the core support mater-` ial, thereby leaving a coating on the core support, the coating havin~ the metal oxide derived from the cal-cination of the metal alkoxide.

31,912D-F -6--7- ~25~9 Surprisingly, the supported catalyst com-position of the present invention exhibits increased catalytic activity compared to supports not treated by the process of this invention. Thus, the catalyst com-position of the present invention is useful in many catalytic processes in which enhanced activity of a supported metal catalyst is desirable. The catalyst composition of the present invention is suitable for use in:
(a) the disproportion of alkenes;
(b) a vapor phase process for the prepara-tion of -(1) ~-substituted acrylate esters; or - (2) methylmethacrylate;
(c) a process for selectivel~ hydrogenating a hydrocarbon feed composition having at least one alkene and at least one alkyne wherein the alkyne is hydrogenated without substantially hydrogenating the alkene; or (d) a process for preparing increased yields of methane by reacting carbon monoxide and hydrogen.

The catalyst composition of the present invention has two re~uired components: a catalytic m~tal; and-an alkoxide-modified support. For the pur-poses of the present invention, the term "alkoxide-modified support" means a material prepared by deposit-ing a thin layer of a metal alkoxide on a core support material and then converting the metal alkoxide to the oxide of said metal. Additonally, the term "catalytic metal" refers to any metal-containing compound, complex or other èntity which acts as a catalyst.

31,912D-F -7--8- ~25~

The alkoxide-modified support comprises a core support material having on its outer surface a thin layer of a metal oxide produced from a precursor metal alkoxide. The core support material can be any material, such as a refractory oxide, which will not decompose or melt when subjected to calcination.
Examples of typical core support materials include alumina, zirconia, boria, thoria, magnesia, titania, tantala, chromia, silica, kieselguhr and mixtures of these materials. The aluminas and silicas are pre-ferred in view of their low cost. The core support material typically has a surface area which is greater than about 5 m2/g, preferably about 10 to S00 m2/g, more preferably 20 to 200 m2/g, and most preferably over 100 m2/g prior to the deposition of the metal alkoxide salt precursor. These surface areas are as measured by the Brunauer-Emmett-Teller (BET) method.
The BET method is described by R. B. Anderson, Experi-mental Methods in Catalytic Research, pp. 48-66, Academic Press, 1968.

The precursor metal alkoxide salt can be the alkoxide of almost any metal so long as said metal alkoxide will thermally decompose to form a metal oxide. For example, the metal of the metal alkoxide can be a metal of Group IIA. Examples of preferred metals for use in the precursor metal alkoxide include the metals of Groups IIIA, IVA, IVB and VB of the Perodic Table of the elements. Examples of typical precursor metal alkoxides include Al[OCH~CH2CH3][CH3~]3, Ti[OCH(CH3~2]4, Ta[OCH(CH3)2~s, Si(OC2H5~4, Nb2(C2~I5~10' Ta (OC H5~10' Si(C4Hg~4, Al(oc5Hll~3l Typically, the alkoxide moiety has from 1 to about 10 carbon atoms, preferably from about 2 to about 4 carbon atoms. Mixtures of metal alkoxidrs can be 31,912D-F -8-9 125~

employed. Typi cally, the metal of the metal alkoxide is not a catalyst for the reaction in which the cata-lyst composition will be employed.

The alkoxide-modified support is prepared by technigues known in the art, e.g., incipient wetness impregnation techni~ues. Metal oxide precursors are deposited on the selected core support material fol-lowed by conversion into the oxide form b~ calcination.
The alkoxide-modified support is prepared by impregna-ting the desired core support material with a solutionof an alkoxide precursor of the desired metal oxide.
The solution used in impregnating the core support material preferably is organic , the only requirement being that an adequate amount of precursor compound for the selected metal oxide is soluble in the solvent used in p~eparing the impregnating solution. Hydrocarbon or alcohol solutions, preferably hexane solutions, are normally used for convenience. When using the impre-gnation technique the metal alkoxide impregnating solution is contacted with the core support material for a time sufficient to deposit the metal alkoxide precursor material onto the carrier either by selective adsorption or, alternatively, the excess solvent may be evaporated during drying leaving behind the preGursor metal alkoxide. Advantageously, the incipient wetness technique may be used whereby just enough of a precur-sor metal àlkoxide solution is added to dampen and fill the pores of the powder of the above-recited core support material.

The composite thus prepared by any of the above-recited techniques, or by any other technique 31,912D-F -9--10- ~25~ 9 known in the art, is dried, typically at a temperature of from 50 to 300~C, to remove the excess solvent.
The solvent can be removed ln vacuo. The dried metal alkoxide can then be converted into the oxide form by exposure at temperatures typically of from 150 to 800C, preferably 300 to 700C in an atmosphere such as 2' air, He, Ar or combinations thereof. This exposure is for a time sufficient to convert essentially all of the metal alkoxide precursor into metal oxide. The calcination is useful to decompose the metal precursor to the oxide form.

The catalytic metal can be any metal or metal compound having catalytic activity. Typical catalytic 'metals include the transition metals. Examples of pre-ferred catalytic metals include the metals of Group VIIIof the Periodic Table of the elements, i.e~, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum, and the metals of Group VIIB, e.g. rhenium. The catalytic metal is deposited on the alkoxide-modified support via methods known in the art such~as, for example, impregnation of the alkoxide-modified support with a salt of the catalytic metal.
The salt of the catalytic metal is converted to the metal by exposing the salt to a reducing atmosphere via methods known in the art. It is preferred to reduce the salt of the catalytic metal in situ, i.e., while the salt is in the reaction vessel.

The precursor metal alkoxide is employed in an amount sufficient to result in a finished alkoxide-modified support which, after calcination, can beemployed with a catalytic metal to form a composite catalyst composition having improved activity, which 31,912D-F -10-125~

may be evidenced, e.g., by increased conversion or lifetime. Typically, the support has up to about a molecular monolayer of the metal oxide, formed from the metal alkoxide, covering the entire outer surface of the core support material. If desired, more than a molecular monolayer of the metal oxide from the metal alkoxide can be employed. Typically, the catalytic metal is employed in a catalytic amount. Pre~erably, the finished catalyst of the present invention will have a composition as follows: from about 0.01 to a~out 20 weight percent catalytic metal; from about 0.1 to about 50 weight percent of metal oxide from alkoxide precursor; and the remainder being core support material-.
More preferably, the finished catalyst of the present invention will have a composition as follows: from about 0.02 to about 10 weight percent catalytic metal;
from about 1 to about 5 weight percent metal oxide from alkoxide precursor; and the remainder being core support material.

A. Methanation The catalyst composition of the present invention is useful in many applications in which enhanced activity of a supported catalytic metal is desirable. The production of methane from C0 and H2 is an example of a preferred use of the catalyst composi-tion of the present invention. The art contains many examples of metals known to be useful in reac-ting carbon monoxide with hydrogen to produce a variety of compounds, including hydrocarbons and oxygenated com-pounds. These metals include, among others, Mo, W, Rh,Ru, Re, Pd, Ni, Co, and Fe. In what has come to be called the Fischer-Tropsch ~ynthesis, carbon monoxide and hydrogen are reacted over a me-tal catalyst to produce saturated an~ unsaturated hydrocarbons and oxygenated compounds containing from 1 to as many as 31,91~D-F -11-~25~

1000 carbon atoms. The hydrocarbons can be aliphatic, alicyclic, or aromatic. Commercial utilization of this synthes-s prior to 1950 was accomplished largely in Germany and is summarized in Storch, Columbic, and Anderson: The Fischer-Tropsch and Related Synthesis, John Wiley and Sons, New York, 1951.

The major disadvantage in the prior art pro-cesses and catalysts is that most of th~m are not capable of selectively producing methane. Surpris-ingly, at least one catalyst of the present inventionmay be used to produce methane ~electively by con-tacting carbon monoxide and hydrogen in the presence of said catalyst under reaction conditions.

The carbon monoxide required for the process can be obtained from any carbon source, such as from the degradation of coal. The molar ratio of hydrogen to carbon monoxide ranges generally from at least about 0.1 to about 10, and preferably is from about 1 to about 3.

Process reaction conditions can vary over a rather wide range. The pressure can vary from at least about 1 psig up to about 1500 psig (108 to 10,436 kPa).
Atmospheric pressure is preferred for convenience.
The reaction temperature typically ranges from at least about 200C to about 600C and preferably is from about 200C to about 300C. Ruthenium is the preferred catalytic metal for use in the production of methane via the process of the present invention.

31,912D-F -12--13- l~S~

B. Olefin Metathesis The disproportionation, or metathesis, of olefins is another example of an advantageous use of the supported catalyst composition of the present invention. In a typical olefin metathesis process an olefin of at least 3 carbon atoms is converted into a mixture of new products comprising olefins of both higher and lower molecular weight compared to the olefin fed. Olefin metathesis was discovered in the early 1960s. The metathesis xeaction is well known, as is evidenced by the numerous publications which are reviewed in Catalysis, Yol. 4, pp. 101-130, 1980. A
review of the prior art indicates that it would be desirable to have a catalyst having a longer lifetime or which would require fewer regenerations per unit time. Surprisingly, at least one catalyst of the - present invention may be employed in the metathesis of olefins for increased lengths of time while maintaining an acceptable rate of olefin conversion.

The olefin metathesis process of the present invention involves contacting at least one alkene with a catalyst o~ the present invention under reaction con-ditions such that there is formed at least one product of olefin metathesis, i.e., at least one alkene having a molecular weight which is different than the molecular weight of the alkene fed to the reactor.

Alkenes which are subject to disproportion-ation according to the process of the present invention - include acyclic alkenes having at least 3 carbon atoms, and their aryl derivatives and mixtures thereQf.
Preferred are alkenes having from 3 to about 30 carbon atoms and mixtures thereof. More preferred are mono-l-31,912D-F -13-125~

and 2-alkenes, such as, for example, propene, butene-l, and mixtures of these alkenes, such as, for example, a mixture of butene-l and butene-2. Most preferably, the process of the present invention is applied to butene-1 or a mixture of butene-l and butene-2. Optionally, an inert material may be included in the alkene fed to the reactor. Examples of inert materials include inert gases, such as helium, and saturated hydrocarbons, such as hexane, cyclohexane, and the like.

Catalysts suitable or use in the olefin meta-thesis process of the present invention are those materials which catalyze the olefin metathesis reaction;
typically, the catalyst is a conventional catalytic material on an alkoxide-modified support. Examples of said conventional catalysts include materials which contain catalytic metals such as rhenium, molybdenum or tungsten, and which optionally include a promoter, such as tetramethyltin or tetrabutyltin. Preferred catalysts comprise rhenium or a rhenium compound or complex.
Rhenium oxides are preferred for use in the catalysts of the process of the present invention. It is especially preferred to employ from about 1 to about 8 w~ight percent catalytic metal in the composite catalyst for olefin metathesis.

The com~osite olefin metathesis catalyst is prepared by suitable known methods of applying a catalytic material to a support, such as impregnation or coprecipitation, with impregnation being preferred.
Catalytic metal oxides or compounds convertible to catalytic metal oxides by calcination preferably are employed in the catalyst preparation.

31,912D-F -14-.

-15- ~25~

After the catalytic metal oxide, or compound which may be converted to a catalytic metal oxide by calcination, is associated with the alkoxide-modified support, the composite is subjected to a calcination or activation step before being utilized in the 012fin conversion process. The activation technique comprises heating at elevated temperatures in the presence of a suitable flowing gas. Air is a preferred activation gas, although other gases, for example, inert gases such as nitrogPn or the noble gases, may be used, provided that at least part of the catalytic metal present in the catalyst composition is in the oxide form at the com-pletion of the activation. The catalysts are subjected to a temperature which is generally in the range of 300C
15 to 700C for about 0.5 to 20 hours or longer. Generally, longer activation periods are used with lower temper-- atures, and shorter activation periods are used with higher temperatures. In some instances, the catalyst may be heated serially in more than one gas.

The activated catalyst may be used, without regeneration, for runs of up to several days or more, and may be regenerated. The regeneration is accomplished by suitable methods for regenerating oxide catalysts and may comprise the same steps used in the activation procedure.

The reactor employed in the olefin metathesis process o~ the present invention can be of any known design. The reactor is operated so as to dispro-portionate the alkenes in the feed stream. Accordingly, the reactor may be operated under any conditions, at which disproportionation is achieved. Typically, the operating temperature in the reactor ranges from about -50C to about 300C, and preferably will be from about 31,912D-F -15--16- ~2s~

0C to about 150C. The pressure in the reactor typically will be from about zero to about 1000 psig (100 to 7000 kPa) and preferably will be from about 50 to about 3Q0 psig (400 to 2200 kPa). Higher or lower temperatures and pressures may be employed; however, beyond the lower end of the range the reaction will proceed slowly, if at all, and beyond the higher end of the range, undesirable side reactions and coke forma-tion may occur. Additionally, it will probably be more expensive to operate outside the ranges given.

For the purposes of the metathesis process of the present invention, the term conversion refers to the elimination of the alkenes in the feed stream from -the reaction mixture. For example, in the practice of this invention, butene-l may be converted to ethylene and hexene-3 under the proper conditions. For the purposes of the present in~ention, the term selectivity refers to the percentage of the converted feed which goes to the desired major products.

The concept of simultaneous high selectivity and high conversion may be expressed conveniently in terms of yield. For the purposes of the present inven-tion, the term "yield" refers to the numerical product of conversion and selectivity. For example, a process according to the present invention operating at a conversion of 0.75 and a selectivity of 0.90 would have a yield of 0.675, which is the numerical product of 0.75 and 0.90.

C. Carbonylation ~0 The carbonylation of haloalkenes is a further example of an advantageous use of the supported catalyst 31,912D-F -16-125~

composition of the present invention. The carbonyla-tion reaction of the present invention is a process for the preparation of ~-substituted acrylate esters~which involves contacting a haloalkene with carbon monoxide and an alcohol or an ether in the presence of a catalyst of the present invention under reaction conditions such that an ~-substituted acrylate ester is prepared.

The preparation of acrylate esters by con-tacting haloalkenes, carbon monoxide, and an alcohol or ester in the presence of a heterogeneous catalyst is generally known. For example, see U.S. Patent 4,480,121 for a description of reactants and reaction conditions employed in the preparation of acrylate esters.

The haloalkenes useful in this invention include any halogenated olefinic compound wherein the halogen is substituted on an olefinic carbon atom, wherein such carbon atom is further substituted with a Cl 10 alkyl, C3 10 cycloalkyl~ C6_l0 aryl~ C7_10 alkaryl~
C7 10 aralkyl, cyano, or trihalomethyl group. The haloalkene preferably is vaporizable under the reaction conditions. Olefinic carbon atoms means herein a carbon a-tom which is doubly bonded to another carbon atom. Haloalkenes useful in this i~vention include those which correspond to the formula (Rl)2-c=c-R2 31,912D-F -17--13- 125~3~r~

wherein ~ 7-10 aryl, Cl_10 alkyl~ C3 10 cyclo-alkyl, C7_10 alkaryl, C7_10 aralkyl, substituted Cl 10 alkyl, substituted C6 10 aryl, substituted C3 10 cycloalkyl, substituted C7 10 alkaryl or sub-stituted C7 10 aralkyl, wherein the substituent is a nitro, cyano, carbonyloxyhydrocarbyl, formyl, amino, hydroxyl, amido or halo group;
C1_l0 alkyl, C3_10 cycloalkyl, C6 10 aryl, C7 10 alkaryl, C7_10 aralkyl, cyano or tri-halomethyl; and X is halogen.

Examples of preferred haloalkenes useful in this invention include 2-chloropropene, 2-bromopropene, 2-chlorobutene, 2-bromobutene, 2-chloropentene, 3-chlo-ropentene, 2-bromopentene, 3-bromopentene, 2-chlorohex-ene, 3-chlorohexene, 2-bromohexene, 3-bromohexene, and the like. More preferred haloalkenes include 2-chloro-propene~ 2-chlorobutene, 2-chloropentene, and 2-chloro-hexene. A most preferred haloalkene is 2-chloropropene.
.
Alcohols useful in this invention include those which are vaporizable under reaction conditions and which will react under the reaction conditions to esterify the carbonylated haloalkene so as to prepare an ~-substituted acrylate ester. Preferred alcohols include those which correspond to the formula, R30H, wherein R3 is C1 10 alkyl, C3 lO cYClalkYl' C6-10 aryl, C7_10 Y
C7 10 aralkyl. Examples of alcohols useful in ~his invention include methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopro-panol, cyclobutanol, cyclopentanol, cyclohexanol, cyclo-heptanol, cyclooctanol, phenol, be~zyl alcohol, and the 31,91~D-F -18-~ Z5~r6~9 like. Preferred alcohols are methanol, ethanol, propanol, butanol, and pentanol. Methanol is the most preferred alcohol.

Ethers useful in this invention include those which are va~orizable under reaction conditions and which will react under the reaction conditions to esterify the carbonylated haloalkene so as to prepare an ~-substitute~d acrylate ester. Among classes o ethers useful in this invention are the dihydrocarbyl ethers and cyclic ethers.
Preferred dihydrocarbyl ethers include those which correspond to the formula R3-o-R3 wherein R3 is as defined hereinbefore. Examples of dihydrocarbyl ethers useful in this in~ention are dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diphenyl ether, dibenzyl ether and the like. Preferred ethers are dimethyl ether, diethyl ether and dipropyl ether; with dimethyl ether being most preferred.
Unsymmetrical dihydrocarbyl ethers such as methyl ethy~
ether, can be used in this invention although the symmetrical ethers are preferred. Preferable cyclic ethers useful in this process include those which correspond to the formula or 0 ~ 0 ~ ~ R4 J

wherein R4 is a hydrocarbylene radical. The dihydrocar-byl ethers are preferred over the cyclic e~hers. Cyclic ethers useful in this invention include dioxane, tetra-hydrofuran and the like.

31,912D-F -19--20- ~zS~r~

The product o~ the carbonylation process of -the present invention is an acrylate ester. Preferred ~-sub-stituted acrylate esters include those which correspond to the formula (Rl)2-C=C-CoR3 ~2 or (Rl )2-C=C-CoR4-H

wherein R1, R2, R3 and R4 are as hereinbefore defined.

Examples of acrylate esters prepared by this process include methyl methacrylate, methyl 2-methyl-2--butenoate, methyl 2-methyl-2-pentenoate, ethyl methacry-late, ethyl 2-methyl-2-butenoate, ethyl 2 methyl-2-pente-noate, propyl methacrylate, propyl 2-methyl-2-butenoate, propyl 2-methyl-2-pentenoate, butyl methacrylate, butyl 2-methyl-2-butenoate, butyl 2-methyl-2-butenoate, pentyl methacrylate, pentyl 2-methyl-2-butenoate, and pentyl 2-methyl-2-pentenoate. Preferred acrylate esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and pentyl meth-acrylate, more preferred acrylate esters include methyl methacrylate, ethyl methacrylate, and propyl meth-acrylate, with methyl methacrylate bein~ most preferred.

31,912D-F -20--21~ 4~

A co-product of this invention is a hydrocarbyl halide. This halide is the reaction product of an alcohol or an ether and the halogen abstracted from the haloalkene during the carbonylation and esterification process of this invention. The excess alcohol or ether functions as the halogen acceptor for this reaction thereby reducing the concentration of hydrogen halide in the reactor and preventing corrosion. Furthermore, the preparation of an alkyl halide allows the recovery of the halogen in a valuable form. Hydrocarbyl halides prepared in this invention include those which correspond to the formula, R3-X or R4H-X, wherein R3 and R4 are as hereinbefore defined.

Tertiary amines may be used as hydrogen halide acceptors. When tertiary amines are used as acid acceptors, by-products of the process are the quaternary ammonium halides. The use of excess alcohols or ethers to serve as the halogen acceptor is preferred over the use of the tertiary amines in this invention.

Examples of haloalkanes prepared by this pro-cess include chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chloroocatne, chlorononane, chlorodecane, chlorocyclopro-pane, chlorocyclobutane, chloxocyclopentane, chlorocyclo-hexane, chlorobenzene, chloromethylbenzene, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, bromocyclopropane, bromocyclobutane, bromo-cyclopentane, bromocyclohexane, bromobenzene, and bromo-methylbenzene. Examples o~ more pre~erred haloalkanesinclude chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, 31,912D-F -21-~5~..49 chlorooctane, chlorononane, chlorodecane, chlorocyclopro-pane, chlorocyclobutane, chlorocyclopentane, chlorocyclo-hexane, chlorobenzene, and chloromethylbenzene. Even more preferred haloalkanes include chloromethane, chloro-ethane, chloropropane, chlorobutane and chloropentane,with chloromethane being most preferred.

In the process of this invention, the halo-alkene starting material is carbonylated by the insertion of carbon monoxide onto an olefinic carbon atom, and the carbon atom on the carbon monoxide moiety inserted is transesterified with the alcohol or ether. This process can be best illustrated by the following e~uations, X R2 o ..
(Rl)2-C-C-R2 + C0 + 2R30H , (R1~2_C=C - CoR3 + R3-X + ~2 and X R2 o (Rl)2-C=C-R2 + C0 + R30R3 ~ (Rl)2-C=C - CoR3 + R3-X
. .
wherein Rl, R2, R3, and X are as hereinbefore defined.

In the hereinbefore defined formulas, Rl is preferably hydrogen or Cl 10 alkyl. Rl is more prefer-ably hydrogen or Cl 5 alkyl and most preferably hydrogen.
R is preferably Cl 10 alkyl. R2 is more preferably C1 5 alkyl and most pre~erably methyl. R3 is preferably Cl 10 alkyl, R3 is more preferably Cl 5 alkyl and most pre-- ferably methyl. R4 is preferably C2 10 alkylene and more preferably C2 5 alkylene. X is preferably chlorine or bromine and most preferably chlorine.

- 31,912D-F -22-~L25~ 9 For the purposes of the present invention, the term "hydrocarbyl" means an organic radical containing carbon and hydrogen atoms. The term hydrocarbyl includes the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cyclo-aliphatic aralkyl and alkaryl. Aliphatic refers herein to straight- and branched-, and saturated and unsaturated, hydrocarbon chains, that is, alkyl, alkenyl or alkynyl. Cycloaliphatic refexs herein to saturated and unsaturated cyclic hydrocarbons, that is, cyclo-alkenyl and cycloalkyl. The term aryl refers herein to biaryl, biphenylyl, phenyl, naphthyl, phenanthranyl, anthranyl and two aryl groups bridged by an alkylene group. Alkaryl refers herein to an alkyl-, alkenyl- or alkynyl-substituted aryl substituent wherein aryl is as defined hereinbefore. Aralkyl means herein an alkyl, alkenyl or alkynyl group substituted with an aryl group, wherein aryl is as defined hereinbefore. Cl 20 alkyl includes straight- and branched-chain methyl, ethyl, propyl, buty~, pentyl, hexyl, heptyl, octyl, nonyl, decyl, und~cyl, dodecyl, tridecyl, tetradecyl, pent-adecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups. Cl 5 alkyl includes methyl, ethyl, propyl, butyl and pentyl.

Cycloalkyl refers to alkyl groups containing one, two, three or more cyclic rings. Cycloalkenyl refers to mono-, di- and polycyclic groups containing one or more double bonds. Cycloalkenyl also refers to cyclo-alkenyl groups wherein two or more double bonds are present.

_ The catalytic metals useful in the carbonyl-ation process are palladium, platinum, rhodium, 31,~12D-F -23--24- 1~5~ 4~

ruthenium, nickel and mixtures thereof. Preferred catalytic metals are palladium and nickel, with palladium being most preferred.

The carbonylation catalyst comprises an alkoxide--modified support with a sufficient amount of one of the hereinbefore described metals loaded thereon to give the - desired catalyst productivity for the claimed process.
The catalyst preferably comprises an alkoxide-modified support with between about 0.1 and 10 percent by weight of the hereinbefore described metal, more preferably between about 1 and 10 percent by weight, and most pre-ferably between about 3 and 7 percent.

The carbonylation catalysts preferably are prepared by incipient wetness techniques, which are - 15 well-known in the art. In particular, a salt of the - metals described hereinbefore is dissolved in water or an aromatic hydrocarbon and thereafter contacted with the particular support. Exampies of salts which can be used include metal acetates, metal halides, metal nitrates, and the like.

A particularly preferred catalyst comprises palladium deposited onto an alkoxide-modifed support wherein the core support is ~-alumina and the metal of the metal alkoxide is alumina. Preferred supports have a surface area from about 10 m2/g to about 350 m2/g and more preferably from about 100 m2/g to about 300 m2/g.

In a preferred carbonylation catalyst pre-paration procedure, a previously prepared alkoxide-modified support and an aqueous hydrochloric acid solution of a palladium salt ha~ing a pH of 3.0 or less 31,912D-F -24-are contacted at elevated temperatures. Preferably, the support is heated to a temperature from about 75C to about 150C and the aqueous hydrochloric acid solution is heated to a temperature of from about 50C to about 95C
at the time th~ support and solution are contacted. Onlv sufficient solution so as to result in incipient wetness of the substrate is employed. Accordingly, the volume and metal concentration of the aqueous solution are adjusted to provide sufficient metal loadings and sufficient volume of liquid to completely wet the support, but not provide more liquid than can be absorbed by the support. Preferably, the agueous solution has a pH of 2.0 or less.

After impregnation with the palladium solution, the catalyst preferably is dried in flowing air at ele~ated temperatures up to about 300C for several hours. Reduction may then occur employing hydrogPn under the temperatures and conditions described hereinafter.

The carbonylation catalyst preferably is activated by passing hydrogen gas over the impregnated catalystic support at a temperature of between about 150C and 350C, for a period of time to reduce a sig-nificant amount of the metal salt impregnated on the support. Preferably, the hydrogen gas is passed over the support at a temperature of between about 225C and 300C, with between about 240C and 280C being most preferred. It is preferable to flow hydrogen gas over the catalyst for a time period of between about 1 and 10 hours.

It is believed that during the activation procedure the metal is reduced to the zero valence state, which is believed to be the catalytic species.

31,912D F -25-~SB~

In general, the support is impregnated with a sufficient amount of metal so as to create a carbony-lation catalyst which is active under the reaction conditions. The amount of active metal on the carrier can be between about 0.01 and 99 percent by weight of the support. Preferably, the catalyst contains between about 0.1 and 10 percent by weight of active metal. Even more preferably, the catalyst contains between about 1 and 10 percent by weight of the active metal, with between about 3 and 7 percent by weight of the active metal on the catalyst being most preferred.

It has been discovered that the presence of an alcohol or ether in the reactants results in significant increases in the productivity of the catalyst for the 15 ~-substituted acrylate ester. The mole ratio of the alcohol to the haloalkene in the feed composition has a significant effect on the productivities, conversions and selectivities. The productivities, conversions and selectivities are enhanced as the equivalent ratio of alcohol or ether to haloalkene increases from 1:1 to 2:1, at 2:1 the productivities, conversions and selectivities are optimized. The ratio of alcohol or ether to olefin can be any ratio which gives a d~sired conversion and selectivity. Preferably, the equivalent ratio of alcohol or ether to haloalkene is 1.5:1 or above. More pre-ferably the alcohol or ether to haloalkene ratio is 2.0:1 or greater. An equivalent with respect to the alcohol or ` ether, refers herein to that amount of alcohol or ether which provides one mole of hydocarbyl radicals. In particular, one mole of a dihydrocarbyl ether provides two equivalents of hydrocarbyl radicals, while one of an alcohol provides one equivalent of hydrocarbyl radicals.

31,912D-F -26--27- 1 25 ~

At least a stoichiometric ratio of carbon monoxide to haloalkene is needed for this process to give good selectivities and conversions.

The temperature used for the carbonylation process has a significant effect on the conversions, selectivities, catalyst productivity and catalyst life-time. In practice, any temperature at which the de~sired - conversions, selectivites, productivity, and catalyst lifetime are achieved can be used. Preferable reaction temperatures are between about 125C and 250C, with 170C to 240C being more preferred. In general, above 250C the rate of reaction significantly decreases.
Below 125C, the reaction rate is extremely slow.

The reaction pressure also has a significant effect on the selectivities, conversions, catalyst pro-ductivity and catalyst lifetime. Any reaction pressure which gives the desired selectivities, conversions, catalyst productivity and catalyst lifetime can be used. Preferred pressures are between about 100 and 800 psi, (689 to 5512 kPa), with between about 300 and 600 psi (2067 to 4134 kPa) being most preferred. Above 800 psi (5512 kPA) the rate of reaction drops dramati-cally and below 100 psi (689 kPa) the selectivity of the reaction is very poor.

The flow rate over the catalyst can be any flow rate which gives the desired conversions and selectivities. In practice, the flow rate of carbon monoxide is between about 15 gas volumes of carbon monoxide per volume of catalyst per hour and 1500 gas volumes of carbon monoxide per volume of catalyst per hour. Preferably, the flow rate is between about 100 31,912D-F -27--28- ~5~"~

and 200 gas volumes of carbon monoxide per volume of catalyst per hour.

It is preferable that the alcohol or ether and haloalkene be vaporized by preheating before contacting

5 them with the carbon monoxide in the presence of the catalyst, i.e. it is preferred to operate in the vapor phase. The combined alcohol or ether and haloalkene feed to the preheater is preferably between about 0.1 and 10 liquid volumes per volume of catalyst per hour. More 10 preferably the feed rate is between about a .5 and 1.5 liguid volumes of haloalkene and alcohol or ether per volume of catalyst per hour.

This process can be performed in a batch or continuous mode. Furthermore, the catalyst can be used as 15 a fixed bed catalyst or in a fluid bed. It is preferred to use a continuous mode with a fixed bed catalyst.

In one preferred embodiment, methylmethacrylate is prepared by contacting 2-chloropropene, carbon mono- d xide and methanol, or dimethyl ether in the vapor phase 20 over a catalyst which comprises palladium on A10x/alumina wherein the concentration of palladium on the support is between about-l and 7 percent by weight. In this embodiment, the catalyst is prepared by impregnating palladium chloride onto the support. The catalyst is activated by 25 passing hydrogen gas over the supported palladium chloride at a temperature of between about 240C and 280C for a period of between 1 and 3 hours. In this embodiment, the contacting of the reactants takes place at between about 170C and 240C under a pressure of 300 to 600 psi (2067 to 4134 kPa).

31,912D-F -28--29- ~5~ 9 The carbonylation process of this invention results in a process for the preparation of acrylate esters wherein the catalyst exhibits long lifetimes, with good productivities and selectivities. The pro-cess of this invention results in catalyst productiv-ities of at least about 0.06 g of product per gram of catalyst per hour, under more preferred conditions a productivity of at least about 0.10 g of product per gram of catalyst per hour, and under most preferred conditions at least about 0.25 g of product per gram of catalyst per hour. The process of this invention results in selectivities toward ~-unsubstituted acryl-ate ester of 70 percent or greater, under preferred conditions, of 80 percent or greater, and under most - 15 preferred conditions 85 percent or greater.

Referring to the carbonylation reaction, Con-version refers to the amount of haloalkane converted to products, and selectivities refer to the percentage of acrylate esters in the products prepared.

D. Hydrogenation The selective hydrogenation of alkynes amidst major proportions of alkenes is a known reaction. For example, the manufacture of unsaturated hydrocarbons usually involves cracking higher hydrocarbons and produces a crude product containing, as impurities, hydrocarbons that are more unsaturated than the desired product but which are very difficult to separate by fractionation. A common example is the manufacture of ethylene in which acetylene is a contaminant. In a similar way, the formation of propylene is accompanied by hydrocarbons of the empirical formula C3H4(e.g.

31,912D-F -29-~ 25B~rfi'9 methyl acetylene and allene~, and the formation of butadiene by vinyl acetylene. The content of the undesired hydrocarbons depends upon the severity of the conversion treatment, but is always too low to - 5 permit their separation economically by conventional means such as distillation. However, such highly unsaturated hydrocarbons can be removed by hydrogenation using process conditions and a carefully formulated catalyst such that no significant hydrogenation of the desired hydrocarbon takes place.

United States Patent 4,347,392 discloses a hydrogenàtion catalyst which is palladium on alumina with the average size of the palladium crystallites being at least 50 angstroms. However, the preparation of said catalyst is disadvantageous in that the catalyst must be subjected to heat activation at a temperature of 600C to 1100C.

United States Patent 4,126,645 discloses a hydrogenation catalyst which comprises palladium supported on particulate alumina, the catalyst having a surface area in the range of 5 to 50 m2/g, a helium density of under 5 g/cm 3, a mercury density of under 1.4 g/cm 3 and a pore volume of at least 0.4 cm3/g, at least 0.1 cm3/g of which is in pores of radius over 300 Angstrom units, the palladium being present mainly in the region o~ the`catalyst particles not more than 150 microns beneath their geometric surface. The alumina can be a coating on the surface of a honeycomb.

United States Patent 4,410,g55 discloses a hydrogenation catalyst support prepared by applying a specified calcium aluminate material to a honeycomb.

- 31,912D-F -30--31- ~25B~"~

It would be desireable to have an improved catalyst for the selective hydrogenation of alkynes and dienes amidst a major proportion of alkenes. Surprisingly, the catalyst of the present invention exhibits improved selectivity and/or activity relative to commercially available catalysts for the hydrogenation of acetylenic impurities.

The hydrogenation process of the present invention is a process for hydrogenating a hydrocarbon composition comprising at least one alkene and at least one alkyne,~ the process comprising contacting the hydro-carbon composition with a catalyst of the present inyention under reaction conditions to selectively hydro-genate the alkyne without substantially hydrogenating the alkene.

Two general types of gaseous selective hydro-genation processes for purifying unsaturated hydrocarbons have come into use. One, known as "front-end" hydro-genatio~, involves passing the crude gas from the initial cracking step, after removal of steam and condensible organic matter, over a hydrogenation catalyst. The crude gas normally contains a relatively large amount of hydrogen, far in excess of that required to hydrogenate a substantial part of the olefin present. Despite this hydrogen excess, operation with sufficient selectivity to give olefins of polymerisation quality is well established - and catalyst lives of many years are obtained. In the other type, known as "tail-end" hydrogenation, the crude gas is fractionated and the resulting product streams are reacted with hydrogen in slight excess over the quantity ~ required for hydrogenation of the highly unsaturated hydrocarbons present. The tail-end hydrogenation is less 31,912D-F -31--32- ~25~u~9 critical than front-end hydrogenation in that at the low hydrogen excess a runaway reaction is not possible;
` however, there is a greater tendency to deactivation of the catalyst and formation of polymers from the highly - 5 unsaturated hydrocarbons may occur as an alternative to the hydrogenation thereof. Consequently periodic regeneration of the catalyst is required.

When the process is a "front-end" hydro-genation the temperature is suitably up to 250C, for example 60-150C; the pressure is suitably in the range 1-70 atm (101-7070 kPa), for example 8-40 atm (808-4040 kPa); and the space velocity is suitably in the range 100-20000, for example 5000-15000 hour 1, that is, liters per liter o~ catalyst-filled space per hour, calculated for 20C, 1 atm pressure. The volume percentage composition of the gas fed to the catalyst is suitably as follows for a process producing ethylene and/or propylene as main products:

ethylene or propylene: 10-45 propylene or ethylene: up to 20 (when both are present) higher hydrocarbons up to 2 acetylene and/or C3H4:0.01 to 2 hydrogen: 5-40 unreactive gases (e.g. alkanes, nitrogen):balance For long catalyst life without regeneration the hydro-` gen content is preferably at least 5 times by volume as much as the content of acetylene and C3H4.

When the process is a tail-end hydrogenation the temperature is suitably in the range 40-150~C; the 31,912D-F -32--33~ 1 ~5 ~2~

pressure is suitably in the range 1-70 atm (101-7070 kPa), for example 8-40 atm (808-4040 kPa); and the space velocity is suitably in the range 500-7000 hour 1, that is, liters of gas per liter of catalyst-filled space per hour. The hydrogen content should be at least sufficient to hydrogenate to mono-olefin all the highly unsaturated hydrocarbons present and is prefer-ably from about 1.0 to about 1.5 times that content for acetylene. The life of the catalyst between regener-ations is longer the higher the hydrogen content of thegas, but this advantage is counter-balanced by the expense of separating and recycling greater quantities of saturated hydrocarbon. The gas passed over the catalyst typically contains up to about 6 percent (for example 0.1 to 3.0 percent) of highly unsaturated hydrocarbons and at least 50 percent, sometimes over 95 percent, of the desired mono-olefin or conjugated diolefin.

When the process is a tail-end liquid-phase selective hydrogenation the temperature is typically 0-50C, the pressure up to about 50 atm ~5050 kPa), and the space velocity typically 5-40 kg. per hour per liter of catalyst-filled space. The li~uid hydrocarbon suitably trickles downwards over the catalyst in a substantially stationary hydrogen atmosphere.

Whichever type of hydrogenation is used, it appears to be advantageous to have present a small quantity of carbon monoxide. In a front-end hydro-genation the proportion of carbon monoxide is suitably 0.03 to 3.0 percent v/v of the total gas mixture. Such a content commonly enters in as a by-product of the initial cracking reaction.

31,912D-F -33--34- ~ ~5 ~

In a tail-end hydrogenation the proportion is suitably in the range 4.0 to 500 ppm v/v; it may be added deliberately if fractionation of the crude gas has removed it or left too little of it.

The composite hydrogenation catalyst typi-Gally is prepared using a core support material having a surface area of from about 5 to about 400 m /g, and - preferably from about 30 to about 200 m2/g Catalysts which can be employed in the hydro~
genation process of the present invention include catalysts comprising known catalytic materials for the selective hydrogenation reaction which catalytic mater-ials are supported on an alkoxide-modified support.
Examples of said catalyic materials include, for example, materials comprising palladium nickel, platinum, osmium, rhodium, and others, with palladium being preferred. A
promoter is optionally employed. Example of typical promoters include Mo, Fe, Cr and metals of Group IB.

The catalytic material is employed in a catalytic amount. Preferably, from about 0.01 to about 1 weight percent catalytic metal is employed in the composite catalyst for selective hydrogenation, more preferably from about 0.02 to about 0.5 wt percent catalytic metal is employed.

The composite catalyst is prepared according to known methods of applying a catalytic material to a support. This may be effected by a dry procedure, such as sputtering, but is preferably effected by a wet pro-cess, in which a solution of a palladium compound, for example the chloride or nitrate, is applied to the 31,912D-F -34--35~ 125~4~

support by, for example, dipping or spraying. Spraying is preferred in order to obtain more reliably the desired uptake of palladium. Penetration of palladium can be controlled by suitable adjustment of the acidity of the solution, the acidity level being dependent on the alkali-content of the alumina. If desired the deposition of the palladium can be aided by a pre-cipitant such as a slow-acting alkali (~or example urea) or a reducing agent.

A preferred hydrogenation catalyst has the catalytic metal located below the surface of the alkoxide-modified composite support, and is prepared using an acidic solution of an acid such as, for example, HF, which is preferred, or citric or other acids. For example, the typical concentration of HF in the catalytic metal-containing solution is from about 1 to about 8 weight percent. The average penetration of palladium into the support preferably is from about 0.01 mm to about 1 mm below the surface of the composite catalyst.
The method of preparing such a penetrated layer catalyst is well known. See, e.g., Journal of Catalysis, V. 51, pp. 185-192 (1978).

After application of the palladium content to the support, it is drained, may be dried at a tempera-ture in the range 25C. to 150C., conveniently atabout 100C., and may, without or with a distinct drying step, be heated to decompose the palladium com-pound, suitably at a temperature up to 500C., espe-cially in the range 150C. to 450C. The pieces may be treated with hydrogen to complete reduction to palla-dium metal for example during the heating step just mentioned and/or during an additional heating step (in 31,912D-F -35--36- ~ 2 5 ~r,~ ~

which the temperature should be in the range 25 C. to 450 C.) after the first heating step but before use.
If there is not preliminary reduc-tion step, reduction takes place under the reducing conditions in the selec-tive hydrogenation process. If the catalyst is reducedbefore use it may be stored under an inert atmosphere but should preferably not be kept for prolonged periods in hydrogen. If desired, the composite catalyst can be reduced in the known manner using a known reducing agent such as hydrazine or sodium borohydride, NaBH~.
The use of NaBH4 as a reducing agent is well known.
See, e.g., Catal. Rev. - Sci. Eng~, 14(2), 211-246 (1976).

For the purposes of the hydrogenation process of the present invention, the terms conversion and selectivity are as defined in Applied CatalYsis~ V~2 pp. 1-17 (1982). Surprisingly, the hydrogenation catalyst of the present invention produces relatively little green oil, i.e. alkyne oligomers.

The following examples and comparative experi-ments are given to illustrate the invention and should not be construed as limiting its scope. All parts and percentages are by weight unless otherwise indicated.

Specific Embodiments Preparation of Alkoxide-Modified Supports Preparation 1 A solution 4.5 g of Al[OCH(CH2CE3)(CH3)]3 (obtained from Alfa Products, a Division of Morton Thiokol, Inc.), in 20 ml of hexanes is added to a suspension of 10 g of y-Al2O3 core support material (obtained from Strem Chemicals, Inc.), and having a BET

31,912D-F -36-surface area of 100 m2/g in 125 ml of hexanes to form a mixture. The mixture is stirred for 2 hours at room temperature under an inert atmosphere. Then the hexanes are removed under vacuum to yield a white powder. The powder is calcined in air at 450C for 15 hours to form an AlOx/y-Al2O3 alkoxide-modified support having a BFT
surface area of 120 m2/g. The weight ratio of AlOX to y-aluminum is approximately 0.05. The BET surface area of the modified support is 120 m2/g, versus 100 m2/g for the unmodified alumina. Thus, the alkoxide modi-fication does not significantly alter the overall surface area of the support. Other physical data for -the treated and untreated aluminas of Preparation 1 are as follows:

~alumina A10x/y-alumina pore volume 0.27 0.23 (cc/g) average pore 60 45 size (A) For the purposes of the present invention, the subscript "x" in the term A10X represents the relative ratio of oxygen atoms in an alkoxide-modified support to the metal of the metal alkoxide. It is believed that the metal(s) of the metal oxide layer of the modified support are in the highest oxidation state, based on calcination conditions. While this example uses A10x, additional examples of prefered metals of the metal alkoxide are listed hereinabove.

31,912D-F -37-~25~ 9 Preparation 2 The procedure of Preparation l is followed except that the precursor metal alkoxide is Ti[OCH(CH3)2]4, and the final product alkoxide-modified support is TiOX/~-Al2O3-Preparation 3 The procedure of Preparation 1 is repeatedexcept that -the precursor metal alkoxide is Ta~OCH(CH3)2]4, and the alkoxide-modified support is TaOx on y-Al2O3.

Preparation 4 The procedure of Preparation l is repeated with the following exceptions:
a) 9 g of the aluminum alkoxide is employed;
b) the core support material is 20 g of 30-80 - mesh y-Al2O3 (obtained from United Catalyst, Inc. under the designation T-374 and having a surface area of approximately 100 m2/g) and is suspended in 50 ml of hexane; and (c) the powder is calcined at 550C for 5 hours.

The resulting alkoxide-modified support con-tains 5 weight percent (~ased on aluminum~ of aluminum oxide ~AlOX) coating.

Preparation 5 The procedure of Preparation 4 is repeated expect that 50 grams of the core support material are treated with 4.5 grams of the aluminum alkoxide~ and the powder is calcined at 450C in air over night.

31,912D-F -38--39~ 1~5~49 Example l - Methanation Catalyst Preparation Five grams of the support of Preparation 1 are added to a 100 ml solution of 0.64 g of RuCl3 (1-3 H20) in H20. The mixture is stirred for an hour and the water is removed under vacuum with steam heat. The solids are dried overnight at 110C in air. Analysis indicates that the solids contain 5 weight percent Ru.

General Methanation Reaction Procedure A 16-inch (41 cm) long piece of 9/16 inch (1.43 cm) tubing of type 316 stainless steel is employed vertically as a reactor. The reactor is equipped with a means for tèmperature control, and has 1 g of catalyst held in place by quartz wool in the center of the reactor. The catalyst is reduced in situ at 400C for 15 hours with hydrogen at 50 cc/min. Then the reactor is cooled to 300C in flowing hydrogen gas. Then a feed stream consisting of 2 moles hydrogen per mole of C0 is fed to the reactor under a pressure of 1 atmosphere (14.~ psig) at 100 cc/min (gas hourly space velocity =
6000/hr). The product stream is analyzed using gas chromatographic methods capable of detecting C1-C5 hydrocarbons, C1-C5 alcohols, H2, Co, and C02.

Examples 2-5 and Comparative Experiments 1-4 The General Methanation Reaction Procedure is followed for Examples 2-5 and Comparative Experiments 1-4, and each run is conducted for a 24-hour period.
` The results of each run are summarized in Table I.

Example 2 The catalyst of Example 1 is employed.
.

31,912D-F -39--40_ 125~

Comparative Experiment l The catalyst is 5 weight percent Ru on the ~-Al2O3 core support material of Preparation l with no alkoxide modification.

Example 3 The catalyst is 5 weight percent Ru on the support of Preparation 2.

Comparative ExPeriment 2 The catalyst is 5 weight percent Ru on TiO2, 10the untreated Tio2 having a BET surface area of 100 m2/g.

Example 4 The catalyst is 5 weight percent Ru on the support of Preparation 3.

Comparative Experiment 3 15The catalyst is 5 weight percent Ru on Ta205, the untreated Ta2O5 having a BET surface area of 5 m2/g.

TABLE I
Methanation Results with 5 Weight Percent Ruthenium Catalysts 20Selectivity Conversion to Methane Run Catalystof CO (mole %) (mole %) Ex. 2 Ru/AlOx/y-Al~203 99 100 C.E. 1 Ru/y-Al2O3 62 99 Ex. 3 Ru/TiOx/y-Al2O398 100 C.E. 2 Ru/Tio2 58 100 Ex. 4 RU/Taox/y-Al2o397 100 C.E. 3 Ru/Ta2O5 17 37 31,912D F -40--41- ~5~ 9 The results summarized in Table I indicate that the catalyst of the present invention unexpectedly and significantly outperforms, under identical conditions, conventional catalysts supported on materials used as the core support material of the catalyst of the present invention.

Example 5 and Comparative Experiment 4 Example 2 and Comparative Experiment 1 are repeated except that the catalyst has 1 weight percent ruthenium. The results are summarized in Ta~le II.

TABLE II
Methanation with 1 Weight Percent Ruthenium Catalyst Selectivity Conversion to CH
Run Catalyst of Co (mole O (mole4%?
Ex. 5Ru/AlOx/y-Al2O3 90 99 C.E. 4 Ru/y-Al2O3 3 81 Surprisingly, at the lower catalyst loading, 1 weight percent ruthenium, the catalyst of the present invention significantly outperforms the e~uivalent catalytic metal on the conventional support. More surprisingly, a loading of 1 weight percent ruthenium on an alkoxide modified support outperforms a conven-tional catalyst having a loading of 5 weight percentruthenium (see Comparative Experiment 1).

31,912D-F -41--42~

Comparative Experiment 5 - Comparative Olefin Metathesis Catalyst Preparation Three grams of the T-374 alumina employed in Preparation 4 is added with stirring to a 30 ml aqueous solution of perrhenic acid for 1 hour. The acid per-rhenic solution contains 0.096 grams of rhenium metal.
The mixture is evaporated to dryness on a steam bath.
The dry powder is calcined in a 50 ml per minute stream of air at 575QC for 9 hours, and for 3 hours in a 50 ml per minute stream of nitrogen. The calcined powder is then cooled to room temperature under a nitrogen atmos~
phere. Analysis by plasma emission spectroscopy indi-cates a 2.96 weight percent rhenium loading.

Example 6 - Olefin Metathesis Catalyst Preparation The catalyst is prepared using the procedure of Comparative Experiment 5 except that the support is 2.1 grams of the modified gamma alumina of Preparation 4, and the perrhenic acid solution contains 0.13 grams of rhenium and 50 ml water. Analysis by plasma emission spectroscopy indicates a 3.01 weight percent rhenium loading.

General Olefin Metathesis Reaction Procedure A reactor is employed which is similar to the reactor of the general methanation reaction procedure except that the diameter is 3/8 inch (0.9 cm). The catalyst is activated ln situ at 550C for 2 hours with nitrogen at 50 ml per minute. The reactor is then cooled to 87C in flowing nitrogen. A feed stream is then fed to the reactor under a pressure of 1 atmosphere gauge (101 kPa) and a gas hourly space velocity of from 100 to 1000 hours 1 The product stream is analyzed using a capillary gas chromatograph.

31,912D-F -42--43- ~25~

Comparative Experiment 6 and Exam~le 7 The general olefin metathesis reaction pro-cedure is followed. The feed stream is a mixture of 25 mole percent propylene in helium. ~ata obtained using the comparative catalyst of Comparative E~periment 5 is summarized in Table III. Data obtained using the catalyst of Example 6 is summarized in Table IV. In each case, the conversion is monitored by the disap-pearance of propylene *om the reactor effluent.
Ethylene and 2-butenes are the only products observed.
The conversion is thermodynamically limited to 37 percent under the given reacton conditions. The con-version is calculated according to the formula:

moles of propylene converted 15 % conversion = moles of propylene fed x 100 TABLE III
Propylene Metathesis Over Re2O7/A12O31 Time (H) GHSV (H 1)Conversion (%) 1 100 17.7 16 100 13.8 23.5 100 12.0 23.6 500 3.6 23.8 800 1.6 42.7 100 8.8 46.8 ~100 9.6 1) 1.0 gram catalyst, 2.96 weight percent Re, 30-8Q mesh, 360 K, 0.1 MPa.

31,912D-F -43-~~44~ 1 Z5 TABLE IV

Propylene Metathesis over Re207/Modified A12032 Time ~H) GHSV (H 1)Conversion (%) 50.5 110 27.2 68 300 14.6 500 6.5 70.8 -1000 3.4 71.5 100 16.1 73.8 100 17.6 2) 1.0 gram catalyst, 3.01 weight percent Re, 5.0 weight percent Al coating, 30-80 mesh, 360 K, 0.1 MPa.

From ~ables III and IV it is observed that the catalyst of the~present invention unexpectedly gives higher convers~on over a longer period of time as compared to a comparative catalyst prepared using a conventional support material.

Comparative Exp~riment 7 and Experiment 8 Following the General Olefin Metathesis Reaction Procedure, the reactor is fed pure isobutylene at 10 millileters per minute. Only oligomerization of isobutylene is observed. After a period of time, as mentioned hereinbelow, the propylene/helium feed of Example 7 is resumed and the isobutylene feed is dis-continued. Significant deactivation of the catalyst of 31,912D-F -44--45- ~25~z~9 Comparative Experiment 6 is observed after isobutylene has been fed to the reactor for 5 hours. Specifically, the activity for the metathesis reaction decreases 80 mole percent, based on propylene converted. After 15 hours of prior isobutylene feed, the catalyst is totally deactivated. In contrast, the catalyst of Example 7 exhibits much less deactivation with isobutylene and after 23 hours of prior isobutylene feed the activity decreases by only 25 percent. Thus, the catalyst of the present invention is shown to be less prone -to deactivation.

General CarbonYlation Reaction Procedure The reactor is a Hastelloy B 1/2 inch (1.27 cm) diameter fixed bed tubular reactor. The fixed bed of the reactor is created by first loading 5.0 ml of ~-alumina pellets, then 10.0 ml of 10-20 mesh catalyst, and finally 3 ml of quartz chips. The catalyst is first reduced under flowing hydrogen at 400 cc per minute at 250C for 2 hours. The reaction is carried out at a temperature of 210C, a total pressure of 600 psig (4235 kPa), a carbon monoxide flow rate of 25 cc per minute (GHSV = 150), and at a liquid feed rate of 7.2 cc per hour. The molar ratio of the liquid feed is 2.0 methanol: 0.2 cyclohexane (internal standa.rd): and 1.0 2-chloropropene.

Example 9 Preparation of Carbonylation Catalyst An 11.1~ g sample of an alkoxide modified support prepared according to the procedure of Prepara-tion 4 is heated to 120C and is held at that tempera-ture for several hours. A solution having a pH of 3 is prepared by adding 0.57 g of PdC12 to 15 ml of deionized water and 1.2 ml of concentrated hydrochloric acid, and 31,912D-F -45-l;~S~

heating the resulting mixture to 70C. The heated support is contacted with the hot palladium chloride solution using the incipiant wetness technique. The impregnated palladium catalyst is allowed to cool to room temperature and then is heated to 120C for 2 hours in a stream of air. The catalyst is loaded into the reactor and is reduced as described in the general carbonylation reaction procedure. Measurements of crystallites sized by hydrogen chemisorption show that the catalyst has a palladium dispersion of 56 percent and a loading of 3.0 weight percent palladium based on total catalyst weight. The results which are obtained usin~ this catalyst in the General Carbonylation Reac-tion Procedure are summarized in Table V.

Comparative Experiment 8 Comparative Carbonylation Catalyst Preparation The comparative carbonylation catalyst is prepared using a 3.2 weight percent Pd on y-alumina catalyst available from the Calsicat Division of Mallinckrodt, Inc. under the designation: sample #
21C-095B.

The catalyst is reduced according to the procedure of Example 9. The palladium dispersion is 38 percent. The results obtained using this catalyst in the General Carbonylation Reaction Procedure are sum-marized in Table V.

31,912D-F -46-~.25~

TABLE V
CARBONYLATION

Ex. 9 C.E. 8 Time (~1 ~ Converslon Time (h)% Conversion 42 ~ 45 7 47 100 28 ~0 25 Inorganic [Cl ~ in product stream:
Ex. 9 - < 120 mg/l C.E. 8 - > 360 mg/l It is apparent from Table V that the carbonyla-tion catalyst of the present invention exhibits greater activity and has a longer lifetime than the comparative catalyst. It is noted that use of the catalyst of Example 9 results in a lower chloride ion concentration in the product stream, i.e. the product stream advan-tageously is less corrosive when employing the catalyst of Example 9.

Comparative Experiment 9 Comparative Hydrogenation Catalyst A 10 cc sample of the untreated T-374 alumina of Preparation 4 is impregnated for 15 minutes with an excess of an aqueous solution of palladium nitrate which contains 0.08 weight percent palladium. Then, the impregnated support is separated from the excess solution and is rinsed with distilled water. The 31,912D-F -47--48- l~S~

resulting wet catalyst is then placed in a solution of NaBH4 at (least 10 molar equivalents based on palladium) to reduce the palladium ions to palladium metal. The wet catalyst remains in solution for a period of thirty minutes. The excess solution is then separated from the catalyst pellets and the pellets are rinsed with acetone, to deactivate any residual NaBH4, and are allowed to dry in air. The resulting catalyst has about 0.05 weight percent Pd by analysis.

Example 10 Hydrogenation Catalyst Preparation The procedure of Comparative Experiment 9 is repeated except that the catalyst support is the alkox-ide modified support of Preparation 5.

ExamPle 11 Hydroqenation Catalyst Having Sub-surface Palladium The procedure of Comparative Experiment 9 is repeated except that the catalyst support is the alkox-ide modified support of Preparation 5. An additional exception is that the palladium solution contains four weight percent hydrofluoric acid.

The catalyst of Example 11 is in the form of cylindrical pellets 1/8" by 1/8"(0.3 x 0.3 cm~. The color is gray to gray/white. Cutting a pellet in half exposes a dark-gray to black band of reduced palladium - which is approximately 0.1 to 0.5 mm below the surface.
The band is very narrow, having a width of approximately 0.05 to 0.1 mm. The light-gray coloration may penetrate to about 1 mm below the surface and the inside of the pellet is white. The alkoxide treatment deposits one weight percent, based on aluminum, of A1203 on the 31,912D-F -48-lZS~

surface of the gamma alumina core support. The impr.eg-nation using 0.08 weight percent palladium and a four weight percent HF solution produces a palladium loading of about 0.05 weight percent.

General Hydrogenation Reaction Procedure Ten cc of catalyst is placed into a 300 cc Berty reactor. A feed stream containing 0.5 mole percent H2, 0.5 mole percent C2~2, 5 ppm C0, and approx-imately 99.5 mole percent ethylene (containing small amounts of ethane and methane) is introduced to the reactor at a rate of 0.5 liters per minute (gas hourly space velocity equal 3,000 hours 1) and a pressure of 250 psig (1824 kPa). The reactor effluent is analyzed by gas chromatograph. The conversions of acetylene and hydro-gen are measured directly, as is the selectivity toethane and C4 compounds. The change in ethylene con-- centration and green oil production values are calculated, assuming no hydrogen is consumed in the green oil, using the method of Battiston et al. in Applied catalysis, Vol. 2, pages 1-17 (1982). The results in mole percent are summarized in Table VI.

31,912D-F -49-~25~34~

TABLE VI

Hydrogenation with Pd on y-Alumina Catalyst Conversion Selectlvity Exam- Temp ple (C) C2H2 H2 C2H4 C2H6 C4's* G0*

33.1 19.6 41.5 8.8 8.5 41.5 C.E.9 50 54.4 32.4 42.5 6.7 11.6 39.5 80.1 49.5 45.6 6.1 12.1 36.g 89.7 50.1 38.8 8.4 12.1 40.9 Ex.10 50 95.6 75.1 31.512.6 16.7 28.4 97.4 84.0 36.126.7 15.2 22.4 87.2 53.0 41.5 8.3 16.2 34.2 Ex.11 50 93.8 69.4 36.121.4 12.4 30.4 95.8 83.9 26.433.6 14.6 26.3 *Expressed as moles of C2H2 G.O. = green oil.

From Table VI it can be seen that the catalysts of the present invention (Examples 10 and 11) are more active and produce relatively less green oil, or oligomers, as compared to the catalyst of C.E.9., which has a conventional support.

Comparative Experiments 10-12 _ Comparative catalysts are prepared using the methods of Examples 10 and 11, except that the alumina 31,912D-F -50--51- ~25B~s~

core support is ~-alumina having a surface area of about 4 m2/g. (The ~-alumina is obtained from Harshaw Chemical Company under the designation Al-3980.) Specifically, the catalyst of Comparative Experiment 10 is prepared in a manner similiar to the manner in which the catalyst of Example 10 is prepared. The catalyst of Comparative Experiment 11 is prepared in a manner similiar to the manner in which the catalyst of Example 11 is prepared.

The catalysts of Comparative Experiments 10-11 are employed in the General Hydrogenation Reac-tion Procedure, and the results are summarized in Table VII.

TABLE VII

Hydrogenation with Pd on ~-Alumina Catalyst Conversion Selectivity Exam Temp ple (C) C2H2 H2 C2H4 C2H6C4's* GO

2040 20.6 19.1 28.837.5 5.0 30.
C.E.10 50 32.6 29.4 24.735.7 9.0 32.2 45.9 41.7 21.735.611.1 32.9 24.3 15.3 50.512.8 6.9 35.8 C.E.ll 50 43.8 25.8 42.410.8 10.9 40.9 67.1 42.6 44.913.011.0 37.0 *Expressed as moles of C2H2.
GØ = green oil.

31,912D-F -51--52- ~ ~S ~

A comparison of the results of Tables IV and VII surprisingly indicates that alkoxide-modified catalysts with the ~-alumina core support having a surface area of ~ m2/g are not drastically improved as in the case when using ~-alumina having a surface area .of 100 m2/g as the core support material.

Example 12 An~ Comparative Experiment 12 Extended Hydrogenation Run The catalyst of Exàmple 11 and a comparative catalyst are employed in the General Hydrogenation Reaction Procedure. The comparative catalyst is a commerical catalyst available under the designation G-58B, and is available from United Catalysts, Inc.
Two runs are done for each catalyst. Fresh catalysts are used in the first runs. The catalysts are regener-ated prior to the second runs. The summarized results indicate that the catalyst of the present invention is generally superior to the commercial catalyst regarding conversion of acetylene and selectivity to ethylene.
.
A review of the Examples indicates that catalysts employing an alkoxide-modified support com-prising alumina on alumina having a surface area greater than about 5 m2/g surprisingly out perform similar catalysts having conventional supports. This is unex-pected in that a metal oxide/metal oxide support having the same metal, e.g. alumina on alumina, would behave in a manner similar to an untreated support. Thus, one preferred embodiment of the present invention is a catalyst composition wherein the alkoxide-modified 31,912~-F -52-~S~r~

support employs the same metal in the metal alkoxide and the core support.

The preceding examples serve only to illus-trate the invention and its advantages, and they should not be interpreted as limiting since further modifica-tions of the disclosed invention will be apparent to those skilled in the alt. All such modifications are - deemed to ~e within the scope of the invention as defined by the following claims.

31,912D-F -53-

Claims (12)

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

1. A catalyst composition which comprises a catalytic metal and alkoxide-modified support, which support comprises a core support material having on its outer surface a thin layer of a metal oxide produced from a precursor metal alkoxide and having a surface area of at least about 5 m2/g.

2. The composition of Claim 1 wherein the core support material has a surface area of at least about 10 to 500 m2/g.

3. The composition of Claim 1 wherein the metal is a Group VIII metal.

4. The composition of Claim 1 wherein the core support is a metal oxide.

5. The composition of Claim 1 or 4 wherein the alkoxide moiety of the metal alkoxide has from 1 to about 10 carbon atoms.

6. The composition of Claim 1 wherein the catalytic metal is from about 0.01 to about 20 weight percent of the total composition.

7. The composition of Claim 6 wherein the metal oxide prepared from the metal alkoxide is from about 0.1 to about 50 weight percent of the total composition.

8. The composition of Claim 7 wherein the core support material is silica or alumina, the catalytic metal is from about 0.02 to about 10 weight percent of the composition, and the metal oxide from metal alkoxide is from about 1 to about 5 weight percent of the composition.

9. The composition of Claim 1 or 8 wherein the metal of the metal alkoxide is a metal of Group IIIA, IVA, IVB or VB.

10. The composition of Claim 1 or 8 wherein the metal of the metal alkoxide is aluminum, tantalum, or titanium and the catalytic metal is ruthenium, nickel, palladium, or rhenium.

11. The composition of Claim 10 wherein the metal of the metal alkoxide is aluminum, the core support is alumina, and the catalytic metal is rhenium.

12. A process for increasing the catalytic activity of a catalytic metal which comprises supporting the catalytic metal on a support prepared by contacting a metal alkoxide with a core support material, then calcining the mixture of the metal alkoxide and the core support material, thereby leaving a coating on the core support, the coating having the metal oxide derived from the calcination of the metal alkoxide.