Introduction and Background The present invention relates to a method for the production of fixed bed activated base metal catalysts and the use of granulated forms. These granulated forms could either be filled into the reactor as is, or they can be sintered together to form a desired structure. The common forms could include spheres, cylinders, ovals, and other forms as well. The main advantages of these catalysts are their relatively low production costs, low bulk density and high porosity.

Activated metal catalysts are known in the field of chemical engineering as Raney-type catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization and hydration reactions of organic compounds.

These powdered catalysts are prepared from an alloy of a catalytically-active metal, also referred to herein as a catalyst metal, with a further alloying component which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.

These so-called Raney alloys are generally prepared by the ingot casting process. In that process a mixture of the catalyst metal and, for example, aluminum are first melted and casted into ingots.

Typical alloy batches on a production scale amount to about ten to one hundred kg per ingot. According to DE 21 59 736 cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0. 2/s.

In contrast to this, rates of 102 to 106 K/s are achieved in processes where rapid cooling is applied (for example an atomizing process). The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. W. Chan, P.

Haasen, E. J. Kramer, Vol. 15, Processing of Metals and Alloys, 1991, VCH-Verlag Weinheim, pages 57 to 110).

A process of this type is used in EP 0 437 788 B 1 in order to prepare a Raney alloy powder. In that process the molten alloy at a temperature of 50 to 500°C above its melting point is atomized and cooled using water and/or a gas.

It is also possible to produce rapidly cooled alloys where the molten alloy is added dropwise to a liquid coolant, such as water, to form rapidly cooled granules. These rapidly cooled granules may be ground for use in the production of catalysts.

To prepare a catalyst, the Raney alloy is first finely milled if it has not been produced in the desired powder form during preparation. Then the aluminum is partly (and if need be, totally) removed by extraction with alkalis such as, for example, caustic soda solution to activate the alloy powder. Following extraction of the aluminum the alloy power has a high specific surface area (BET), between 20 and 100 m2/g, and is rich in active hydrogen.

The activated catalyst powder is pyrophoric and stored under water or organic solvents or is embedded in organic compounds which are solid at room temperature.

Powdered catalysts have the disadvantage that they can be used only in a batch process and, after the catalytic

reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration.

Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed. Thus, for example, coarse particulate Raney alloys, i. e. , Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution. Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.

Substantial disadvantages of catalysts prepared by these known methods are their poor mechanical stability of the activated outer layer, their low level of porosity, and their relatively very low percentage of activated metal.

Since only the outer layer of these catalysts are catalytically active, abrasion leads to rapid deactivation and renewed activation of the deeper lying layers of alloy with caustic soda solution only leads, at best, to partial reactivation.

Patent application EP 0 648 534 B1 describes shaped, activated Raney metal fixed-bed catalysts and their preparation. To avoid the disadvantages described above, e. g. , poor mechanical stability resulting from activating the outer layer of the particle, these known catalysts were stabilized with the appropriate amount of binder.

These known catalysts were prepared by forming a homogeneous mixture of at least one catalyst alloy powder, pore builders, and a binder. The catalyst alloys each contain at least one catalytically active catalytic metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components can be used as binders. The use of binder

material in an amount of 0.5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation.

After shaping the catalyst alloy and the binder with conventional shaping aids and pore producers, the freshly prepared items which are obtained are calcined at temperatures below 850°C. As a result of sintering processes in the finely divided binder, this produces solid compounds between the individual particles of the catalysts alloy.

These compounds, in contrast to catalyst alloys, are non- extractable or only extractable to a small extent so that a mechanical stable structure is obtained even after activation.

As taught in european patent EP 984831 B1, rapidly cooled alloys with very fine phase structures can be used to produce formed bodies without metallic binders and such technology may also be applicable to the current invention.

An object of the present invention is therefore to provide fixed bed activated base metal catalysts in the form of designed granules which largely avoids the disadvantages of the above known fixed-bed catalysts.

Summary of the invention Subject of the invention is a method for the preparation of fixed bed activated base material granules consisting via mixing of - a precursor alloy powder - optionally with an organic binder and/or - optionally with an inorganic binder to form granules that are dried, - calcined - optionally promoted by the addition of metal salts - activated in a caustic solution - optionally promoted by the addition of metal salts, - whereby the precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one/or more promoters.

The above and other objects of the invention are achieved by producing granules out of particles of the desired alloys along with organic and/or inorganic binders, calcining these granules, and activating them in caustic solution in order to make them catalytic active.

Depending on the conditions of catalyst preparation, the desired catalyst properties, and the catalyst alloys being used, the use of organic and/or inorganic binders may or may not be necessary to obtain the appropriate catalyst granules.

These granules are formed by mixing the desired alloy powder (s) with organic and/or inorganic binders and water in such a way that the particles agglomerate into granules.

These granules can be made by mixing the above mentioned mixture between two parallel plates (plate granulator), or

in any other suitable pieces of equipment such as Eirich or Lodige mixers.

Such mixers form granules by the use of aggitators in combination with a rotating bottom plate, only a rotating bottom plate where variously oriented baffles may be put in place, or only aggitators.

It would also be possible to use aggitators, rotating bottom plates, and their combination in various sequences in order to create various effects with the structure of the resulting granules.

After mixing, the granules are dried, calcined, activated in caustic, and washed.

The organic binder can be chosen such that it expands or , foams up"during either mixing, drying or calcination thereby producing a metallic foam structure that exhibits a high porosity while maintaining its mechanical strength.

The major advantages of this invention are its low bulk density, its high porosity, its relatively high percentage of activated metal, its relatively low production cost, and the activity these materials exhibit per kilogram of metal as well as the activity the have on a per liter of catalyst basis.

The performance of these catalysts may be enhanced by the addition of promoters either in the alloy before activation or their adsorption of the active catalyst after it has been leached with alkalis. Suitable promoters include metallic elements from the groups 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8,1B, 2B, 3A, 4A, 5A, the rare earth elements and 6A of the periodic table.

The resulting granules of the above mentioned material may be screened to remove the remaining powder and this powder may also be recycled back into granulation process so that

the yield of the granules with respect to the alloy powder is very high and commercially viable.

Another aspect of this invention is that the granulation can be started with one type of powder and the type of powder added to the granulation process may be changed as the granules reach a specific size. This change of granulation powder may be performed a number of times and this could be done continuously during the granulation, or the granules may be removed, dried and optionally calcined before they are added again to the granulation apparatus for the addition of new granulation powders.

In these two ways, one could optain granules with layering effects that have specific types of powders and/or various mixtures thereof at different depths of the granules. The approprite granulation powders for this process include Raney-type catalytic metal/A1 alloys, inert powders, pore builders and binders. The Raney-type catalytic metal/Al alloys may be slowly cooled or rapidly cooled alloys as described above, and its average particle size may range from-1 to 200 Am or more as required by the desired catalyst properties.

During granulation, the granules may be heated for the removal of the suspending liquid (e. g. , water) during granulation so that the granules may proceed directly to calcination and/activation. The suspending liquid may also be left in the granules after granulation and in this case it may be removed by drying before or during calcination.

The suspending liquid may be left in the granule so as to facilitate the formation of granule clusters that provide structures that pack looser in a reactor and lead to lower pressure drops in comparison to other fixed bed geometries.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy <BR> <BR> can be either slowly_c_oled r_rpidly cooled v a contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.

The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, lib, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowlZ cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in a Lodge mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and Iva.

The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder in a Lodge mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be e t_er slowly_cooled or rapidly-c--o-oled-via-contact quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.

The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist Ni, Co, Cu, Fe or combinations therof that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa.

The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. This granulation process, the choice of the possible binders, the drying procedure and the calcination procedure are performed in such a way that the granules form foam-type structures with high macroporosity. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.

The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib,

IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. After activation, the catalyst can be promoted by the addition of salts of one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, Ilia and IVa to the catalyst. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements and the caustic leachable component can consist of Al, Si, Zn or mixtures therof.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. The precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.

The precursor alloy can be comprised of a catalytic component, a caustic leachable component and one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb,

VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof. In this case, the catalyst can be promoted by the addition of one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa to the alloy before caustic activation.

According to the invention the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution. After activation, the catalyst can be promoted by the addition of salts of one or more elements from the periodic groups la, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, lib, IIIa and IVa to the catalyst. The precursor alloy can be either slowly cooled or rapidly cooledlvia contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water. The precursor alloy can be comprised of a catalytic component, a caustic leachable component and one or more promoters. The catalytic component can consist of one or more metals from groups VIII and Ib of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa and IVa. The caustic leachable component can consist of Al, Si, Zn or mixtures therof. In this case, the catalyst can be promoted via both the addition of one or more promoters to the alloy before activation and the addition of salts of one or more promoters to the catalyst afer caustic activation.

According to the invention the fixed bed granules of catalyst precursors are formed by the addition of one or more Raney-type alloy (s) to a mixture of an organic binder (e. g. , polyvinyl alcohol), water, optionally an inorganic binder (e. g. , Ni, Co, Fe, Cu or other metal powders),

optionally promoters, and optionally pore builders followed by the aggitation of this mixture for the formation of granules. The aggitation of this mixture into granules can be performed by placing the powder between two plates where one rotates differently than the other or by mixing this powder with aggitators, a rotating bottom plate with and without baffles and/or with both the aaaitator and the forementioned rotating bottom plate together. Plate granulators, Eirich mixers und Lodge mixers are examples of such equipment that may be used in this granulation process. These resulting granules are then calcined to the desired temperature (e. g. from 100 to 1200°C), activated with an alkali leaching solution (e. g. an aqueous caustic solution), and washed with basic (e. g. , caustic) and/or pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst. The choice of an organic binder, the types of other components, the ratio of the various components and the treatment of the resulting granules may be done so that the final fixed body foams up and create a metallic foam structure that has a high porosity and lower bulk density. This higher porosity can lead to a more complete leaching process and it leads to a catalyst with a higher activity for catalytic chemical reactions.

The bulk density of the resulting fixed bed catalyst is very important for highly active catalysts. While the standard fixed bed activated base metal catalysts have bulk densities ranging from 2.4 to 1.8 kg/l, bulk densities similar to other fixed bed applications such as 1.0 to 1.8 kg/l are highly desirable to keep the cost to fill a commercial reactor at a minimum.

The ratio by weight of catalyst metal to extractable alloying component in the catalyst alloy is, as is conventional with Raney alloys, in the range from 20: 80 to 80: 20. Catalysts according to the invention may also be

doped with other metals in order to have a positive effect on the catalytic properties of the invention. The purpose of this type of doping is, for example, to improve the activity, selectivity, and lifetime of the catalyst in a specific reaction. Doping metals are frequently also called promoters. The doping or promoting of Raney catalyst is described for example in U. S. patent 4, 153, 578 and DE-AS 21 01 856 in DE-OS 21 00 373 and in the DE-AS 2053799.

In principle, any known metal alloys with extractable elements such as aluminum zinc and Silicon maybe used for the present invention. Suitable promoters are transition elements in groups of 3B to 7B and 8 and group 1B of the Periodic Table of Elements and also the rare-earth metals.

The other elements mentioned previously in this document are also considered to be suitable promoters. They are also used in an amount of up to 20 wt% or more, with respect of the total weight of catalyst. Chromium, manganese, iron, cobalt, vanadium, tantalum, titanium, tungsten, rhenium, platinum, palladium, ruthenium, nickle, copper, silver, gold, and/or molybdenum and metals from platinum group are preferably used as promoters. The promoting elements could be added as alloying constituents in the catalyst alloy or they could be added to the catalyst after activation. In addition, promoters may be added as binders, they may be present as separate alloy powders with extractable elements and/or, they may be added to the catalyst after calcination and before activation. Optimum adjustment of the catalyst properties to the particular catalyst process is thus possible.

The Raney-type catalyst precursors resulting from calcination are also very important with regard the economic viability of invention. They are not pyrophoric and can be handled and transported without difficulty.

Activation can be performed by the user shortly before use.

Storage under water or organic solvents or embedding in

organic compounds is not required for the catalyst precursors.

A further subject of the invention is the use of the catalyst prepared by the method according to the invention for the transformation of organic compounds, preferred the use of the catalyst according to the invention for the hydrogenation of organic compounds.

The catalysts made according to the method of the invention can be used - for the partial hydrogenation of organic compounds, - for the hydrogenation of carbonyl groups in organic compounds, - for the hydrogenation of acetone, - for the hydrogenation of aldehydes, - for the hydrogenation of ketones, - for the hydrogenation of glucose, - for the hydrogenation of sugars to polyols, - for the hydrogenation of aldoses to polyols, - for the hydrogenation of ketoses to polyols, - for the hydrogenation of monosacharide aldoses to polyols, - for the hydrogenation of monosacharide ketoses to polyols, - for the hydrogenation of disacharide aldoses to polyols, - for the hydrogenation of disacharide ketoses to polyols, - for the hydrogenation of multisacharide aldoses to polyols, - for the hydrogenation of nitriles, - for the hydrogenation of imines, - for the hydrogenation of dinitriles, - for the hydrogenation of adiponitrile, - for the hydrogenation of alkene moeities in organic compounds, - for the hydrogenation of alkyne moeities in organic compounds,

for the hydrogenation of aromatics, for the hydrogenation of 2-butyne-1, 4-diol, for the hydrogenation of nitro groups in organic compounds, for the hydrogenation of dinitro compounds, for the hydrogenation of aromatic nitrocompounds, -for the hydrogenation of aromatic dinitrocompounds, for the hydrogenation of dinitrotoluene.

Another part of this invention is the use of these activated metal granules for catalytic chemical reactions such as the hydrogenation, isomerization, hydration, reductive amination, reductive alklyation, dehydration, oxidation and dehydrogenation of organic compounds. These catalysts are preferred for the continuous hydrogenation of organic, compounds such as nitro compounds, nitriles, imines, carbonyl compounds, alkenes, alkynes and aromatic compounds. These moeities may have already existed in the reactant (s) or they may have been incorporated into the reactant (s) just prior or during the reaction. These reactants may be sugars, nitriles, dinitriles, nitro compound, dinitro compounds and multifunctional compounds.

These catalysts may also be used for the removal of some groups, such as, halides and sulfur containing compounds (e. g. , thiols) via their hydrogenolysis.

The examples which follow are used to explain the invention in more detail. Although only a few prepared embodiments of the invention are presented in the examples, the present invention enables a person skilled in the art to prepare activated Raney-type fixed-bed catalysts with a wide range of parameters which can be adapted to the particular requirements of the application.

Example 1: Activated Ni/Al granules from a casted Ni/Al alloy (lßt Ni catalyst version) In an Eirich mixer 925 grams of a 53% Ni/47% Al casted alloy were mixed together with 75 grams of Ni powder and 60.2 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at This was followed by the careful addition of 85 grams of water while the mixture continued to mix. After mixing for 45 additional minutes, various amounts of 53% Ni /47osa1 casted alloy, Ni powder, polyvinyl alcohol and water were added carefully to the agitated mixture until the process was stopped after 145 minutes from the start.

From start to finish 1248.75 grams of 53% Ni/47% A1 casted alloy, 101.25 grams of Ni powder, 82.2 grams of polyvinyl alcohol and 177 grams of water were added to the mixture and the above mentioned mixing rpm settings were kept constant throughout the whole procedure. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. At the end of the process the granule sizes between 2 and 4 mm were sieved out for catalyst preparation. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was

initially washed with a caustic solution and this was followed by washing with water.

Example 2: Activated Ni/Al granules from a casted Ni/Al alloy (2nd Ni catalyst version) In an Eirich mixer heated to 120°C with hot air about 900 grams of a 53% Ni/47% A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 5 minutes the air heater was turned off and after the total mixing time of 10 minutes, the bottom plate was adjusted to a rotation of 43 rpm as 10 more grams of the 5. 7-wt% aqueous polyvinyl alcohol solution were added. At 20 minutes the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 ml of a 5.7-wt% aqueous polyvinyl alcohol solution was added. The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 115 minutes at which time the process was stopped and the granules above 2.24 mm were screened out for the preparation of the catalyst. From start to finish 900 grams of 53% Ni/47% A1 casted alloy, 50 grams of Ni powder and 185 grams of a 5.7- wt% aqueous polyvinyl alcohol solution were added to the mixture. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case

of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2. 24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 3: Activated Ni/Al granules from a casted Ni/Al alloy (3rd Ni catalyst version) In an Eirich mixer heated to 120°C with hot air about 900 grams of a 53% Ni/47% Al casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 5 minutes the air heater was turned off and after the total mixing time of 10 minutes, the bottom plate was adjusted to a rotation of 43 rpm as 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 20 minutes the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the

preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution were added.

The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 115 minutes at which time the process was stopped and the granules above 2. 24 mm were screened out for the preparation of the catalyst. From start to finish 900 grams of 53% Ni/47% Al casted alloy, 50 grams of Ni powder and 185 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution were added to the mixture. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules.

In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 750°C over 90 minutes followed by a 120 minute soak at 750°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 4: Activated Ni/A1 granules from a casted Ni/Al alloy (4th Ni catalyst version) In an Eirich mixer heated to 120°C with hot air about 900 grams of a 53% Ni/47% Al casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86

rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of a warm aqueous 5.7- wt. % polyvinyl alcohol solution while the mixture continued to mix. The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 80 minutes up to which 340 ml of the 5. 7-wt% aqueous polyvinyl alcohol solution have been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After which the undersized material was placed back into the mixer for the addition of 70 more grams of a 5. 7-wt% aqueous polyvinyl alcohol solution at the above mentioned conditions over 30 minutes before this mixture too was screened to the desired granule size of larger than 2.24 mm. The first and second harvests from this process were then mixed for the further preparation of this catalyst.

During the granulation of the first and second harvests of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 5: Activated Ni/Al granules from a casted Ni/A1 alloy (5th Ni catalyst version) In an Eirich mixer heated to 120°C with hot air about 900 grams of a 53% Ni/47% A1 casted alloy were mixed together with 50 grams of Ni powder and 30 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 86 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of a warm aqueous 5.7- wt. % polyvinyl alcohol solution while the mixture continued to mix. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 80 minutes up to which 340 ml of the 5.7-wt% aqueous polyvinyl alcohol solution have been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After which the undersized material was placed back into the mixer for the addition of 70 more grams of a 5. 7-wt% aqueous polyvinyl alcohol solution at the above mentioned conditions over 30 minutes before this mixture too was screened to the desired granule size of larger than 2.24 mm. The first and second harvests from this process were then mixed for the further preparation of this catalyst.

During the granulation of the first and second harvests of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 750°C over 90 minutes followed by a 120 minute soak at 750°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and

activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 6: Activated Co/Al granules from a casted Co/Al alloy (lSt Co catalyst version) In an Lodige mixer heated to 40°C with hot air about 1000 grams of a 50% Co/50% Al casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 90 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 150 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50% Co /50% Al casted alloy, 50 grams of polyvinyl alcohol and 110 grams of water were added to the mixture and the agitators spun constantly at 390 rpm throughout the whole procedure.

It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and

activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 7 LiOH doped activated Co/Al granules from a casted Co/Al alloy In an Lodige mixer heated to 40°C with hot air about 1000 grams of a 50% Co/50% Al casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 90 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 150 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50% Co /50% Al casted alloy, 50 grams of polyvinyl alcohol and 110 grams of water were added to the mixture and the agitators spun constantly at 390 rpm throughout the whole procedure.

It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and

activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Before use, the catalyst was treated for 3 hours in a 10% LiOH solution followed by being washed with water.

Example 8: Activated Cu/Al granules from a casted Cu/Al alloy (Ist Cu catalyst version) In an Lodge mixer heated to 40°C with hot air about 1000 grams of a 50% Cu/50% A1 casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50% Cu /50% Al casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a

stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 9: Pt doped activated Cu/Al granules from a casted Cu/Al alloy In an Lodige mixer heated to 40°C with hot air about 1000 grams of a 50% Cu/50% Al casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390. rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50% Cu /50% Al casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and

activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. The washed catalyst was then treated in a circulating aqueous solution containing hexachloroplatinum, whose pH value was adjusted up. The doped catalyst was then washed and the final platinum content of the catalyst was 0. 3% Pt.

Example 10: Fe doped activated Cu/Al granules from a casted Cu/Al alloy In an Lodge mixer heated to 40°C with hot air about 1000 grams of a 50% Cu/50% Al casted alloy were mixed together with 50 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. The careful addition of water continued to the mixing time of 90 minutes and this was followed by the continued agitation of the mixture until 130 minutes after which the granule sizes between 2 to 4 mm were screened out. From start to finish 1000 grams of 50% Cu /50% Al casted alloy, 50 grams of polyvinyl alcohol and 106 grams of water were added to the mixture. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch, and the oversize particles can be ground before being recycled in the same manner. The 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes

followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. The washed catalyst was then treated in a circulating aqueous solution containing Iron (III) chloride, whose pH value was adjusted up. The doped catalyst was then washed and the final iron content of the catalyst was 1. 0% Fe.

Example 11 Activated Ni/A1 granules from a rapidly quenched N2 sprayed Ni/A1 alloy (6th Ni catalyst version) In an Lodige mixer heated to 40°C with hot air about 1000 grams of a rapidly quenched N2 sprayed 50% Ni/50% Al alloy were mixed together with 100 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. At 70 minutes of mixing the agitator was adjusted to 166 rpm, at 75 minutes of mixing the excess water was allowed to evaporate out and after 80 minutes of agitation the mixing process was stopped followed by sieving out the granule sizes greater than 2.24 mm. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it. is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch. The > 2.24 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 700°C over 60 minutes followed

by a 120 minute soak at 700°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 12: Activated Ni/Al granules from a rapidly quenched N2 sprayed Ni/A1 alloy (7th Ni catalyst version) In an Lodige mixer heated to 40°C with hot air about 1000 grams of a rapidly quenched N2 sprayed 50% Ni/50% Al alloy were mixed together with 100 grams of polyvinyl alcohol for 2 minutes while the agitators spun at 390 rpm. This was followed by the careful addition of 80 grams of cold water while the mixture continued to agitate. At 70 minutes of mixing the agitator was adjusted to 166 rpm, at 75 minutes of mixing the excess water was allowed to evaporate out and after 80 minutes of agitation the mixing process was stopped followed by sieving out the granule sizes greater than 2.24 mm. It is important to avoid adding too much water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be recycled to the next batch. The > 2.24 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 120 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for

this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 13: Activated Cu/Al granules from a rapidly quenched water sprayed Cu/Al alloy (2nd Cu catalyst version) In an Eirich mixer about 700 grams of a 50% Cu/50% Al rapidly quenched water sprayed alloy were mixed together with 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 80 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes the agitator was adjusted to 3010 rpm, at 95 minutes the rotating bottom plate was adjusted to 86 rpm and these settings were kept for the remainder of the catalyst's preparation. The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 170 minutes up to which 155 ml of the 5. 7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm.

After which the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The undersized material was placed once more back into the mixer for 15 minutes of additional mixing with the addition of 5 grams of the 5. 7-wt% aqueous polyvinyl alcohol solution. After mixing the granules larger than 2.24 mm were sieved out for third harvest from the starting material. The first, second and third harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first and third

harvests of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules.

In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 14: Zn doped activated Cu/A1 granules from a rapidly quenched water sprayed Cu/Zn/A1 alloy In an Eirich mixer about 800 grams of a 50% Cu/35% Al/ 15% Zn rapidly quenched water sprayed alloy were mixed together with 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 85 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 70 minutes the rotating bottom plate was adjusted to 86 rpm, and at 110 minutes the rotating bottom plate was adjusted once more to 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5.7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 125 minutes up to which 165 ml of the 5.7-wt%

aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm.

After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 15 Cr doped activated Co/Al granules from a rapidly quenched water sprayed Co/Cr/Al alloy In an Eirich mixer about 800 grams of a 30% Co/69% Al/ 1% Cr rapidly quenched water sprayed alloy were mixed together with 45 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition

of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 65 minutes the rotating bottom plate was adjusted to 86 rpm, and at 85 minutes the rotating bottom plate was adjusted once more to 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 140 minutes up to which 200 ml of the 5. 7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm.

After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 16: Cr and Li doped activated Co/A1 granules from a rapidly quenched water sprayed Co/Cr/Al alloy In an Eirich mixer about 800 grams of a 30% Co/69% A1/ 1% Cr rapidly quenched water sprayed alloy were mixed together with 45 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 65 minutes the rotating bottom plate was adjusted to 86 rpm, and at 85 minutes the rotating bottom plate was adjusted once more to 43 rpm for the remainder of the catalyst's preparation. The careful addition of the 5. 7-wt% aqueous polyvinyl alcohol solution continued to the mixing time of 140 minutes up to which 200 ml of the 5. 7-wt% aqueous polyvinyl alcohol solution had been added to the mixture and at that time a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm.

After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the granulation of the first harvest of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a

stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Before use, the catalyst was treated for 4 hours in a 10% LiOH solution followed by being washed with water.

Example 17: Mo doped activated Ni/Al granules from a rapidly quenched nitrogen sprayed Ni/Mo/Al alloy (lest Mo doped Ni catalyst version) In an Eirich mixer about 900 grams of a 39% Ni/60% Al/ 1% Mo rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 35 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest. The undersized material was placed in the mixer for a third time for continued agitation as 10 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution were given to it. This third mixing period lasted for 10 minutes and at the end all of the granules larger than 2.24 mm were sieved out for a third harvest. The first, second and third harvests from this process were then mixed for the further preparation of this catalyst. During the initial mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming

and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 18: Activated Ni/A1 granules from a rapidly quenched nitrogen sprayed Ni/A1 alloy (8th Ni catalyst version) In an Eirich mixer about 900 grams of a 40% Ni/60% Al rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing as 20 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution were given to it followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed

for the further preparation of this catalyst. During the mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.

Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 19: Cr doped activated Ni/Al granules from a rapidly quenched nitrogen sprayed Ni/Cr/Al alloy (lSt Cr doped Ni catalyst version) In an Eirich mixer about 900 grams of a 38.5% Ni/60. 3% A1/ 1. 2% Cr rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 105 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of

additional mixing as 20 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution were given to it followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 90 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 20: Cr doped activated Ni/A1 granules from a rapidly quenched nitrogen sprayed Ni/Cr/Al alloy (2nd Cr doped Ni catalyst version) In an Eirich mixer about 900 grams of a 38. 5% Ni/60. 3% Al/ 1.2% Cr rapidly quenched nitrogen sprayed alloy were mixed together with 35 grams of polyvinyl alcohol and 100 grams of Ni powder for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 105 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture

continued to mix. At the mixing time of 45 minutes a pause in the process was taken in order to sieve out all the granules larger than 2.24 mm. After that the undersized material was placed back into the mixer for 15 minutes of additional mixing as 20 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution were given to it followed by sieving out the granules larger than 2.24 mm for a second harvest. The first and second harvests from this process were then mixed for the further preparation of this catalyst. During the mixing and granulation of this material, it is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it s better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 21: Cr and Fe doped activated Ni/Al granules from a rapidly cooled water sprayed Ni/Cr/Fe/Al alloy In an Eirich mixer about 600 grams of a 40% Mi/1% Cr/ 0. 5% Fe/58. 5% Al rapidly cooled water sprayed alloy were mixed together with 66.6 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate

rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 45 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 10 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution were added and at 90 minutes 12 more ml of the 5. 7-wt% aqueous polyvinyl alcohol solution were added. At 120 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 30 minutes of agitation where 10 grams of water were steadily added to the mixture. After the 30 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution or water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution or water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.

Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 22: Activated Ni/A1 granules from a rapidly cooled water sprayed Ni/A1 alloy (9eh Ni catalyst version) In an Eirich mixer about 850 grams of a 49. 1% Ni/50. 9% A1 rapidly cooled water sprayed alloy were mixed together with 150 grams of Ni powder and 40 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 130 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix After mixing for 100 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 130 minutes of mixing 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 150 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 15 minutes of agitation where 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 15 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules.

In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 120 minutes followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH

aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 23: Mo doped activated Ni/Al granules from a rapidly cooled water sprayed Ni/A1 alloy (2nd Mo doped Ni catalyst version) In an Eirich mixer about 850 grams of a 49. 1% Ni/50. 9% Al rapidly cooled water sprayed alloy were mixed together with 150 grams of Ni powder and 40 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 130 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 100 minutes 20 grams of the 5. 7-wt% aqueous polyvinyl alcohol solution were added. At 130 minutes of mixing 20 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution were added and at 150 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 15 minutes of agitation where 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 15 minute agitation period the process was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules.

In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 775°C over 120 minutes

followed by a 120 minute soak at 775°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. This catalyst was doped with a sodium molybdate solution and after this post activation doping, the molybdenum content of the catalyst was 0.3%. The procedure can also be carried out with other Mo containing compounds such as ammonium heptamolybdate.

Example 24: Activated Ni Al granules from a rapidly cooled, water sprayed Ni/Al alloy (10th Ni catalyst version) In an Eirich mixer about 900 grams of a 49. 1% Ni/50. 9% A1 rapidly cooled water sprayed alloy were mixed together with 100 grams of Ni powder and 40 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 140 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 40 minutes 20 grams of the 5. 7-wt% aqueous polyvinyl alcohol solution were added. At 70 minutes of mixing 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added, at 110 minutes 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added and at 140 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 20 minutes of agitation where 20 grams of the 5. 7-wt% aqueous polyvinyl alcohol solution were steadily added to the mixture. After the 20 minute agitation period the process

was stopped and the granules above 2.24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 1000°C over 240 minutes followed by a 120 minute soak at 1000°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.

Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 25: Mo doped activated Ni Al granules from a rapidly cooled nitrogen sprayed Ni/Mo/Al alloy (3rd Mo doped Ni catalyst version) In an Eirich mixer about 850 grams of a 39oNi/1% Mo I 60% Al rapidly cooled nitrogen sprayed alloy were mixed together with 150 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 50 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 20 more grams of a 5.7- wt% aqueous polyvinyl alcohol solution were added and at

140 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. It is important to avoid adding too much solution at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 120 minutes followed by a 240 minute soak at 1000°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.

Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water.

Example 26: Pd, Cr and Fe doped activated Ni/A1 granules from a rapidly cooled water sprayed Ni/Cr/Fe/Al alloy In an Eirich mixer about 600 grams of a 40% Ni/1% Cr/ 0. 5% Fe/58. 5% Al rapidly cooled water sprayed alloy were mixed together with 66.6 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This was followed by the careful addition of 100 grams of an aqueous 5.7-wt. % polyvinyl alcohol solution while the mixture continued to mix. After mixing for 45 minutes 20 grams of the 5. 7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 10 grams of a 5. 7-wt% aqueous polyvinyl alcohol solution were added and at 90 minutes 12 more ml of the 5. 7-wt% aqueous polyvinyl alcohol

solution were added. At 120 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out. The undersized particles and powder were fed back into the mixer for 30 minutes of agitation where 10 grams of water were steadily added to the mixture. After the 30 minute agitation period the process was stopped and the granules above 2. 24 mm were screened out and added to the first harvest of granules. It is important to avoid adding too much solution or water at once because this will cause excessive foaming and inhibit the formation of the desired granules. In the case of solution or water addition to the granule formation procedure, it is better to add too little than it is to add too much. The remaining powder and the undersized granules could be then recycled to the next batch. The > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C. The granules were then cooled, packed into a basket that was lowered into a stirring 20-wt. % NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.

Another option for this activation would be to circulate the 90°C 20-wt. % NaOH aqueous solution through a fixed bed of the catalyst for 1 hour. The catalyst was initially washed with a caustic solution and this was followed by washing with water. This catalyst was then doped with a palladium nitrate solution that previously had its pH to 6 with sodium carbonate adjusted. The end Pd content of the catalyst was 0. 2%.

Comparative Example 1: Shell activated Ni/Al tablets from a rapidly cooled water sprayed Ni/A1 alloy In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Ni/Al shell activated tablets started with a homogeneous mixture of 1000 grams of

a 50% Ni/50% Al rapidly cooled water sprayed alloy, 75 grams of a pure Ni powder (99% Ni and D50 = 21 ym) and 50 grams of ethylene bis-stearylamide that was tableted to 3 by 3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt. % caustic solution for 2 hours at 80°C, washed in a caustic solution, washed in water and stored under a mildly caustic aqueous solution (pH-10. 5) until use. The bulk densities of four different batches made in this way were 1. 56,1. 58,1. 75 and 1.79 grams per mL.

Comparative Example 2 Shell activated Cu/A1 tablets from a rapidly cooled water sprayed Cu/Al alloy In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Cu/Al shell activated tablets started with a homogeneous mixture of 1000 grams of a 50% Cu/50% Al rapidly cooled water sprayed alloy, 75 grams of a pure Ni powder (99% Ni and D50 = 21/im) and 50 grams of ethylene bis-stearylamide that was tableted to 3 by 3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt. % caustic solution for 2 hours at 80°C, washed in a caustic solution, washed in water and stored under a mildly caustic aqueous solution (pH-10. 5) until use.

Comparative Example 3: Shell activated Co/A1 tablets from a slowly cooled casted Co/A1 alloy In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the Co/Al shell activated tablets started with a homogeneous mixture of 1000 grams of a 50% Co/50% Al slowly cooled casted alloy and 50 grams of ethylene bis-stearylamide that was tableted to 3 by 3 mm tablets, calcined for 2 hours at 700°C, activated in a 20 wt. % caustic solution for 2 hours at 80°C, washed in a

caustic solution, washed in water and stored under a mildly caustic aqueous solution (pH-10. 5) until use.

Application Example 1: The hydrogenation of acetone The trickle phase hydrogenation of acetone was carried out over the activated base metal catalysts in a tube reactor in the presence of hydrogen at 75°C and 5 bar. The data from these tests are displayed in table 1.

Table 1: The acetone hydrogenation data. Catalyst Density LHSV % Con. B IPA Activity per Activity g/mlA tSel. C graH permlE Example 2 1.56 3.46 62.03 100 18.8 29.2 Comparative 1.56 3.43 56.32 100 16.9 26.3 Example 1 Example 8 1.58 2.97 32.20 98.2 8.3 13.0 Example 10 1. 52 3.13 95.0 99.9 26.6 40.5 Comparative 1.76 3.09 27.6 99.3 6.6 11.6 Example 2 A. The catalyst's bulk density.

B. The percentage of acetone conversion during the reaction.

C. The percent isopropanol selectivity.

D. The mmoles of acetone reacted per gram of catalyst per hour.

E. The mmoles of acetone reacted per ml of catalyst per hour.

Application Example 2: The hydrogenation of glucose The trickle phase hydrogenation of glucose was carried out over an activated base metal catalyst in a tube reactor in the presence of hydrogen with a 40% aqueous glucose solution at 140°C and 50 bar. The data from this test are displayed in table 2.

Table 2: The glucose hydrogenation data Catalyst Density g/mlA LHSV % Con. B Activity/gram Activity/mlD Example 23 1. 34 3 23.0 1 1. 30 1 1. 77 A. The catalyst's bulk density.

B. The percentage of glucose conversion during the reaction.

C. The mmoles of glucose reacted per gram of catalyst per hour.

D. The mmoles of glucose reacted per ml of catalyst per hour.

Application Example 3: The hydrogenation of 2-butyne-1, 4- diol The trickle phase hydrogenation of 2-butyne-1, 4-diol was carried out over the activated base metal catalysts in a tube reactor at 135°C and 60 bar in the presence of hydrogen with a 50% aqueous 2-butyne-1, 4-diol solution that was adjusted to a pH of 7 with NaHCO3. The data from these tests are displayed in table 3.

Table 3: The 2-butyne-1, 4-diol hydrogenation data Catalyst Density Through-% Con. c BDO BeD BDO/BeD Activity Acti- g/mlA put'96SelD % SelE RatioF per grant vity per ml' Example 1.37 0.80 99.4 59.6 16.9 3.53 0 584 0.800 12 1. 60 91.1 38.5 33.4 1.16 1.06 1.46 Example 1.39 0.80 97.6 56.6 22.4 2.53 0.565 0.786 22 1. 60 74.7 37.2 35.9 1.04 0.860 1.20 Example 1.09 0. 80 99.2 62.7 10.0 6.26 0.733 0.799 25 1. 60 89.8 45.3 30.0 1.51 1.32 1.44 Comparat 1.75 0.80 83.6 36.6 44.9 0.815 0.384 0.673 ive 1.60 62.8 28.6 49.3 0. 580 0.574 1.01 Example 1 A. The catalyst's bulk density.

B. The throughput of 2-butyne-1, 4-diol in grams per ml of catalyst per hour.

C. The percentage of 2-butyne-1, 4-diol conversion during the reaction.

D. The percent 1,4-butanediol selectivity.

E. The percent 2-butene-1, 4-diol selectivity.

F. The 1,4-butanediol to 2-butene-1, 4-diol ratio.

G. The mmoles of 2-butyne-1, 4-diol reacted per gram of catalyst per hour.

H. The mmoles of 2-butyne-1, 4-diol reacted per ml of catalyst per hour.

Application Example 4: The hydrogenation of adiponitrile via method 1 The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution. The data from these tests are displayed in table 4.

Table 4: The adiponitrile hydrogenation data via method 1

Catalyst Density Time Temp. LHSV HMD ACN % CorP Activity Activity g/ml"h °C% Sel % Sel=pergranf per mlF Example 6 1.29 2.12 109.8 1.00 54.52 34.16 69.86 4.84 6.24 3.20 109.6 1.00 50.24 39.61 63.44 4.41 5.69 4.28 109.5 1.00 47.04 43.25 61.42 4.27 5.51 5.42 109. 3 0.25 72.90 1. 91 99.55 1.72 2.22 6.95 109.4 0.25 72.97 1.99 100.0 1. 73 2.23 Example 11 1.13 2.28 109.9 1.00 34.43 20. 25 73. 56 5.80 6.56 3.83 110.2 1.00 34.29 25. 36 88. 01 7. 00 7.91 4.83 110 0.99 32.00 32.28 88.51 6.97 7.88 6.46 109.5 0.25 37.53 0.24 100 2.00 2.26 7.50 109.5 0.25 37.97 1.75 100 2.01 2.28 Example 19 1. 17 3.55 109.9 1.00 39.94 23.56 72.02 5.52 6.43 4.78 110 1.00 38.14 30.21 72.76 5.60 6.53 6.88 109.6 0.25 46.36 2.82 100 1.92 2.23 7. 78 109.7 0.25 49.48 2. 21 100 1.91 2.23 Example 21 1. 09 2.00 116 1. 00 43.95 17. 73 78.59 6.48 7.03 3. 42 116.2 1.00 41.76 23.52 87.74 7.21 7.83 4.28 116.1 1.01 39.21 29.31 85.15 7.08 7.68 5.53 112.4 0.50 43.77 15.44 96.36 3.98 4.32 7. 08 110.4 0.25 45.95 5.19 100 2.06 2. 24 Comparative 1.79 1.37 152.60 0. 26 12. 90 23.14 75.20 0. 97 1.74 Example 1 2.80 152.20 0.25 17.90 14.90 93.30 1.19 2.13 4.65 153.90 0.51 29.64 10. 57 96.50 2.48 4. 43 5. 92 151.40 0.13 12.55 0.00 99.60 0.64 1.15 Example 7 1.30 2.00 109.6 0.98 52.69 38.20 49.73 3.34 4.34 3.00 109.6 0.98 48.26 42.59 47.06 3.18 4.13 4.00 109.6 0.99 46.56 44.17 46.24 3.14 4.08 5.00 109.7 1.00 43.32 45.06 45.12 3.11 4.05 6. 10 109.6 0.97 42. 99 45. 41 44.02 2.93 3.80 Example 15 0. 85 2.03 116.5 1.01 56.04 13.05 92.28 9.83 8.31 3.10 115.9 1.00 55.33 17.27 88.80 9.39 7.94 4.05 115.7 1.00 53.96 20.66 88.75 9.38 7.92 5.28 112.7 0.25 58.69 0.00 100 2.67 2.26 6.67 112. 8 0.25 59.71 0. 00 100 2. 63 2.22 Example 16 0. 77 2.02 117.2 0. 95 65.49 13.52 88.08 9.81 7.51 3.10 116.8 0.96 61.96 17.73 87.75 9.88 7.56 4.00 116.6 0.96 60.72 19.26 85.28 9.60 7.35 5.00 116.3 0.96 59.02 22.32 83.80 9.36 7.16 6. 25 116.3 0.95 58.79 22.49 79.70 8.89 6. 80 Comparative 2.06 2. 70 112 1.03 46.93 43.59 41.98 1.88 3. 86 Example 3 3. 97 111 0.26 70.97 13.61 86.50 0.97 2. 00 A. The catalyst's bulk density.

B. The percent hexamethylendiamine selectivity.

C. The percent aminocapronitrile selectivity.

D. The percentage of adiponitrile conversion during the reaction.

E. The mmoles of adiponitrile reacted per gram of catalyst per hour.

F. The mmoles of adiponitrile reacted per ml of catalyst per hour.

Application Example 5 The hydrogenation of adiponitrile via method 2 The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution, where one liter of this methanol originally contained 1.9 grams of NaOH. The data from these tests are displayed in table 5.

Table 5: The adiponitrile hydrogenation data via method 2 Catalyst Density Time h Temp. LHSV % ConD Activity Activity g/mlA °C %SelB %SelC per per mlF gramE Example 20 1.13 2.00 110.9 1.00 74.58 17.26 84.65 6.72 7.59 3.38 111.1 1.00 77.95 17.48 85.82 6.82 7.71 4.35 110.5 1.00 79.52 17.02 89. 34 7.06 7.98 6.45 109.8 0.25 94.65 0.46 100 1.98 2.24 7. 53 110. 2 0.26 95.86 0.49 100 2. 02 2.29 Example 21 1.04 2.00 109.9 1.01 58.72 37.62 75.61 6.59 6.82 3.00 110.1 1.01 60.21 37.89 82.54 7.17 7.42 4.18 110. 1 1.01 64.61 34.32 86.96 7.58 7.85 5.00 110.2 1.00 67.27 31.69 90.55 7.84 8.11 6.00 110.3 1.00 69.80 29.13 93.07 8.07 8.35 7.07 110. 1 0. 80 85.20 13. 04 100 6.94 7.19 A. The catalyst's bulk density.

B. The percent hexamethylendiamine selectivity.

C. The percent aminocapronitrile selectivity.

D. The percentage of adiponitrile conversion during the reaction.

E. The mmoles of adiponitrile reacted per gram of catalyst per hour.

F. The mmoles of adiponitrile reacted per ml of catalyst per hour.

Application Example 6: The hydrogenation of adiponitrile via method 3 The trickle phase hydrogenation of adiponitrile was carried out over the activated base metal catalysts in a tube reactor at 65 bar in the presence of hydrogen with a 20% adiponitrile in methanol solution, where one liter of this methanol originally contained 1.9 grams of LiOH. The data from these tests are displayed in table 6.

Table 6: The adiponitrile hydrogenation data via method 3

Catalyst Densit Time Temp. ° LHSV HMD ACN % ConD Activit Activit y h C % SelB % SelC y per Y per g/mlA gramE mlF Example 1.19 2.02 110 0.96 72.63 23.58 75. 00 5.43 6.46 6 3.02 110 0.94 72.87 23.73 70.41 4.97 5.91 4.00 110 0.94 71.63 25.30 72.03 5.10 6.07 5.02 109.9 0.95 70.09 27.01 71.28 5.12 6.09 6.08 109.9 0.98 71.16 26.02 69.86 5.15 6.12 7.00 109.8 0.94 69. 61 27.68 69.95 4.94 5. 88 Example 0.73 2.00 110.9 1.02 85.72 8.41 99.35 12.48 9.11 15 3.25 110.8 1.03 84.62 10.79 98. 01 12.32 9.00 4.17 110.7 1.03 84.28 11.62 97.30 12.26 8.95 5.08 110.8 1.07 83.05 13.14 96.41 12,69 9.26 6.35 110.6 1.00 83.15 13.16 96.60 11.89 8.68 A. The catalyst's bulk density.

B. The percent hexamethylendiamine selectivity.

C. The percent aminocapronitrile selectivity.

D. The percentage of adiponitrile conversion during the reaction.

E. The mmoles of adiponitrile reacted per gram of catalyst per hour.

F. The mmoles of adiponitrile reacted per ml of catalyst per hour.

Application Example 7: The hydrogenation of dinitrotoluene The trickle phase hydrogenation of dinitrotoluene was carried out over the activated base metal catalysts in a tube reactor at-80°C and 60 bar in the presence of hydrogen with a 4% dinitrotoluene in methanol solution. The data from these tests are displayed in table 7.

Table 7: The dinitrotoluene hydrogenation data

Catalyst Density Temp. Throughput TDA % ConE Activity Activity g/mlA °C %SelC per gramF per mlG Exanple 21 0. 99 80.0 0. 086 98.756 100 0.474 0. 470 80. 6 0.142 99.144 100 0.785 0.779 81.1 0.236 99.207 100 1.306 1.296 81.3 0.305 97.568 96.24 1.623 1.611 81.7 0.462 93.526 89.17 2.280 2.263 81.9 0.702 92.566 74.19 2.880 2.858 82.0 0.934 90.271 63.71 3.292 3.267 82. 0 1.072 89.505 57.72 3.422 3.396 EXaMple 26 0.99 80.5 0.074 97.944 100 0.412 0.407 81.1 0.144 98.401 100 0.799 0.790 81.9 0.240 98.699 100 1.333 1.317 82.2 0.308 98.752 100 1.713 1.692 82.9 0.466 98.885 96.71 2.505 2.473 83.7 0.695 97.992 95.84 3.703 3.657 83.9 0.921 97.129 90.71 4.646 4.588 84. 2 1.048 96.140 88.57 5.161 5.096 Comparative 1.58 81.0 0. 072 95.240 100 0.250 0. 395 Exanple 1 81.8 0.144 96.144 98.87 0. 493 0. 780 83.0 0.240 95.197 93.98 0.782 1.238 84.2 0.310 95.016 92.32 0.994 1.573 1. The catalyst's bulk density.

2. The dinitrotoluene throughput in grams of dinitrotoluene per ml of catalyst per hour.

3. The percent toluenediamine selectivity.

4. The percentage of dinitrotoluene conversion during the reaction.

5. The mmoles of dinitrotoluene reacted per gram of catalyst per hour.

6. The mmoles of dinitrotoluene reacted per ml of catalyst per hour.