CA1290313C

CA1290313C - Catalytic system for epoxidation of alkenes

Info

Publication number: CA1290313C
Application number: CA000515864A
Authority: CA
Inventors: Thomas Michael Notermann
Original assignee: Union Carbide Corp
Current assignee: Dow Technology Investments LLC
Priority date: 1985-08-13
Filing date: 1986-08-13
Publication date: 1991-10-08
Anticipated expiration: 2008-10-08

Abstract

Abstract:

A process is provided for epoxidation of an alkene in the presence of an oxygen-containing gas which comprises contacting the alkene and the oxygen-containing gas under epoxidation conditions in the presence of at least one gaseous efficiency-enhancing member of a redox-half reaction pair and a supported silver catalyst, the catalyst comprising a cata-lytically effective amount of silver on a solid por-ous support having a stability-enhancing morphology and an efficiency-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair, the support having a surface area of at least about 0.7 m2/g and a particulate matrix which contains particles having at least one substan-tially flat major surface.

Description

1~9~

IMPROVED CATALYTIC SYSTEM FOR
EPOXIDATION OF ALKE~ES
Technical Field:

The present invention is directed to an improved system for the preparation of alkene oxide from al-kene and an oxygen-containing gas employing a sup-portPd silver catalyst and to the catalysts used in the system. More particularly, the present invention relates to the oxidation of alkenes to the cor-responding epoxides in which enhanced performance is attained by combination of a gaseous member of a redox-half reaction pair present in the gaseous mix-ture of oxygen and alkene, a salt of a member of a redox-half reaction ~_r in combination with the catalyst and use of a support having a stability-enhancing morphology.

Background Art:

The production of alkene oxides, or epoxides, particularly ethylene oxide by the direct oxidationof the corresponding alkene in the presence of a silver-containing catalyst has been known for many years. For example, the basic process was described by Lefort in U. S. Patent 1,998,878 and by Van Peski in U. S. Patent 2,040,782. The basic reaction pro-~.

1290:3~ 3 ceeds, as illustrated for ethylene, according to theequation:

2 CH2=CH2 + 2 > 2 ~ 2\CH2 (I) and production of an unwanted by-product according to the reaction:

CH2=CH2 + 3 2 > 2 CO2 ~ 2 H2O tII) or by further oxidation of the epoxide.
In the years between the Van Peski patent and the present inventions, research efforts have been directed to improvin~ both the activity and longevity or useful life of the catalyst and the efficiency of the overall catalytic reaction. As is indicated by reactions I and II, the oxidation of an alkene may produce either the alkene oxide (I) sought in the process or the by-products CO2 and H2O.
Several terms are commonly used to describe some of the parameters of the catalytic system. For in-stance, "conversion" has been defined as the percent-age of alkene fed to the reactor which undergoes reaction. The "efficiency" or, as it is sometimes called, the "selectivity" of the overall process is an indication of the proportion, usually represented by a percentage, of the converted material or product which is alkene oxide. The commercial success of a reaction system depends in large measure on the effi-ciency of the system. At present, maximum efficien-cies in commercial production of ethylene oxide by epoxidation are in the low 80s, e.g., 80 or 81 per-cent. Even a very small increase in efficiency will provide substantial cost benefits in large-scale ~29(~ .3 operation. For example, taking 100,000 metric tons as a typical yearly yield for a conventional ethylene oxide plant and assuming 80 percent conversion, an increase in efficiency of from 80 to 84 percent, all other things being equal, would result in a savings of 3790 metric tons of ethylene per year. In addi-tion, the heat of reaction for reaction II (formation of carbon dioxide) is much greater than that of reac-tion I (formation of ethylene oxide) so heat-removal problems are more burdensome as the efficiency de-creases. Furthermore, as the efficiency decreases, there is the potential for a greater amount of impur-ities to be present in the reactor effluent which can complicate separation of the desired alkene oxide product. It would be desirable, therefore, to de-velop a process for the epoxidatlon of alkene in which the efficiency is greater than that obtained in conventional commercial processes, e.g., with ethy-lene, efficiencies of 84 percent or greater, while maintaining other performance characteristics, parti-cularly the activity, as described below, in a satis-factory range.
The product of the efficiency and the conversion is equal to the yield, or the percentage of the al-kene fed that is converted into the correspondingoxide.
The "activity" of the catalyst is a term used to indicate the amount of alkene oxide contained in the outlet stream of the reactor relative to that in the inlet stream. Activity is generally expressed in terms of pounds of alkene oxide produced per cubic foot of catalyst per hour at specified reaction con-ditions and rate of feed. The activity may also be stated in terms of the amount of ethylene oxide in the outlet stream or the difference between the ethy-~290~3~ 3 lene oxide content of the inlet and outlet streams.
If the activity of a reaction system is low, then, all other things being equal, the commercial value of that system will be low. The lower the activity of a reaction system, the less product pro-duced in a unit time for a given feed rate, reactor temperature, catalyst, surface area, etcetera. A low activity can render even a high efficiency process commercially impractical. For production of ethylene oxide, an activity below 4 pounds of ethylene oxide per hour per cubic foot of catalyst is unacceptable for commercial practice. The activity is preferably greater than 8 pounds, and in some instances an acti-vity greater than 11 pounds of alkene oxide per hour per cubic foot of catalyst is desired.
In some instances, activity is measured over a period of time in terms of the amount of alkene oxide produced at a specified constant temperature. Alter-natively, activity may be measured as a function of the temperature required to sustain production of a specified constant amount of alkene oxide. Plots of such measurements yield "aging rates" which reflect the stability or useful life of the catalyst. The useful life of a reaction system is the length of time that reactants can be passed through the reac-tion system during which acceptable activity is ob-served. The area under a plot of activity versus time is equal to the number of pounds of alkene oxide produced during the useful life of the catalyst per cubic foot of catalyst. The greater the area under such a plot, the more valuable the process is since regeneration or replacement of the catalyst involves a number of expenses, sometimes referred to as turn-around costs. The rate at which activity decreases, i.e., the rate of deactivation at a given point in 1290~ 3 time, can be represented by the slope of the activity plot, i.e., the derivative of activity with respect to time:

deactivation = d[activity]/dt.

The average rate of deactivation over a period of time can be represented then by the change in activity divided by the time period:
average deactivation = a activity/ ~ t.

At some point, the activity decreases to an unacceptable level, for example, the temperature required to maintain the activity of the system be-comes unacceptably high or the rate of production becomes unacceptably low. At this point, the cata-lyst must either be regenerated or replaced. Some of these definitions may be represented as set out be-low:

% Conversion = moles alkene reacted x 100moles alkene fed % Efficiency = moles alkene oxide Produced x 100 moles alkene reacted Yield = moles alkene oxide Produced x 100 moles alkene fed Typically, in commercial production, since the outlet or effluent stream emanating from the reactor may contain substantial amounts of unreacted alkene, the effluent stream is recycled and combined with the feedstream after removal of at least a portion of the ~2~0~3~3 alkene oxide. Generally, as the activity of a cata-lyst decreases with time, in order to obtain the same ultimate yield of epoxide product, the effluent stream must either be recycled a greater number of times or the temperature within the reactor must be raised to increase the activity of the catalyst. The former approach to increasing the yield of product requires additional energy expenditures and the lat-ter, which is most frequently used, causes faster catalyst deterioration.
As used herein, an activity-reducing compound refers to a compound which, when present in an acti-vity-reducing amount, causes a reduction in activity, some or all of which activity may subsequently be regained by returning to a situation in which the concentration of the compound is below the minimum activity-reducing amount. The minimum activity-reducing amount varies depending on the particular system, the feedstream and the activity-reducing compound.
Conversely, deactivation, as used herein, refers to a permanent loss of activity, i.e., a decrease in activity which cannot be recovered. As noted above, activity can be increased by raising the temperature, but the need to operate at a higher temperature to maintain a particular activity is representative of deactivation. Furthermore, catalysts tend to deacti-vate more rapidly when reaction is carried out at higher temperatures.
In contrast to problems associated with low or decreasing catalyst activities, less than satisfac-tory efficiencies result in loss of starting mater-ial, the alkene, as the unwanted product CO2. Ulti-mately, this also increases product costs.

12~0~

To be considered satisfactory, a catalyst must not only have a sufficient activity and the catalytic system provide an acceptable efficiency, but the catalyst must also demonstrate a minimum useful life or stability. When a catalyst is spent, typically the reactor must be shut down and partially disman-tled to remove the spent catalyst. This results in losses in time and productivity. In addition, the catalyst must be replaced and the silver salvaged or, where possible, regenerated. Even when a catalyst is capable of regeneration _ situ, generally production must be halted for some period of time. At best, replacement or regeneration of catalyst requires additional losses in time to treat the spent catalyst and, at worst, requires replacement of the catalyst with the associated costs.
Since even small improvements in activity, ef-ficiency or useful life may have significance in large scale commercial production, such improvements have been the object of a great deal of research in the direct epoxidation of alkenes. The focus of attempts to improve performance, such as the activity and useful life of the catalyst and the efficiency of the system, has included such areas as feedstream additives or removal of components therefrom; methods of preparation of the catalyst; deposition or impreg-nation of a particular type or form of silver; com-position, formation, physical properties and morpho-logy of the support; additives deposited on or im-pregnated in the support; shape of support aggregatesused in the reactor; and various types of reactors and bed designs, such as stationary and fluidized beds.
Early work on the silver-catalyzed direct oxida-tion of alkenes to alkene oxides in many instances ~290~.3 resulted in improvements in activity and particularlythe selectively of the system, in many cases the efficiency increasing by several percent. However, recent modifications in such systems have resulted in only small incremental improvements in efficiency.
In terms of operating costs, even fractions of a percent improvement in efficiency can translate into large savings in production. Accordingly, current research is still being directed to improvements in the activity and useful life of the catalyst and selectivity of the system.
Although a vast number of elements and compounds are known to have effective catalytic properties in various reactions, many have at least one shortcom-ing, such as very high cost and/or limited availabil-ity, ther~al instability in the temperature ran~e in which the reaction is to be conducted, low mechanical strength, small surface area per unit of volume, susceptibility to poisoning, short useful lifetime, etcetera. Such undesirable characteristics make such substances of limited utility as catalysts. Some of these shortcomings, however, may be overcome and in some instances the effectiveness of the catalvst may be improved by applying the substance to a carrier or support.
New support materials are continuously being tried. However, many of those which were employed in the early development of the silver-bearing catalysts are, with some modifications, still being used.
Materials which have found most widespread use are typically inorganic and generally are of a mineral nature. Such materials commonly include alumina, fire brick, clay, bauxite, bentonite, kieselguhr, carbon, silicates, silica, silicon carbide, zirconia, diatomaceous earth, and pumice.

~290~3~ 3 g In addition to the physical strength of the support materials, other physical properties, such as surface area, pore volume, pore dimensions, and par-ticle size have drawn considerable attention. These properties have been examined with great scrutiny when evidence indicated that there was a correlation between the size of silver particles and the effici-ency of the overall system or useful life of the catalyst. Some materials are also preferred for their chemical properties, i.e., their "inertness" or "promoting" properties.
The support serves a number of functions in a heterogeneous catalytic system. Ease of handling is facilitated by a support which generally takes the form of discrete particles or aggregates of varying shape or size which, depending on usage, have a major dimension of about 1 millimeter to about 20 milli-meters. Thus it is not necessary for the catalyst to form a permanent or semi-permanent part of the reac-tor.
The support, however, serves primarily to in-crease the surface area of the "active" component of the catalyst, silver, which is important in that most epoxidation occurs at the silver surface-fluid inter-face. Many of the substances commonly employed ascatalyst supports not only have the usual external surface, which provides a varying surface area, de-pending on the shape of the support bodies and the packing of the bodies, but are also of a porous na-ture and, therefore, have a large internal surfacewhich contributes to the overall surface area of the supported catalyst. Such support materials provide a greater capacity for sorbing not only the catalyst material during catalyst preparation, when the sup-port is impregnated with a solution containing the ~ 2~0~.3 catalyst component(s) in soluble form, but also a greater capacity for the flow of the fluid reactants within the catalyst during the reaction for which the catalyst is intended. The support also improves performance by lowering the pressure drop through the reactor and by facilitating heat and mass transfer.
Among the large variety of substances employed in the past as supports for catalytic materials, alumina has exhibited superiority in many respects as a catalyst support material. In addition to the low cost of the material, alumina has good thermal sta-bility and some forms have a relatively large surface area.
Alumina, in its various forms, particularly alpha-alumina, has been preferred as a support mater-ial for silver-containing catalysts in the prepara-tion of alkene oxides. Numerous variations of sur-face area~ pore dimensions, pore volume and particle size have been suggested as providing the ideal phys-ical property or combination of properties for im-proving efficiency, activity or useful life of the catalyst.
Holler (U. S. Patent 3,908,002) discloses an al-pha-alumina, useful as a catalyst support for reac-tions conducted at temperatures below 800 degrees C,such as oxidation reactions of hydrocarbons to oxyhy-drocarbons. The support, having a surface area re-ported to be at least about 40 m2/g, is produced by thermally decomposing a porous aluminum ion chain-bridged, polymeric carboxylate. Indicating that alarge surface area in a carrier may be detrimental to its efficient operation and catalyst activity, Belon (U. S. Patent 3,172,866) describes a method of pro-ducing a macroporous catalyst carrier which may be used in the catalytic production of ethylene oxide ~2~t0~ .3 having pore diameters of between 0.1 and 8.0 microns and a specific surface area between a few square meters and one square decimeter per gram. The sup-port is prepared by heating a mixture of active and calcined aluminum oxides and a small amount of boron oxide at temperatures of between about 1,600 and 1,800 degrees C. Waterman (U. S. Patent 2,901,441) describes a process for preparing highly active and selective catalysts for the oxidation of olefins to olefin oxides on a support having an average porosity of at least 35 percent. The method involves washing an alpha-alumina or silicon carbide support having an average porosity of between 35 and 65 percent with an aqueous solution of lactic acid, washing with water until neutral, and then impregnating the support with an aqueous solution of silver lactate. The impreg-nated support is thereafter heat-treated to deposit elemental silver. A silver-supported catalyst for the vapor phase oxidation of ethylene to ethylene oxide, exhibiting improved production of ethylene oxide and catalyst longevity, is described by Brown et al (U. S. Patent 3,725,307). The catalyst is disclosed as being formed from support part~ s having an average pore diameter of at least 10 mi-crons up to, preferably, 70 microns and a surfacearea of less than about 1 m2/g. The selectivities reported do not range above about 73 percent. The support is preferably composed of silica-alumina. A
silver-supported catalyst which includes a support of alpha-alumina, silicon carbide, fused aluminum oxide, or mixtures of alumina and silica was asserted by DeMaio (U. S. Patent 3,664,970) to eliminate the need for halogenated inhibitors in the oxidation of ethy-lene to ethylene oxide. The support is composed of particles having a minimum apparent porosity of about ~290~3~.3 30 percent and wherein at least 90 percent of the pores have diameters in the range of 1 to 30 microns, the average of the diameters being in the range of 4 to 10 microns. Wattimena (U. S. Patent 3,563,914) 5 discloses silver catalysts using aluminum oxide sup-ports having pore volumes between 15 and 30 ml/g and surface areas below about 10 m2/g.
Hayden et al (U. R. Patent Application 2,014,133) disclose a silver catalyst employing a support having a specific surface area in the range of 0.05 to 10 m2/g, an apparent porosity of at least 20 percent, and mean pore diameters of 0.1 to 20 microns, the pore size distribution being bimodal, in which the smaller pores preferably account for at least 70 percent of the total pore volume. Alpha-alumina supports are describ~d by Rashkin (U. K.
Patent Application 2,122,913A) having a "relatively low surface area" of less than 30 m2/g. Mitsuhata et al (Japanese Published Patent Application 56-089843) and Mitsuhata et al (U. S. Patent 4,368,144) describe supported silver catalysts in which the support is formed from alpha-alumina having a specific surface area of 0.5 to 5 m2/g. Watanabe et al (Japanese Published Patent Application 56-105750) employ a similar catalyst support having a surface area of 1 to 5 m2/g. Hayden et al (U. S. Patent 4,007,135) describe silver-containing catalysts in which the porous heat-resisting support has a specific surface area in the range of 0.04 to 10 m2/g, an apparent porosity of at least 20 percent, and a median pore diameter of 0.3 to 15 microns. Mitsuhata et al (U. S. Patent 4,248,740) describe the use of high alpha-alumina content supports having a specific surface area of not more than 10 m2/g~ an apparent porosity of 40 to 60 percent by volume, and a pore 12~30~ .3 volume of 0.1 to 0.5 cc/g. Armstrong et al (U. S.
Patent 4,342,667) disclose a supported silver cata-lyst, useful in the oxidation of ethylene to ethylene oxide, in which the support has a surface area of 0.02 to 2 m2/g, an average pore diameter of 0.5 to 50 microns and an average pore volume of 0.2 t~ 0.5 cc/g.
There has also been some interest in the purity of supports employed, both as to composition and phase. Examples of high purity alumina include U. S.
Patent 2,901,441 which uses alpha-alumina having a purity of about 99.5 percent as a support for cata-lysts used to oxidize olefins to olefin oxides. An ethylene oxidation catalyst is disclosed in German Patent Publication DE 2,933,950 which attains a long catalyst life without a loss in activity or selec-tivity by using an alpha-alumina support having less than 0.001 weight percent of alkali-soluble silicon compounds. The catalyst is prepared by boiling com-mercial quality alpha-alumina with 1 weight percent sodium hydroxide solution and washing to a pH value of 8. If desired, the silicon compound concentration may be reduced below 1 part per million (ppm) by washing further with 1 weight percent HF. U. K.
Patent Application 2,122,913A describes supported silver catalysts in which the support is composed of silica, alumina or mixtures thereof, one example of which i5 an alumina having a purity of 99.3 percent by weight. The silver-supported catalyst described in Japanese Published Patent Application 56-089843 employs an alpha-alumina carrier having a sodium content of less than 0.07 weight percent. ~apanese Published Patent ~pplication 56-105750 describes the use of an alpha-alumina support in conjunction with a silver catalyst for producing ethylene oxide, which 1~0~

support has a sodium content less than 0.07 weight percent. A silver catalyst including an alpha-alumina carrier having a sodium content of not more than 0.07 percent is described by Mitsuhata et al (U.
S. Patent 4,368,144). The support also has a surface area within the range of 0.5 to 5 m2/g, an apparent porosity of 25 to 60 percent, a specific pore volume of 0.2 to 0.5 cc/g, and a particle diameter within the range of 3 to 20 mm. An alpha-alumina support having a purity of 98+ weight percent, for use with silver in the catalytic oxidation of ethylene, is -described by Warner et al in U. S. Patent 4,455,392. The patent additionally discloses that - the carrier is generally a conventional microporous support with surface areas of less than 10 m2/g, pore volumes ranging from about 0.15 to 0.8 cc/g, and pore diameters of about 0.1 to 100 microns.
In addition to compositional purity, both phase purity and morphology of the support have been areas in which improvements in efficiency, selectivity or stability of the catalyst have been sought. Examples include U. S. Patent 2,901,441 in which aluminum oxide is substantially completely convert~ o the alpha form of alumina by heating aluminum oxide to a temperature of about 1,500 to 2,050 degrees C. Weiss (U. S. Patent 2,209,908) and Carter (U. S. Patent 2,294,383) describe the use of "Tabular Corundum" as a catalyst support for metallic oxides, such as those oxides of metals selected from the fifth and sixth group of the periodic system, for example, vanadium, molybdenum, uranium, etcetera, in the oxidation of various organic materials to maleic acid and maleic anhydride and silver for the catalytic oxidation of ethylene to ethylene oxide, respectively. Weiss indicates that Tabular Corundum, which is almost ~29{)~.3 entirely aluminum oxide and has the alpha-corundum crystalline form of aluminum oxide, may be formed by mixing aluminum oxide with one or more of several compounds, such as sodium oxide and chromic oxide, and heating the mixture to a temperature in the range of about 800 to about 1,800 degrees C. Tabular Co-rundum is further described as having impurities present in only small quantities, the material also includes "readily bonded surfaces and consisting essentially of interlocked corundum crystals in tabu-lar form, having the contained impurities dis-seminated in minute globules throughout the crystal-line alumina". Brengle et al (U. S. Patent 2,709,173) also employ Tabular Corundum as a support in one of their examples.
U. S. Patents 4,039,481 and 4,136,063 to Kimura et al disclose a catalyst carrier and a method for making same, the catalyst being the type used in catalytic converters in automobile exhaust systems.
Specifically, the catalysts have a surface layer containing alpha-phase alumina and an inner portion consisting essentially of alùmina of a phase other than that of the alpha phase. The pores in the al-pha-alumina surface layer are larger than those in the inner portion of the catalyst body. A method of preparing the phase gradient support particles is described which provides for treating the surface of the alumina to a depth of about 400 microns with a transition element, particularly iron, and thereafter firing the carrier particles.
Weber et al (U. S. Patent 4,379,134) describe high purity alpha-alumina bodies, at least 85 percent of the pore volume of the bodies having pores with a diameter of from 10,000 to 200,000 Angstroms. The high purity alpha-alumina bodies are prepared by ~2~03~.3 peptizing boehmite in an acidic aqueous, fluoride anion-containing mixture. An extrudable mixture is formed thereby which is extruded and shaped into formed bodies which are thereafter dried at 100 to 300 degrees C, calcined at a temperature of from 400 to 700 degrees C to convert the alumina to the gamma phase, and subsequently calcined further at a temper-ature of from 1,200 to 1,700 degrees C to convert the gamma phase to alpha-alumina phase.
A method of producing granulated porous corundum having a homogeneous porous structure with a total pore volume of 0.3 to 1.0 cm3/g and a predominant pore size of 5,000 to 30,000 A is described by Bores-kov et al (U. S. Patent 3,950,507~. The method of preparing the alpha-alumina includes treating active alumina or aluminum hydroxide having a porous struc-ture to a first heat treatment in which the tempera-ture is increased from 20 to 700 degrees C, a second heat treatment in the range of from 700 to 1,000 degrees C, and a third treatment in the range of from 1,000 to 1,400 degrees C. Each of the heat treat-ments is for a period of at least one-half hour, the first hea~ treatment being conducted in an atmosphere of hydrogen fluoride in which the alumina absorbs the hydrogen fluoride and the second heat treatment de-sorbs the hydrogen fluoride. The patent also de-scribes a similar procedure employing stationary thermal conditions in which the granules of alumina or aluminum hydroxide are impregnated with other fluorine-containing substances prior to the first thermal treatment. The recommended starting mater-ials used to form alpha-alumina include granulated pseudo-boehmite, boehmite or bayerite as the granu-lated aluminum hydroxide and granulated alpha-, eta-, or theta-alumina as the acti~e alumina.

~29(~ .3 -17~

Although alpha-alumina has been considered by most to be the preferred alumina support material, Smith et al (U. S. Patent 2,422,172) have suggested that beta-aluminas are more desirable than the alpha phase as a support material for catalysts, particu-larly those used in catalytic conversion processes such as dehydrogenation and hydroforming.
In seeking the ideal support material, there has been some departure from the commonly employed sub-stances. For example, some use has been made ofalkali metal and alkaline earth metal carbonates, both as the sole support material and in combination with other materials as the carrier for processes such as direct oxidation of alkenes to epoxides.
A number of supported silver-containing cata-lysts haYe been employed for epoxidation of alkenes in which the carrier includes, sometimes labelled as a promoter, a carbonate of a metal, generally an alkali metal or alkaline earth metal. Some examples of the use of one or more alkali and/or alkaline earth carbonates may be found in U. S. Patents 2,424,084, 2,424,086, 2,~15,900, 2,713,586, 3,121,099, 3,258,433, 3,563,913, 3,563,914, 3,585,217, 4,007,135, 4,033,903, 4,039,561, 4,066,575, 4,094,889, 4,123,385, 4,125,480, 4,168,247, 4,186,106, 4,226,782, 4,229,321, 4,324,699, European Patent Publications 0,003,642 and 0,011,356, Japanese Patents 41-11847 and 57-107242, U. K. Patents 590,479, 1,571,123 and 2,014,133A, and Murray, "A 5tudy Of The Oxidation Of Ethylene To Ethylene Oxide On A Silver Catalyst", Australian Journal of Scientific Research, Volume 3A, Pages 433-449 ~1950). In addition, U. S. Patent 3,332,887 employs zinc and/or cadmium carbonates, Gelbstein, (DS 2,352,608) discloses the use of the latter car-12~ .3 bonate and European Patent Publication 0,003,642 mentions the use of molybdenum carbonate.
Several patents have described the use of fluo-rine-containing substances to treat support mater-ials, in some cases to provide a compositionally puresupport, and in other cases as a fluxing agent to improve the phase purity of the support. Thus, U. K.
Published Patent Specification 590,479 and U. S.
Patent 2,424,085 indicate that a more active catalyst is formed if the support material has undergone a preliminary treatment with a dilute solution of hy-drofluoric acid prior to impregnation with silver.
U. S. Patent 4,379,134 teaches the preparation of high purity alpha-alumina bodies by peptizing boeh-mite alumina in an aqueous acidic mixture containingfluoride anions and water. German Patent 2,933,950 teaches the reduction of silicon content by treatment with HF. U. S. Patent 3,950,507 teaches the prepara-tion of granulated porous corundum by a multiple step heat treatment in which initial steps may be carried out in an atmosphere of hydrogen fluoride. Hosoda et al ~U. S. Patent 3,144,416) suggest that a small amount of a halogen compound, sulfur compound, nitro-gen compound, or phosphorous compound may be added either to the reaction gas or the catalyst to improve the selectivity of the catalyst.
The nature of the silver itself has also been examined and modified in attempts to improve the efficiency and stability of the catalyst. Cavitt (U. S. Patent 4,229,321) teaches that a supported silver catalyst of improved selectivity and activity may be prepared by mechanically removing the outer surface or skin of the catalyst after the impregnated catalyst has been heated to evaporate volatile mater-ial and reduction of the silver salt to silver metal, 12~ .3 thereby activating the catalyst.
Since the early work on the direct catalyticoxidation of ethylene to ethylene oxide, workers in the field have suggested that the addition of certain compounds to the gaseous feedstream or direct incor-poration of metals or compounds in the catalyst could enhance or promote the production of ethylene ox-ide. Such metals or compounds have been known vari-ously as "anti-catalysts", "promoters" and "inhi-bitors". These substances, which are not themselvesconsidered catalysts, have been proposed by prior workers to contribute to the efficiency of the pro-cess by inhibiting the formation of carbon dioxide or promoting the production of ethylene oxide. The lS scientific literature is replete with examples of the use of alkali metals and alkaline earth metals and their cations to promote the efficiency of silver catalysts used in epoxidation reactions. For exam-ple, sodium, potassium and calcium were disclosed as 20 being suitable promoters in U. S. Patent 2,177,361.
Numerous examples may be found in literature of pref-erence for one or several metals or cations and ex-clusio- c one or more metals or cations as promoters in silver catalysts.
Among those anions associated with the cation promoters used in preparing silver-containing cata-lysts employed in direct epoxidation reactions that have been suggested as being suitable include car-boxylates, for example, formate, acetate, malonate, oxalate, lactate, tartrate, and/or citrate, and inor-ganic salts, such as carbonates, bicarbonates, phos-phates, nitrates, and/or nitrites, chlorides, io-dides, bromates, and isopropoxides. However, al-though many examples may be found in the literature indicating that such compounds are suitable, numerous ~3 -20~

patents, such as U. S. Patents 3,962,136; 4,012,425;
4,0~6,575; 4,207,210; and 4,471,071, suggest that no unusual effectiveness, particularly with regard to catalytic activity, is observed with any particular anion of an alkali metal promoter. U. S. Patents 4,007,135; 4,094,889; 4,125,480; 4,226,782;
4,235,757; 4,324,6g9; 4,342,667; 4,356,312;
4,368,144; and 4,455,392 disclose that potassium nitrate may be added to the catalyst as a suitable promoting material. Potassium nitrate may also be formed in situ when a carrier material is treated with certain amines in the presence of potassium ions as, for instance, when silver is introduced to a carrier material in a silver-impregnating solution containing an amine and potassium ions, followed by roasting.
A number of compounds have been proposed in the literature as additives to the feedstream or re-actants to improve the efficiency of the direct, silver-catalyzed oxidation of alkenes to alkene ox-ides. For example, Law and Chitwood (U. S. Patent 2,194,602) disclose the use of a "repressantn, i.e., anti-catalyst, such as ethylene dich~oride, chlorine, sulfur chloride, sulfur trioxide, nitrogen dioxide, or other halogen-containing or acid-forming mater-ials. Numerous additional anti-catalysts are pre-sented by the same patentees in U. S. Patent 2,279,469. The anti-catalysts, broadly listed in categories such as halogens and compounds containing halogen, hydrocarbons, compounds containing carbon, hydrogen and oxygen, compounds containing sulfur, and compounds containing nitrogen are represented and, in addition to those compounds already mentioned above, additional representative compounds include, as ni-trogen-containing compounds, nitric oxide, ammonia, ~2~0~

amines such as ethylenediamine, diphenylamine and analine, nitro compounds such as o-nitroanisole and o-nitrotoluene as organic oxygen-containing organic compounds, alcohols such as methyl, ethyl and iso-5 propyl alcohols, ethers such as isopropyl and dibutyl ethers, as well as glycol ethers, ketones such as methyl ethyl ketone and acetone, as hydrocarbons such as benzene, and N-hexane; sulfur compounds such as sulfur dioxide, hydrogen sulfide and diethylsulfide;
10 chlorine-containing compounds such as carbon tetra-chloride, chlorobenzene and dichloroethyl ether.
Berl (U. S. Patent 2,2700780) lists a number of com-pounds as anti-detonating or anti-knock materials to control the oxidation of ethylene and propylene to 15 their oxides. Disclosures of other feedstream addi-tives used in the production oE alkene oxldes, parti-cularly halogen compounds, may be found in U. S.
Patents 2,279,470; ~,799,687; 3,144,416; 4,007,135;
4,206,128; and 4,368,144. In addition, EPO Patent 0,003,642 and U. R. Patent Application 2,014,133A
disclose processes for the production of olefin ox-ides employing silver-containing catalysts in which a chlorine-containing reaction modifier and a nitrite or nitrite-form~ng substance are described. Rumanian Patent 53012, published December 2, 1971, discloses a direct, silver-catalyzed direct epoxidation procedure which employs oxides of nitrogen in the feedstream.
U. R. Patent 524,007 includes ethylene dichloride or nitrogen dioxide in the feedstream of a silver-cata- r 30 lyzed epoxidation procedure.
Although much of the art discussed above has resulted in improvements in the efficiency, activity G
or stability of the catalytic system, many of the ~ ~ ~ 0~.3 improvements have individually been rather slight.
In some of the catalytic systems, gains in one of these performance parameters have been frequently offset by losses in another; that is, enhancement of one index of performance has been accompanied by a deleterious effect on another of the indices. For example, if a reaction system is designed which has a very short useful life, the system may be commer-cially impractical even though the efficiency and initial activity of the catalyst are outstanding.
Accordingly, a system that provides an increase in the efficiency of the overall catalytic reaction system, while only minimally decreasing the activity and useful life of the catalyst would be particularly beneficial.

Disclosure Of The Invention:

The present invention is directed to a catalytic process for epoxidation of alkene in the presence of an oxygen-containing gas and to the catalyst used therefor. The process comprises contacting an alkene with an oxygen-containing gas under epoxidation con-ditions in the presence of at least one gaseous effi-ciency-enhancing member of a redox-half reaction pair of a redox-half reaction pair and a solid catalyst.
The catalyst comprises a catalytically effective amour,t of silver on a solid support and an effi-ciency-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair. The support employed for the catalyst has a surface area of at least about 0.7 m2/g and is formed from particles, many of which are interfused or in-terpenetrating, that is, particles which project from opposing sides of other particles as if passing 2 ~ ~3~

through or "growing" out of other particles. In addition, such particles have at least one substan-tially flat major surface.
The present invention is also directed to a catalyst for use in epoxidation of alkene with an oxygen-containing gas which comprises a catalytically effective amount of silver on a solid support and at least one efficiency-enhancing salt of a member of a redox-half reaction pair~ The efficiency-enhancing salt is present in an amount which provides an effi-ciency of at least about 84 percent under Standard Test Conditions. The support has a surface area of at least about 0.7 m2/g and is formed from interfused particles having at least one substantially flat major surface. The combination of a support having a surface area of at least about 0.7 m2/g in which particles have at least one substantially flat major surface and the presence of a salt of a member of a redox-half reaction pair produces a catalyst of en-hanced performance which is both highly active andcapable of maintaining such activity for extended periods of time. In addition to those indices of performance, a catalytic system employing such a catalyst, particularly when used in the presence of a gaseous member of a redox-half reaction pair, also results in enhancement of efficiency. Thus, effi-ciencies on the order of about 84 percent are the norm under Standard Test Conditions and of about 88-92 percent or greater are not uncommon. In addition, the catalysts of the present invention are capable of maintaining a high activity or short term stability as well as a long term stability.

~2~0~

Brief DescriPtion Of The Drawinq:

The figure is a scanning electron micrograph, taken at a magnification o~ 2000 X, of alpha-alumina 5 support particles having a platelet morphology ac-cording to the present invention.

Detailed DescriPtion Of The Invention:

The present invention is directed to a process for the vapor phase oxiAation of alkenes to alkene oxides, i.e., an epoxidation process, in the presence of an oxygen-containing gas and to the silver cata-lysts employed therein.
The process and catalyst of the present inven-tion are useful in the epoxidation of the alkenes ethylene and propylene, the epoxides of which are in great demand for use as intermediates in producing such materials as polymers, surfactants, synthetic fibers and antifreeze. However, the present inven-tion is not limited to these compounds but may be used to oxidize cyclic and acyclic alkenes which are in the gaseous state or have significant vapor pres-sures under epoxidation conditions. Typically these compounds are characterized as having on the order of 12 carbon atoms or less which are gaseous under epox-idation conditions. In addition to ethylene and propylene, examples of alkenes which may be used in the present invention include such compounds as bu-tene, dodecene, cyclohexene, 4-vinylcyclohexene, sty-rene and norbornene.

2 ~0~.3 suPPort:

The support material used in the present inven-tion may be selected from suitable solid, porous, refractory material which can withstand roasting tem-peratures, if that is the method employed to reduce the silver present to its free metallic state. Re-gardless of the method used to reduce the silver, the support should also be able to withstand the tempera-tures employed within the reactor under epoxidationprocess conditions. Preferably, the support should not have any undue deleterious effect on the per-formance of the system. Examples of suitable mater-ials include magnesia, zirconia, silica, silicon carbide, and alumina, preferably alpha-alumina.
Su~table support materials also have a surface area of at least about 0.7 m2/g and preferably about 0.7 to about 16 m2/g, particularly preferred are those materials having surface areas in the range of about 0.7 to about 7 m2/g. The surface area is measured by the conventional B~ E. T. method using nitrogen de-scribed by Brunauer, Emmet and Teller in J. Am. Chem~
Soc., 60, 309-16 (1938).
The support should be composed of a particulate matrix which includes particles having at least one substantially flat major surface. Preferably, at least about 50 percent of particles of the support having a particle size of at least Q.l micron com-prise particles having at least one substantially flat major surface~ As used herein, "particle size"
refers to the diameter or major dimension of the particle.
The support particles of the present invention, which are provided with at least one substantially flat major surface, may be characterized as having a 2 ~ 0~.3 lamellate or platelet-type morphology wherein some of the particles have two, or sometimes more, flat sur-faces. The "substantially flat major surface" re-ferred to herein may be characterized by a radius of curvature of at least about twice the length of the major dimension of the surface. Preferably, the particles also have aspect ratios of at least about 4:1, the aspect ratio being the ratio of the longest or major dimension to the smallest or minor dimen-sion. The particles preferably have aspect ratiosexceeding about 10:1. In some aspects of the present invention, the major dimension of a major portion of the particles having platelet-type morphology is less than about 50 microns, preferably less than about 20 microns. When alpha-alumina is employed as the sup-port material, the platelet-type particles frequently have a morphology which approximates the shape of small plates or wafers. The configuration of these plates is shown in Figure 1. A portion of the sup-port particles preferably are formed as "interfused"or "interpenetrated" platelets, that is, having the appearance of platelets growing out of or passing through one another at various angles. This is par-ticularly true of the preferred material, alpha-alumina. In some cases the edges of some of theplatelet or wafer-like particles contact or are fused to the faces of other particles to provide a struc-ture which appears to be an irregular "house of cards" structure. It is this morphology or structure which is believed to account for the crush strength, pore volumes and surface areas which provide the high performance characteristics of the present invention such as the short term stability or high activity and long term stability.

15~13 ~X90~ .3 These platelet-type particles frequently have substantially angular edge portions, as contrasted with amorphous or rounded edge portions of conven-tional support materials, including conventional 5 alpha-alumina supports. The higher surface energies associated with the former type of edge portions may contribute to the enhanced performance of the subject invention.
The carrier materials of the present invention 10 may generally be described as porous or microporous, having median pore diameters of about 0.01 to about 100 microns, preferably about 0.5 to about 50 mi-crons, and most preferably about 1 to about 5 mi-crons. Generally, they have pore volumes of about 0.6 to about 1.4 cc/g, preferably about 0.~ to about 1.2 cc/g. Pore volumes may be measured by any con-ventional technique, such as conventional mercury porosity or water absorption technique.
Generally improved results have been demon-strated when the support material is compositionally pure and also phase pure. By "compositionally pure"
is meant a material which is substantially a single substance, such as alumina, with only trace impuri-ties being present. "Phase purity" or like terms refer to the homogeneity of the support with respect to its phase. In the present invention, alumina, having a high or exclusive alpha-phase purity (i.e., alpha-alumina), is preferred. Most preferred is a material composed of at least 98 percent, by weight, of alpha-alumina. Under some conditions as when used in conjunction with the salt and gaseous members of redox-half reaction pairs, the presence of even small amounts of sodium can adversely affect the activity and useful life of the catalyst, i.e., have a deacti-vating effect on the catalyst. Improved results have lZ~ 3~3 been observed when the support contains leachable sodium levels less than about 50 parts per million (ppm) by weight, preferably less than 40 ppm, and most preferably less than about 20 ppm based on the weight of the total support. Supports which are also useful in the present invention are those having less than a catalyst-deactivating amount of total so-dium. This corresponds, in some instances, to a con-centration of total sodium of about 200 ppm. Suit-able alpha-aluminas having concentrations of leach-able sodium below 50 ppm may be obtained commercially from suppliers, such as the Norton Company. Alter-natively, suitable alpha-alumina support materials may be prepared so as to obtain leachable sodium concentrations below 50 ppm by the method described by Weber et al in U. S. Patent 4,379,134. In brief, a suitable procedure involves treatment of a support material, particularly alpha-alumina, with an organic or inorganic fluorine-containing material in any solvent capable of dissolving the fluorine-containing substance, preferably in aqueous solution, and there-;er firing the treated support material at a suit-able temperature. In the present invention, the support material may either be extruded and formed into pellets after fluorine treatment and before firing or formed, i.e., extruded, pellets may be fluorine-treated and then fired.
Most of the materials found suitable as carriers having flat surfaces may be formed by treating mater-ial having another morphology or material lacking thedesired flat surface with a suitable agent which serves to recrystallize the material to the desired form. When alpha-alumina is the support to be em-ployed in the catalyst, conversion may be effected by treating other forms of alumina, such as boehmite, 129()3~.3 aluminum hydroxide, pseudo boehmite, or beta-alumina, preferably gamma or impure alpha-alumina or mixtures of alpha and another alumina, such as mixed alpha/theta-alumina, with an organic or inorganic fluorine-containing substance capable of catalyzing the conversion or transition, i.e., recrystallizing, of the other alumina or impure alumina to alpha-alumina. Suitable fluorine-containing substances include organic or inorganic substances and may be ionic, covalent or polar covalent compo~nds as well as F2. The fluorine-containing substance should, preferably, be a somewhat volatile material or one which can be readily volatilized under process rondi tions. Examples of such fluorine-containing sub-stances which can be employed as recrystallizingagents include aluminum fluoride, ammonium fluoride, hydrofluoric acid, and dichlorodifluoromethane.
The fluorine recrystallizing agent is used in an amount sufficient to effect conversion of the alumina to alpha-alumina having at least one substantially flat surface. This will vary with such factors as the process conditions under which the conversion is effected, such as the firing t~,rerature and heating rate, as well as the bed depth of the material to be transformed, the amount of alumina being treated, the level of contamination of the alumina, and how well the firing chamber is sealed. Typically, a suitable amount of fluorine recrystallizing agent is not more than about 3 percent, by weight, based on the weight of support material being treated. Preferably, the recrystallizing agent is present in an amount of about 0.8 to about 2 percent, by weight.
To effect conversions to alpha-alumina, the fluorine-treated alumina is fired at a temperature of less than about 1,200 degrees C, preferably from a temperature of about 750 to about 1,000 degrees C.
The properties of the alpha-alumina depend not only on the firing temperature but also, in part, on the rate of heating. With lower levels of fluorine, plate-like crystals having high strength and surface area can be o~tained with rapid heating. As used herein, ~rapid heating" refers to heating from room temperature to the desired temperature in about 1 hour. However, with lower concentrations of fluorine recrystallizing agent, slower heating rates are gen-erally preferred to achieve the same type of pro-duct. The "slow heating~ treatments generally con-sist of heating from roo~ temperature to about 700 degrees C in about 0.5 to 1 hour and from about 700 degrees C to the final temperature at a rate of about 100 degrees C per hour.
Treatment of an alumina to convert it to alpha-alumina produces not only an alpha-alumina having a flat, platelet-like morphology, but also an alpha-alumina having a relatively large surface area andincreased crush strength.
The support particles are preferably formed into aggregates or "pills" of a size and configuration to be usable in com~ercially operated ethylene dioxide tubular reactors. These pills may be formed by con-ventional extrusion and firing, as discussed above.
When alpha-alumina is the support material, treatment with the fluorine recrystallizing agent may be per-formed before or after extrusion. The pills general-ly range in size from about 2 mm to about 15 mm,preferably about 3 mm to about 12 mm. The size is chosen to be consistent with the type of reactor employed. In general, in fixed bed reactor applica-tions, sizes ranging from about 3 mm to about 10 mm have been found to be most suitable in the typical 12~03~.3 tubular reactors used in commerce. The shapes of the carrier aggregates useful for purposes of the present invention can vary widely. Common shapes include spheres and cylinders, espécially hollow cylinders.
Other shapes include amphora (such as defined in U.
S. Patents 3,848,033, 3,966,639 and 4,170,569), amor-phous, Raschig rings, saddles, cross-partitioned hollow cylinders (e.g., having at least one partition extending between walls), cylinders having gas chan-nels from side wall to side wall, cylinders havingtwo or more gas channels, and ribbed or finned struc-tures. While the cylinders are often circular, other cross-sections, such as oval, hexagonal, quadrilater-al, trilateral, etcetera, may be useful.
atalYsts:

The catalysts of the present invention are con-ventional to the extent that silver is coated or deposited on and/or within a solid porous carrier.
Any known method of introducing the silver to the atalyst support may be employed. Numerous examples and procedures are given in the patents discussed above. In brief, in a coating or suspension process a slurry, preferably aqueous, of the active catlytic material, such as silver or its oxide, is applied to the support to form a coherent silver layer on the support. In the preferred impregnation process, a solution of a soluble salt or complex of silver in an amount sufficient to deposit the desired weight of silver upon the carrier is dissolved in a suitable solvent or "complexing/solubilizing" agent. This solution may be used to impregnate a porous catalyst support or carrier by immersing the carrier in the silver-containing impregnating solution. The impreg-~2~0~3~.3 nating solution is preferably introduced to the cata-lyst support in a container which has been previously evacuated. Alternatively, the support may be sprayed or sprinkled with the impregnating solution. The 5 excess solution may then be allowed to drain off or the solvent may be removed by evaporation under re-duced pressure at a suitable temperature. The silver salt or compound used to form the silver-containing impregnati:ng solution in a solvent or a complex-ing/solubilizing agent is not particularly criticaland any silver salt or compound generally known to the art which is both soluble in and does not react with the solvent or complexing/solubilizing agent to form an unwanted product may be employed. Thus, the silver may be introduced to the solvent or complex-ing/solubilizing agent as an oxide or a salt, such as nitrate or carboxylate, for example, an acetate, propionate, butyrate, oxalate, malonate, malate, maleate, lactate, citrate, phthalate, generally the silver salts of higher fatty acids, and the like.
The chemical practitioner may choose from a large number of suitable solvents or complexing/solu-bilizing agents to form the silver-containing impreg-nating solution. Besides adequately dissolving the silver or converting it to a soluble form, a suitable solvent or complexing/solubilizing agent should be ~apable of being readily removed in subsequent steps, either by a washing, volatilizing or oxidation proce-dure, or the like. The complexing/solubilizing agentr preferably, should also permit solution to provide silver in the finished catalyst to the extent of about 2 to about 60 percent silver or higher, based on the total weight of the catalyst. It is also generally preferred that the solvents or com-plexing/solubilizing agents be readily miscible with 12~03~ 3 water since aqueous solutions may be conveniently em-ployed. Among the materials found suitable as sol-vents or complexing/solubilizing agents for the pre-paration the silver-containing solutions are alco-hols, including glycols, such as ethylene glycol (U. S. Patents 2,825,701 to Endler et al and 3,563,914 to Wattimena), ammonia (U. S. Patent 2,463,228 to West et al), amines and aqueous mix~ures of amines (U. S. Patents 2,459,896 to Schwartz, 3,563,914 to Wattimena, 3,702,259 to Nielsen, and 4,097,414 to Cavitt, and carboxylic acids, such as lactic acid (U. S. Patents 2,477,435 to ~ries and 3,501,417 to DeMaio).
Typically, a silver-containing solution is pre-pared by dissolving silver in a suitable solvent orcomplexing/solubilizing agent as, for exam~le, a mixture of water, ethylenediamine, oxalic acid, sil-ver ox~de, and monoethanolamine. The solution is then mixed with support particles and drained.
~0 Thereafter the particles are suitably dried.
After impregnation, the silver-impregnated car-rier particles are treated to convert the silver salt or complex to silver metal and thereby effect deposi-tion of silver on the surface of the support. As used herein, the term "surface", as applied to the support, includes not only the external surfaces of the carrier but also the internal surfaces, that is, the surfaces defining the pores or internal portion of the support particles. This may be done by treat-ing the impregnated particles with a reducing agent,such as oxalic acid or alkanolamine and/or by roast-ing, at an elevated temperature on the order of about 100 to about 900 degrees C, preferably about 200 to about 650 degrees C to decompose the silver compound and reduce the silver to its free metallic state.

The duration of roasting is generally for a period of about 1 to about lO minutes, depending on the temper-ature used, and is commonly effectuated in a hot-air belt roaster.
The concentration of silver in the finished catalyst may vary from about 2 percent to 60 percent, by weight, based on the total weight of the catalyst, more preferably the silver concentration ranges from about 8 percent to about 50 percent, by weight~ When 10 a "high silver" content catalyst is preferred, the silver ranges from about 30 to about 60 percent, by weight. The preferred concentration for "low silver"
content catalyst ranges from about 2 to about 20-weight percent. When a catalyst having a silver 15 concentration in this preferred range is prepared, the silver is preferably introduced in a series of at least two sequential impregnation and roasting cy-cles, as discussed in greater detail below. Lower silver concentrations are preferred from a capital expense standpoint. However, the optimum silver concentration for a particular catalyst should also take into consideration increased productivity re-sulting from performance characteristics, such as catalyst activity, system efficiency and the rate of catalyst aging. In many instances higher concentra-tions of silver are preferred since they demonstrate levels of enhanced performance, particularly catalyst stability, which compensates for the greater capital expenditure~

~290~ 3 Efficiency-Enhancinq Compound.

A preferred aspect of the present invention includes an efficiency-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair. The term "redox-half reaction"
is defined herein to mean half-reactions like those found in equations presented in tables of standard reduction or oxidation potentials, also known as standard or single electrode potentials, of the type found in, for instance, "Handbook of Chemistry", N.
A. Lange, Editor, McGraw-Hill Book Company, Inc., pages 1213-1218 (19611 or "CRC Handbook of Chemistry and Physics", 65th ~dition, C~C Press, Inc., Boca Raton, Florida, pages D155-162 (1984). The term "redox-half reaction pair" refers to the pairs of atoms, molecules or ions or mixtures thereof which undergo oxidation or reduction in such half-reaction equations. A member of a redox-half reaction pair is, therefore, one of the atoms, molecules or ions that appears in a particular redox-half reaction e~uation. Such terms as redox-half reaction pairs are used herein to include tnose members of the class of substance which provide the desired performance enhancement, rather than a mechanism of the chemistry occurring. Preferably, such compounds, when associ-ated with the catalyst as calts of members of a half-reaction pair, are salts in which the anions are oxyanions, preferably an oxyanion of a polyvalent atom; that is, the atom of the anion to which oxygen is bonded is capable of existing, when bonded to a dissimilar atom, in different valence states. Potas-sium is the preferred cation and the preferred anions are nitrate, nitrite and other anions capable of undergoing displacement or other chemical reaction lZ90~3~3 and forming nitrate anions under epoxidation or cata-lyst preparation conditions. Preferred salts include KNO3 and RNO2, with RNO3 being most preferred.

Introduction Of Efficiency-Enhancing Salt To The Carrier:

The efficiency-enhancing salt of a member of a redox-half reaction pair may be introduced to the catalyst in any known manner. Various sequences of impregnating or depositing silver and efficiency-enhancing salt on the surfaces of the carrier may be employed. Thus, impregnation and deposition of sil-ver and an efficiency-enhancing salt of a member of a redox-half reaction pair may be effected coinciden-tally or sequentially, i.e., the salt or salts may be deposited prior to, during or subsequent to silver addition to the carrier. When more than one salt of a member of a redox-half reaction pair is employed, they may be deposited together or sequentially. It is preferred, however, to introduce the salts to the support in a single solution, rather than use sequen-tial treatments using more than one solution and a drying step between impregnation steps, since the latter technique may result in leaching of the first introduced salt by the solution containing the second salt. Typical, and in many cases preferred, of such methods include concurrent, or coincidental, impreg-nation in which the solution which is used to impreg-nate the support with silver also contains at leastone dissolved efficiency-enhancing salt member of a redox-half reaction pair. This procedure permits introduction of both the silver compound and the efficiency-enhancing salt simultaneously to the sup-port in a single step and solution. The other com-1~013 129(~ .3 monly employed method is the sequential impregnationof the support in which initial introduction of the silver-containing solution or efficiency-enhancing salt solution (depending upon the sequence employed) is followed by drying of the silver-containing sup-port (and heating and/or chemical reduction of the silvet if this is the first added substance). This support is then impregnated with a solution of the second substance, that is, the efficiency-enhancing salt (if the silver was the first added substance).
In order to perform the former procedure, i.e., coin-cidental impregnation, the efficiency-enhancing salt must be soluble in the same solvent or complex-ing/solubilizing liquid used with the silver-impreg-15 nating solution. With the sequential procedure inwhich the silver is added first, any solvent capable of dissolving the salt which will neither react with the silver nor leach it from the support is suit-able. Aqueous solutions are generally preferred, but organic liquids, such as alcohols, may also be em-ployed. Suitable procedures for effecting introduc-tion of the efficiency-enhancing salt to the solid support may be found in many of the patents listed above.
In some instances, the coincidental method of preparation of the catalys~ is decidedly less prefer-red or may not be used as, for example, where a bari-um, calcium or magnesium salt is intended to be solu-bilized and the solution contains materials which may precipitate the cation as, for instance, a carboxylic acid or dicarboxylic acid such as oxalic acid.
The salt of a member of a redox-half reaction pair is added in an amount sufficient to enhance the efficiency of the epoxidation reaction. The precise amount will vary depending upon such variables as the 12~0~3~.3 gaseous efficiency-enhancing member of a redox-half reaction pair of a redox-half reaction and concentra-tion thereof employed, the concentration of other components in the gas phase, the amount of silver 5 contained in the catalyst, the surface area of the support, the process conditions, e.g., space velocity and temperature, and morphology of support. General-ly, however, a suitable range of concentration of the added efficiency-enhancing salt, calculated as cat-ion, is about 0.01 to about S percent, preferablyabout 0.02 to about 3 percent, by weight, based on the total weight of the catalyst. Most preerably the salt is added in an amount of about 0.03 to about 2 weight percent.
It has been noted that when conventional analyses have been conducted with catalysts prepared by co-impregnation with silver and efficiency-enhancing salt, not all th~ anion associated with the cation has been accounted for. For example, cata-lysts prepared by co-impregnation with a potassium nitrate solution have been analyzed by conventional techniques and about 3 ~oles of the nitrate anion have been observed for every 4 moles of the potassium cation. This is believed to be due to limitations in the conventional analytical techniques and does not necessarily mean that the unaccounted for anions are not nitrate. For this reason, the amount of the efficiency-enhancing salt in the catalyst is given, in some instances, in terms of the weight percentage of the cation of the efficiency-enhancing salt (based on the weight of the entire catalyst), with the un-derstanding that the anion associated with the cation i5 also present in the catalyst in an amount roughly proportional (on a molar basis) to the cation.

~2 ~ 0~.3 As indicated above, when the catalyst is in-tended to contain higher concentrations of silver, for example, equal to or above about 30 percent, by weight, it is generally preferred to ~se multiple 5 cycles of impregnation and reduction to elemental silver. This seems to result in a more uniform dis-tribution of silver throughout the catalyst pill. As with the catalyst containing lower amounts of silver introduced in a single impregnation, the introduction 10 of the efficiency-enhancing salt of a member of a redox-half reaction pair may also be introduced in a sequential or coincidental procedure. Regardless of the method employed, a first cycle includes impregna-tion only with silver in an appropriate complex-ing/solubilizing agent followed by reduction tometallic silver, such as by roasting. ~This is designated a "silver only" procedure.) If the se-quential procedure is to be followed, the first cycle of impregnation and reduction is repeated one or more times. The final step includes impregnation with a solution of the efficiency-enhancing salt of a member of a redox-half reaction pair only, followed by draining and drying, as discussed above.
When pre~aring a catalyst containing a high concentration of silver and the coincidental or con-current procedure is employed, the first cycle is the same as with the sequential procedure, i.e., an im-pregnation with silver and reduction (silver only).
This is then followed either directly by a conven-tional coincidental impregnation (i.e., impregnationwith a solution containing both silver in a soluble form and the efficiency-enhancing salt of a member of a redox-half reaction pair, followed by a reduction of silver to its elemental form, as by roasting) or by one or more repetitions of the impregn~tion cycle ~2~ .3 with a silver only procedure interposed between the first silver only cycle and the coincidental impreg-nation and reduction cycle. Suitable results have been obtained with both the sequential and coinciden-tal procedures with two silver impregnation cycles,although theré are indications that greater amounts of silver with more uniform distribution of silver throughout the pill can be obtained by three or pos-sibly more silver-impregnation cycles. High silver-containing catalysts prepared by the coincidentalimpregnation technique provide somewhat better per-formance than those pr~pared by the sequential tech-nique.

~Poxidation Procedure:

As in conventional processes of this type, an alkene and an oxygen-containing gas are brought to-gether in a reactor in the presence of a suitable epoxidation catalyst under epoxidation conditions.
Typical epoxidation conditions include temperatures within the reaction zone of the reactor on the order of about 180 to 300 degrees C and pressures from about 1 to about 30 atmospheres.
The gaseous efficiency-enhancing member of a redox-half reaction pair of a redox-half reaction pair may generally be supplied to the reaction zone with~n the reactor by introducing the component to the feedstream containin~ alkene and oxygen. Under commercial epoxidation conditions, such as those used in the present invention, the feedstream also con-tains a gas phase halogen compound, such as an alkyl halide, a hydrocarbon, and, when the effluent stream from the reactor is recycled, unreacted alkene. When recycle of the effluent stream is used, carbon diox-~2~0~3~ 3 ide may also be present. The presence and amount of carbon dioxide depends on, among other things, whether a scrubbing device is used.
The terms "gaseous member of a redox-half reac-5 tion pairn, "gaseous efficiency-enhancing member of a redox-half reaction pair of a redox-half reaction pair", or like terms referred to herein have a mean-ing similar to that for the "salt of a member of a redox-half reaction pair" or like terms, defined 10 above. That is, these terms refer to members of half-reactions, represented in standard or single electrode potential tables in standard reference texts or handbooks which are in a gaseous state and are substances which, in the reaction equations represented in the texts, are either oxidized or re-duced. The preferred gaseous efficiency-enhancing materials are compounds containing an element capable of existing in more than two valence states, prefer-ably nitrogen and another element which is, prefer-ably, oxygen. Examples of preferred gaseous effi-ciency-enhancing member of a redox-half reaction pairs of redox-half reaction pairs include at least ' 2~ N2O4, ~23 or any gaseous substance capable of forming one of the aforementioned gases, 25 particularly NO and NO2, under epoxidation condi-tions, and mixtures of one of the foregoing, particu-larly NO, with one or more of CO, PH3, SO3 and SO2.
NO is most preferred as the gaseous efficiency-enhancing member of a redox-half reaction pair.
Although in some cases it is preferred to employ members of the same half-reaction pair in the reac-tion system, i.e., both the efficiency-enhancing salt member associated with the catalyst and the gaseous member in the feedstream, as, for example, with a 35 preferred combination of potassium nitrate and nitric - ~ ~90~3~.3 oxide, this is not necessary in all cases to achieve satisfactory results. Other preferred combinations, such as RNO3/N2O3, RNO3/NO2, KNO3/N2O4, RNO2/NO, KNO2/NO2, and KNO3/a mixture of SO2 and NO, may also be employed in the same system. In some instances, the salt and gaseous members may be found in differ-ent half-reactions which represent the first and last reactions in a series of half-reaction equations of an overall reaction.
The gaseous efficiency-enhancing member of a redox-half reaction pair of a redox-half reaction pair is also present in an amount sufficient to en-hance the performance, such as the activity of the catalyst, and, particularly, the efficiency of the epoxidation reaction. The precise amount is deter-mined, in part, by the particular efficiency-enhancing salt of a member of a redox-half reaction pair used and the concentration thereof, the particular alkene undergoing oxidation, and by other factors noted above which influence the amount of efficiency-enhancing salt of a member of a redox-half reaction pair. Typically a suitable concentration of the gaseous member of a redox-half reaction pair foL
epoxidation of most alkenes, including propylene, is about 0.1 to about 2,000 ppm, by volume, when N2 is used as ballast. When a preferred gaseous member of a redox-half reaction pair, such as N~, is used in the epoxidation of propylene, the preferred concen-tration i5 about 5 to about 2,000 ppm, by volume, with an N2 ballast. However, when ethylene is being oxidized, a suitable concentration is in the range of from about 0.1 to about 100 ppm, by volume, of the gaseous fecdstream components; Preferably, when ethylene is being oxidized, the gaseous efficiency-enhancing member of a redox-half reaction pair is ~290~3~.3 present in an amount of about 1 to about 80 ppm when about 3 percent, by volume, CO2 is present. When nitric oxide is employed as the gaseous efficiency-enhancing member of a redox-half reaction pair in an 5 ethylene epoxidation system, it is present in an amount of about 0.1 to about 60 ppm, preferably about 1 to about 40 ppm, when CO2 is present.
The "oxygen-containing gas" employed in the reaction may be defined as including pure molecular 10 oxygen, atomic oxygen, any transient radical species derived from atomic or molecular oxygen capable of ~xistence under epoxidation conditions, mixtures of another gaseous substance with at least one of the foregoin~, and substances capable of forming one of 15 the foregoing under epoxidation conditions. Such oxygen-containing gas is typically introduced to the reactor either as air, commercially pure oxygen or other substance which under epoxidation conditions both exists in a gaseous state and forms molecular 20 oxygen. The gaseous components which are supplied to the reaction zone, or that region of the reactor where reactants and catalyst are brought together under epoxidation conditions, are generally combined before being introduced to the reactor. The reactors in which the process and catalyst of the present invention are employed may be of any type known to the art. A brief description of several of the reac-tor parameters which may be used in the present in-vention are presented below.
In addition to an alkene, oxygen, and the gas-eous efficiency-enhancing member of a redox-half reaction pair, the feedstream also contains a per-formance-enhancing halogen-containing compound, pre-ferably an organic halide, including both saturated 35 and unsaturated halides, such as ethylene dichloride, 2 ~0~ 3 ethyl chloride, vinyl chloride, methyl chloride and methylene chloride. Preferably, in commercial pro-duction, ethylene chloride is employed as the halo-gen-containing compound. The amount of halide em-5 ployed will vary depending upon a variety of factors,including the particular alkene being oxidized and the concentration thereof, the particular efficiency-enhancing salt and gaseous members of redox-half reaction pairs and the concentrations thereof, as 10 well as other factors noted above as influencing the amount of efficiency-enhancing salt and gaseous com-pound. However, a suitable range of concentration for the halogen-containing compound in the oxidation of most alkenes, including propylene, is typically about 0.1 to about 2,000 ppm, b~ volume, of the gas-eous makeup feedstream. When ethylene is oxidized, the range of concentration for the halogen-containing compound is, however, about 0.1 to about 60 ppm, by volume. In addition, a hydrocarbon, such as ethane, 20 can be included in the feedstream. The feedstream may also contain a ballast or diluent, such as nitro-gen, or other inert gas, particularly when air is used as the oxygen-containing gas. Varying amounts of carbon dioxide and water vapor may also be present, depending upon whether means have been pro-vided to remove such substances from the effluent stream prior to combination of at least a portion of the effluent stream with the inlet stream. Other than the gaseous efficiency-enhancing member of a redox-half reaction pair of a redox-half reaction pair, the other components are typically present in amounts shown in the following tables for propylene and ethylene.

~ 2~0~.3 Volume Percent (or ppm) Component for Propylene Oxidation propylene about 2 to about 50 5 oxygen about 2 to about 10 alkyl halide about 5 to about 2,000 ppm hydrocarbon 0 to about 5 carbon dioxide up to about 15 nitrogen or remainder.
10 other ballast gas, e.g., methane Volume Percent (or ppm) 15 ComPonent for Ethvlene Oxidation ethylene at least about 2, often about 5 to about 50 oxygen about 2 to about 8 20 alkyl halide about 0.1 to about 60 ppm hydrocarbon 0 to about 5 carbon dioxide up to about 7 nitrogen or remainder.
other ballast 25 gas, e.g., methane When higher alkenes, such as those previously - discussed, are epoxidized, conditions and concentra-tions typically used for the epoxidation of propylene may be employed.

2 ~ .3 Standard Alkene Oxide Process Test Conditions:

The successful commercial production of alkene oxides, particularly ethylene oxide, by the silver-catalyzed oxidation of alkene, particularly ethylene, depenas upon a variety of factors. Many of these factors influence, either directly or indirectly, the efficiency of the catalytic system, the activity or the aging rate of the catalyst. The manner in which catalysts and catalytic systems are evaluated in the laboratory strongly influences the values obtained for these parameters. Techniques and experiments designed to assess such catalysts and catalytic sys-tems commonly employ microreactors (i.e., tiny tubu-lar reactors for testing crushed catalyst particles) or back-mixed autoclaves of the 8erty type (i.e., larger reactors which test full-sized catalyst pel-lets and generally employ full gas recycle) as de-scribed in Figure 2 of the article by J. M. Berty,"Reactor For Vapor Phase-Catalytic Studies", Chemical Engineerinq ~rogress, _, Number 5, pages 78-84 (1974), and particularly Figure 2. Microreactors are capable of yielding, in most test situations, the ~5 highest efficiency numbers, typically approximately the same as or somewhat greater than those obtainable in commercial tubular reactor operations employing the same catalysts in non-crushed condition. Back-~ixed autoclaves commonly provide lower efficiency values because, although conditions can be varied, generally the entire catalyst is exposed to the out-let gas which has the lowest concentration of reactants and the highest concentration of products. Values obtained using one type of reactor 3s are seldom identical to those obtained in another 2 9~ .3 reactor system. As a result, claims of superior results or the desirability of one catalyst over another are preferably based on tests conducted under controlled and comparable conditions.
Although the conditions set forth supra may be employed both for reactors employed in commercial production as well as those employed in a laboratory, as a basis of comparison, the catalysts and catalytic systems for epoxidation of ethylene employed in the examples set forth below have been tested under com-parable conditions known as Standard Alkene Oxide Process Test Conditions, or Standard Test Conditions (referred to hereinafter as STC). The STC employed for testing and characterizing the catalysts and the catalytic systems of the present invention involve the use o a standard back-mixed bottom-agitated "Magnedrive" autoclave or Berty autoclave, as de-scribed above.
In discussing the enhancement of efficiency provided by the present invention, it may be noted that, when an efficiency-enhancing amount of a salt of a member redox-half reaction pair is employed, an efficiency of at least about 84 percent is obtained under Standard Test Conditions. "Standard Test Con-ditions" for ethylene may be defined as comprising the following: by volume, 30 percent C2~4, 8 percent 2' 5 ppm ethyl chloride, 5 ppm, by weight, NO, no added C2H6 or CO2, N2, ballast, 240 degrees C, 275 psig, gas hourly space velocity (GHSV) = 8,000 hr 1 Although the present inven~ion can be used with any size and type of alkene oxide reactor, including both fixed bed and fluidized bed reactors known to the art, it is contemplated that the present inven-tion will find most widespread application in standard fixed bed, multi-tubular reactors. These ~2~

generally include wall-cooled as well as adiabatic or non-wall-cooled reactors. Tube lengths may typically range from about 5 to about 60 feet but will frequently be in the ran~e of from abou~ 15 to about 40 feet. The tubes may have internal diameters from about 0.5 to about 2 inches and are expected to be typically from about 0.8 to about 1.5 inches. GHSV
generally range from about 16,000 to about 1,000 hr~
1. Typically GHSV values range from about 2,000 to about 8,000 hours~l at pressures from about 1 to about 30 atmospheres, commonly about 10 to about 25 atmospheres.
While the invention is susceptible to various modifications and alternative forms, certain specific embodiments thereo~ are described in the examples set forth below. It should be understood, however, that these examples are not intended to limit the inven-tion to the particular forms disclosed but, on the contrary, the invention is to cover all modifica-tions, equivalents and alternatives falling within the spirit and scope of the invention.

Example 1 - Preparation Of A
Fluorine-Containinq AlPha-Alumina Support:
Approximately 1,200 grams of 1/4 inch hollow gamma-alumina pills or rings (obtained from Norton Corporation as Alumina 6~73) were soaked for one-half hour in 1 molar NH4F with occasional shaking to li-berate bubbles that formed during impregnation.
Excess solution was drained fro~ the rings, which were then dried overnight at 120 degrees C. The dried rings were distributed between four 3 inch diameter x 6 inch deep cylindrical alumina crucibles and were fired in a P. ~. H. high-temperature fur-12~()3~3 nace. Lids for the crucibles were placed askew sothat crucible openings were covered approximately 70 percent to maintain a fluoride atmosphere in the crucible but at the same time permit escape of excess fluoride. The firing schedule was one hour to raise the temperature to 700 degrees C, four hours to raise the temperature from 700 to 1,100 degrees C, and a hold temperature at 1,100 degrees C for one hour.
The product had a surface area of 1.56 m2/g and a sodium content of less than 50 ppm.

Example 2 - Sequential Preparation Of A Potassium Nitrate-Containinq 5upPorted Silver CatalYst:

Formation of a potassium nitrate-containing supported silver catalyst resulted from a multi-step procedure in which a support was initially impreg-nated with a silver-containing solution, the impreg-nated support was roasted, and the silver-inpregnated catalyst was thereafter im~regnated with a potassium nitrate solution and then dried.
The silver-containing solution used in the first step was prepared by dissolving 51.49 grams ethylene-diamine in 51.03 grams of distilled water and stir-ring the mixture for a period of 10 minutes. To thestirred solution was slowly added 51.56 grams of oxalic acid dihydrate. The resulting solution was stirred for 10 minutes. To this solution was added, in portions, 90.34 grams silver oxide. ~he resulting silver-containing solution was thereafter stirred for an additional hour and 18.07 grams of monoethanol-amine was then added to the stirred silver-containing solution. Stirring was continued for an additional 10 minutes. This solution was then diluted to a total volume of 437 ml by addition of distilled 1290~ 3 water.
In a catalyst-impregnation tube were placed 177.85 grams of an a~pha-alumina carrier, similar to that prepared in Example 1. A catalyst-impregnation tu~e is an elongated tube, which in use is arranged vertically. The upper end of the tube is provided with àn inlet to supply impregnation solution to the carrier contained in the tube and the lower end with an outlet from which solution may be drained. The tube is also provided with a means to connect the tube to a vacuum source. Prior to introduction of impregnation solution the tube was evacuated. The solution described immediately above was slowly pour-ed into the tube to totally immerse the support. The carrier was allowed to remain in the impregnating solution ~or about 1 hour to achieve saturation of the support. The unabsorbed solution was thereafter drained from the support with draining continuing for about 30 minutes. The wet, impregnated carrier was ~o then roasted in a hot-air belt roaster for 2.5 min-utes at 500 degrees C (66 SCF~ air flow) to produce a catalyst containing 11.39 percent silver.
Upon cooling, 44.57 grams of the roasted, im-pregnated carrier was placed in an impregnation tube and covered with a solution formed by dissolving 2.08 grams potassium nitrate in 100 ml distilled water.
After covering the roasted silver-containing carrier with the KNO3-containing solution and allowing to stand for 15 minutes, the catalyst pellets were 3~ drained on a funnel for 5 minutes. The resulting drained pellets were dried in an oven for 2 hours at 1~0 degrees C, producing a catalyst containing 0.46 percent ~, calculated as 1.20 percent KNO3, by weight.

~2~ .3 Example 3 - Preparation Of A Potassium Nitrate-Containing Silver Catalyst By A Co-Impregnation Technique:

A co-impregnation solution was prepared by plac-ing 18.77 grams of ethylenediamine into a 400 ml beaker and mixing therewith 25 grams of distilled water to form a solution. To the stirred solution was slowly added 18.7 grams oxalic acid and, with continuous stirring, 35.2 grams of silver oxide was slowly added. When solution was complete, 6.55 gra~s of monoethanolamine were added directly to the solu-tion. To the silver-containing solution were added 7.14 grams of a potassium nitrate solution, 10 per-cent with respect to potassium (0.258 grams KNO3/gsolution), To the resulting solution was added suf-ficient water to dilute the solution to 100 ml.
To make 100 ml of finished catalyst, 53.5 grams of an alpha-alumina support material of the type prepared in Example 1 but fired at a temperature of 1,000 degrees C in the form of quarter-inch ring extrudate and having a pore volume of 0.62 g H2O/g support were placed in an impregnation container. A
source of vacuum was attached to the container and evacuated and thereafter the silver/potassium-con-taining impregnating solution was added, completely covering the carrier. After about one hour the ex-cess solution was drained from the catalyst.
~oasting of the impregnated catalyst was con-ducted as indicated above in Example 2. The result-ing catalyst included, by weight, 17.5 percent silver and, as calculated, about 1 percent potassium ni-trate.

~ 2 ~ 3 Example 4 - Sequential Preparation Of A Potassium Nitrate-Containing SuPported Hiqh Silver Concentration CatalYst:

A solution containing 17.5 9 ethylenediamine, 17.3 g distilled water, 17.5 9 oxalic acid, 30.7 g silver oxide, 6.1 9 monoethanolamine, diluted to 125 ml, was prepared in the manner described in Example 2.
Into a catalyst impregnation tube were placed 43.9 9 of an alpha-alumina carrier, similar to that prepared in Example 1, and having a surface area of 1.12 m2/g, a pore volume of 0.8 cc/g, less than 50 ppm, by weight, leachable sodium, and a platelet morphology. The support pellets were initially vacu-um-impregnated at 28 inches mercury vacuum, releaslng the vacuum when the pellets were completely covered with the aqueous silver amine solution, permitting them to stand in the amine solution for an additional hour at 1 atmosphere before draining. The impreg-nated pellets were then belt-roasted at 500 degrees C
in an oven having an air flow of 66 SC~H for 2.5 minutes. The material contained 14.9 percent silver as determined by weight gain. This material was then impregnated a second and third time with fresh sil-ver/amine solution having the composition indicated above. The impregnations and belt-roastings were conducted in the same manner as descrihed above. The catalyst material was then impregnated with KNO3 by placing 67.4 g of the silver-impregnated pellets into a solution containing 2.1 9 KNO3 dissolved in 100 ml distilled water. The KNO3-impregnated silver cata-lyst material was then dried at 120 degrees C for 1 hour to yield a catalyst containing, by weight, 34.7 percent silver and 0.33 percent K (calculated as 0.8 ~2~0~ .3 percent KNO3), as determined by weight gain.

Example 5 - Coincidental Preparation Of A Potassium Nitrate-Containing Supported Hiqh Silver Concentration CatalYst:

A silver impregnation solution was preparea in a manner similar to that described in Example 2 by mixing 196.8 9 ethylenediamine, 195.0 g distilled water, 197.1 9 oxalic acid, 345.2 9 silver oxide, 69.1 9 monoethar.olamine and diluting to a total vol-ume of 780 ml with distilled water. After evacuation of an impregnation tube containing pellets of an alpha-alumina support material (293.1 9) similar to those described in Example 1 and having a B. E. T.
surface area of 1.16 m2/~ as measured by a QUANTA-SORBTM apparatus, the pellets were impregnated by allowing them to stand in the silver impregnation solution for a period of 1 hour and then draining.
The impregnated pellets were then belt-roasted at 500 degrees C in a 66 SCFH air flow for 2.5 minutes. As determined by gain in weight, the material contained 24.6 percent silver.
A co-impregnation solution was prepared in a manner similar to that described in Example 3 by mixing 37.5 g ethylenediamine, 37.2 9 distilled water, 37.6 9 oxalic acid, 65.9 9 silver oxide, 13.2 g monoethanolamine, and 0.80 9 potassium nitrate and diluting to 150 ml total solution with distilled water. The silver-impregnated catalyst pellets (77.8 g) were i~pregnated by immersing them in the sil-ver/potassium nitrate-impregnating solution for 1 ho~r and then draining. The resulting pellets were then belt-roasted as described above. ~he pellets resulting from the two impregnations yielded a mater-~2~0~ 3 ial, as determined by an analysis, containing, by weight, 39.8 percent silver and 0.098 percent K (cal-culated as 0.25 percent KNO3).

Examples 6 to 11 - Production of Ethylene Oxide With Potassium Nitrate-Containing SupPorted Silver Catalyst:

The examples set forth below were conducted employing catalyts using carriers of the type pre-pared in Example 1, the catalysts themselves being prepared in the manner described in Examples 2 and 3 and identified as being prepared hy either a sequen-tial (S) procedure or a coincidental impregnation (C) procedure. The epoxidation studies for which data are presented below were conducted in a continuously stirred tank reactor, also known as a back-mixed autoclave of the type described above. The procedure involved charging approximately 80 ml of catalyst to the autoclave. The volume of catalyst was measured in a one inch I. D. graduated cylinder after tapping the cylinder several times to thoroughly pack the catalyst. The weight of the catalyst was noted and is indicated in the table appearing below. The back-mixed autoclave was heated to about reaction tempera-ture in a nitrogen flow of 11.3 SCFH with the fan operating at about 1,500 rpm. The nitrogen flow was then discontinued and the feedstream was introduced to the reactor.
All ethylene epoxidation reactions, except where indicated otherwise, were examined under Standard Test Conditions comprising, by volume, 30 percent ~l2~0~ 3 C2H4, 8 percent 2' 5 ppm ethyl chloride, 5 ppm, byweight, NO, no added C2H6 or CO2, N2 ballast, degrees C, 275 psig, GHSV = 8,000 hr 1. The data summarized below includes surface areas of the cata-lysts, Ag and calculated KNO3 contents, maximum ob-served outlet ethylene oxide (activity), maximum observed efficiency, and aging rate.

TABLE
Pre- Maximum Maxi-para- mum Example tion S.A. % Ag % RNO3 Activity Effi-Pro- (m2/9) (E.O.) ciency cedure 6 C 0.7 lg.7 2.0 1.18 91.00 7 C 1.4 20.0 2.0 1.41 90.25 8 C 1.1 19.7 2.0 1.23 90.00 9 C 0.8 20.4 2.0 1.35 90.25 S 1.0 15.6 1.0 1.12 86.5 11 S 1.~ 15.6 2.0 1.18 88.5.

Example 12 - Production of Propylene Oxide With Potassium Nitrate-Containing Sup~orted Silver Catalyst:

Into a back-mixed autoclave, having a slightly smaller volume than the autoclave employed in the previous examples, were placed 5.0 grams (10.0 ml) of a catalyst having a support prepared as in Example 1. The support was an alpha-alumina having a surface area of 1.12 m2/g, a pore volume of 0.8 cc/g, less than 50 ppm, by weight, of leachable sodium, a resi-35 dual fluorine concentration of 0.7 percent, and a ~L2903~ 3 platelet morphology. The catalyst included, by weight, a silver concentration of 17.7 percent and a potassium concentration of 0.38 percent (calculated as 1 percent potassium nitrate). A mixture, by vol-ume, of 9.9 percent propylene, 7.75 percent oxygen, 200 ppm ethyl chloride, 200 ppm nitric oxide, 2 per-cent methane, and the remainder being nitrogen bal-last gas, was fed to the reactor at a temperature of 252 degrees C, a pressure of 25 psi and a gas hourly space velocity of 832 hr 1. After 22.5 hours, a selectivity of 47.3 percent was observed with an activity of 0.6 pounds of propylene oxide/cubic foot of catalyst/hour (corresponding to an outlet percent of propylene oxide of 0.465 percentl.

Claims

1. A process for the epoxidation of alkene in the presence of an oxygen-containing gas comprising contacting said alkene and said oxygen-containing gas under epoxidation conditions in the presence of at least one gaseous efficiency-enhancing member of a redox-half reaction pair and a supported silver cata-lyst, said catalyst comprising a catalytically effec-tive amount of silver on a solid porous support hav-ing a stability-enhancing morphology and an efficien-cy-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair, said support having a surface area of at least about 0.7 m2/g and a particulate matrix which con-tains particles having at least one substantially flat major surface.

2. The process of claim 1 wherein said effi-ciency enhancing gaseous member of a redox-half reac-tion pair and said salt member of a redox-half reac-tion pair comprise members of the same redox-half reaction.

3. The process of claim 1 wherein said at least one gaseous member of a redox-half reaction pair comprises NO, NO2, N2O3, N2O4, or a gas capable of generating one of the aforementioned gases under epoxidation conditions.

4. The process of claim 3 wherein said gas capable of generating one of the aforementioned gases generates at least one of NO and NO2.

5. The process of claim 1 wherein said at least one efficiency-enhancing salt of a member of a redox-half reaction pair comprises potassium nitrate.

6. The process of claim 1 wherein said at least one gaseous member comprises nitrogen monoxide or nitrogen oxide and said at least one salt comprises potassium nitrate.

7. The process of claim 1 wherein the support has a surface area of about 0.7 to about 7 m2/g.

8. The process of claim 1 wherein at least about 50 percent of the support particles having particle sizes of at least 0.1 micron have at least one substantially flat major surface.

9. The process of claim 8 wherein the substan-tially flat surfaces of the particles have a radius of curvature of at least about twice the major dimen-sion of the surface.

10. The process of claim 8 wherein the median pore diameter is about 1 to about 5 microns.

11. The process of claim 8 wherein the parti-cles having substantially flat surfaces have plate-let-type morphology.

12. The process of claim 11 wherein the support comprises alpha-alumina.

13. The process of claim 1 wherein the support consists essentially of alpha-alumina.

14. The process of claim 11 wherein the major dimension of substantially all the particles having platelet-type morphology is less than about 50 mi-crons.

15. The process of claim 14 wherein the major dimension of substantially all the particles having platelet morphology is less than about 20 microns.

16. The process of claim 1 wherein said alkene comprises ethylene.

17. The process of claim 1 wherein said alkene comprises propylene.

18. The process of claim 1 wherein said at least one gaseous member comprises nitrogen monoxide, said at least one salt comprises potassium nitrate, and said solid support comprises particles of alpha-alumina having a platelet-type morphology in which at least about 50 percent of the particles having par-ticle sizes greater than 0.1 micron have at least one substantially flat major surface having a radius of curvature of at least about twice the major dimension of the surface and an aspect ratio of at least about 4:1, which major dimension is less than about 50 microns, said support having a surface area of about 0.7 to about 7 m2/g and an average pore diameter of about 1 to about 5 microns.

19. A process for the epoxidation of an alkene in the presence of an oxygen-containing gas compris-ing contacting said alkene and said oxygen-containing gas under epoxidation conditions in the presence of at least one gaseous efficiency-enhancing member of a redox-half reaction pair and a solid catalyst, said catalyst comprising a catalytically effective amount of silver on a solid support having a stability-enhancing morphology and an efficiency-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair, said support comprising particles, at least about 50 percent of those particles having particle sizes greater than 0.1 micron have at least one substantially flat major surface.

20. The process of claim 19 wherein the support consists essentially of alpha-alumina and said parti-cles have a platelet morphology.

21. A catalyst suitable for epoxidation of alkene in the presence of an oxygen-containing gas comprising a catalytically effective amount of silver on a solid support and an efficiency-enhancing amount of at least one efficiency-enhancing salt of a member of a redox-half reaction pair, said inert support having a surface area of at least about 0.7 m2/g and a particulate matrix containing particles having at least one substantially flat major surface.

22. The catalyst of claim 21 wherein the cata-lyst particles are of sufficient size and shape for use in a commercial-sized tubular epoxidation reac-tor.

23. The catalyst of claim 21 wherein said at least one efficiency-enhancing salt of a member of a redox-half reaction pair comprises potassium nitrate.

24. The catalyst of claim 21 wherein the sup-port has a surface area of about 0.7 to about 7 m2/g.

25. The catalyst of claim 21 wherein about 50 percent of the support particles having particle sizes greater than 0.1 micron have at least one sub-stantially flat major surface.

26. The catalyst of claim 21 wherein the aver-age pore diameter is about 1 to about 5 microns.

27. The catalyst of claim 21 wherein the par-ticles having substantially flat major surfaces have platelet-type morphology.

28. The catalyst of claim 27 wherein the sup-port comprises alpha-alumina.

29. The catalyst of claim 21 wherein the sup-port consists essentially of alpha-alumina.

30. The catalyst of claim 28 wherein the major dimension of substantially all platelets is less than about 50 microns.

31. The catalyst of claim 30 wherein the major dimension of substantially all the platelets is less than about 20 microns.

32. The catalyst of claim 21 wherein said at least one salt comprises potassium nitrate, and said solid support comprises particles of alpha-alumina having a platelet-type morphology in which at least about 50 percent of the particles having particle sizes greater than 0.1 micron have at least one sub-stantially flat major surface having a radius of curvature of at least about twice the major dimension of the surface and an aspect ratio of at least about 4:1, which major dimension is less than about 50 microns, said support having a surface area of about 0.7 to about 7 m2/g and an average pore diameter of about 1 to about 5 microns.

33. A catalyst suitable for the epoxidation of ethylene in the presence of an oxygen-containing gas comprising a catalytically effective amount of silver on a solid support and at least one efficiency-enhancing salt of a member of a redox-half reaction pair present in an amount sufficient to provide an efficiency of at least about 84 percent under Standard Test Conditions, said support comprising a substantially inert refractory oxide having a surface area of at least about 0.7 m2/g.

34. A catalyst suitable for the epoxidation of alkene in the presence of an oxygen-containing gas comprising a catalytically effective amount of silver on a substantially inert support and of at least one efficiency-enhancing salt of a member of a redox-half reaction pair present in an amount sufficient to provide an efficiency of at least about 84 percent under Standard Test Conditions, said support compris-ing particles in which at least about 50 percent of the particles having particle sizes greater than 0.1 micron have at least one substantially flat major surface.

35. The catalyst of claim 34 wherein the cata-lyst particles are of sufficient size and shape for use in a commercial-sized tubular alkylene oxide reactor.

36. The catalyst of claim 34 wherein said at least one efficiency-enhancing salt of a member of a redox-half reaction pair comprises potassium nitrate.