Catalysts, preparation method thereof, and selective hydrogenation processes

Abstract

To provide a catalyst for making 1,4-butanediol, and a process for preparing the catalyst.SOLUTION: The present invention provides an alloy precursor for a catalyst for making 1,4-butanediol, comprising a first metal, a second metal, and copper in a range of about 1.0 wt.% to about 10.0 wt.% of the alloy precursor. The catalyst is a skeletal metal catalyst including copper as a promoter, and a process for preparing the catalyst comprises melting and mixing copper, the first metal, and the second metal to form the alloy precursor, wherein the first metal is selected from the group consisting of Ni, Co, Fe, and mixtures thereof, and the second metal is selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst, more specifically, a catalyst for preparing 1,4-butanediol, a method for preparing the same, a selective hydrogenation process using the catalyst, and an alloy precursor for preparing the catalyst.

Background Art

[0002] The granular fixed-bed form of skeletal metal nickel catalyst is generally industrially used to produce butanediol (BDO), which is a component in producing polyester from unsaturated compound 1,4-butynediol (BYD). One form of the skeletal metal nickel catalyst begins with an alloy containing at least two metals such as nickel and aluminum and is produced by the Raney process. Optionally, other metals or compounds are added in a lesser amount as promoters to enhance the activity, selectivity, or durability of the catalyst.

[0003] U.S. Patent No. 6,262,317 discloses a process for preparing 1,4-butanediol by the continuous catalytic hydrogenation of 1,4-butynediol. The process involves reacting 1,4-butynediol with hydrogen in a liquid continuous phase in the presence of a heterogeneous hydrogenation catalyst. The catalyst generally contains one or more elements of transition groups I, VI, VII, and VIII of the periodic table. The catalyst preferably further contains at least one element selected from the elements of main groups II, III, IV, and VI of the periodic table, the elements of transition groups II, III, IV, and V, and a lanthanide as a promoter to increase activity. The promoter content of the catalyst is generally at most 5% by weight. The catalyst can be a precipitation, supported, or skeletal type catalyst.

[0004] Chinese Patent No. 201210212109.2 discloses a method for preparing and activating a skeletal metal nickel-aluminum-X catalyst for the hydrogenation preparation of 1,4-butanediol from 1,4-butynediol. X represents Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo, or Fe.

[0005] U.S. Patent Application No. 62 / 715,926 discloses a process for making 1,4 - butanediol. The process includes reacting a solution containing 1,4 - butynediol with hydrogen in the presence of a catalyst containing cerium as a promoter. The process can reduce the significant formation of butanol by - products.

[0006] This catalyst typically has a predictable limited lifespan. This process produces n - butanol, acetals (e.g., 2 - (4 - hydroxybutoxy)tetrahydrofuran), and other by - products at a gradually increasing rate until the maximum specification limit is reached, which defines the end of the effective lifespan of the catalyst in the bed. Acidic Al species present in the skeletal metal catalyst, such as the hydrated alumina residue from the leaching process, are considered one of the main causes in generating by - products containing butanol and acetals. The skeletal metal catalyst can generally contain a small amount of additive elements as promoters, and its functions include improving the activity, selectivity, and stability of the catalyst in the chemical environment of a given hydrogenation process. Some promoters for conventional skeletal metals such as Mo, Cr, or Fe can actually increase the formation of butanol by - products due to the increase in surface acidity. Operating conditions such as relatively low temperature, relatively high pressure, and control of feed pH have been optimized previously, and their combination still cannot properly suppress the formation of butanol and acetals. Butanediol is a main component in making polyesters. For downstream use, there are impurity limitations on butanediol, so By reducing the contaminants in butanediol during the process for making butanediol, for example, the costs associated with the subsequent separation of impurities (e.g., distillation) from butanediol can be significantly reduced. SUMMARY OF THE INVENTION

[0007] The present invention provides a process for making 1,4 - butanediol from a solution of 1,4 - butynediol in the presence of a catalyst containing copper. The process significantly and unexpectedly reduces the amount of the main by - product acetal (2 - (4 - hydroxybutyl)tetrahydrofuran), in addition to maintaining a desirable low level of another major by - product n - butanol in the final 1,4 - butanediol product.

[0008] Accordingly, an example of the present invention is a process for making 1,4 - butanediol. The process may include reacting a solution containing 1,4 - butynediol with hydrogen in the presence of a catalyst containing copper as a promoter.

[0009] Another example of the present invention is an alloy precursor for a catalyst for making 1,4 - butanediol. The alloy precursor may contain a first metal, a second metal, and copper in the range of about 1 wt% to about 10 wt% of the alloy precursor.

[0010] Another example of the present invention is a catalyst for making 1,4 - butanediol. The catalyst may be a skeletal metal catalyst containing copper as a promoter.

[0011] Another example of the present invention is a process for preparing a catalyst. The process may include melting and mixing copper, a first element, and a second element to form an alloy precursor, and subsequently activating with an alkaline solution to form the catalyst. The first element may be Ni, and the second element may be aluminum.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention is described with reference to embodiments of the invention to provide a better understanding for those skilled in the art of the technical solutions of the present disclosure.

[0013] As used herein, a number modified by "about" means that the number can vary by up to 10%. A numerical range modified by "about" means that the upper and lower limits of the numerical range can vary by up to 10%. Butanol, n-butanol, and 1-butanol are all synonyms and interchangeable for the purposes of the present inventors.

[0014] One example of the present invention is a process for producing 1,4-butanediol. The process can include reacting a solution containing 1,4-butynediol with hydrogen in the presence of an effective amount of a catalyst containing copper as a promoter. As used herein, an "effective amount of catalyst" refers to a process that achieves an overall conversion of at least about 95%, preferably at least about 99% of the starting butynediol, with good selectivity for 1,4-butanediol. A promoter is a minor component in the catalyst compared to other main components such as nickel and aluminum, to enhance the activity, selectivity, or durability of the catalyst.

[0015] The solution containing 1,4-butynediol can be in the form of an aqueous solution and can further contain, as insoluble or dissolved components, components from butynediol synthesis, such as bismuth, aluminum, or silicon compounds, and can be a technical grade 1,4-butynediol. The main solvent for the solution containing 1,4-butynediol is usually water. The solution containing 1,4-butynediol can also contain other solvents such as methanol, ethanol, propanol, butanol, or recycled 1,4-butanediol product. The recycled The solution containing the recycled 1,4-butanediol product can contain a lower 1,4-butynediol content than a solution containing only water as the solvent. The 1,4-butynediol content in the solution is generally 5 to 90 wt%, preferably 10 to 80 wt%, particularly preferably 10 to 50 wt% of the solution. In one embodiment, the solution containing 1,4-butynediol is 100% pure butynediol.

[0016] The solution containing 1,4 - butynediol can have a pH in the range of about 4.0 to about 11.0, preferably about 7.5 to about 10.0. The solution pH can be inherent to process conditions such as butynediol quality, temperature, pressure, etc., or optionally can be achieved by adjusting with a small amount of dilute base such as NaOH solution.

[0017] The hydrogen required for the reaction is preferably used in pure form. However, it can also contain further components such as methane and carbon monoxide. The hydrogen pressure applied to the fixed - bed reactor for this process can be in the range of about 15 to about 30 MPa. The inlet temperature of the fixed - bed reactor can be in the range of about 80 °C to about 120 °C. The flow rate of the feed solution, in combination with an effective amount of catalyst, is selected by those skilled in the art to enable a selected conversion rate, thereby achieving the desired overall conversion level of butynediol, i.e., the reaction with hydrogen to form the product. Next, the selected conversion rate of butynediol depends on whether the process stream is partially recycled to the reactor inlet. In the case of a non - recycled process stream, the selected conversion rate results in a high overall conversion % of, for example, more than 98 wt% of 1,4 - butynediol in a "single pass". Similarly high levels of overall conversion can also be achieved at variable rates using a partially recycled process stream where, for example, 10 - 20% of the process stream at the reactor outlet is taken out as the final product and the other 80 - 90% is returned to the inlet.

[0018] According to the present invention, the catalyst used is one that can hydrogenate C≡C triple and double bonds to single bonds. The catalyst can be in the form of a fixed bed, slurry or suspension, or a combination thereof. In one embodiment, the catalyst is in the form of a fixed bed and can have a particle size in the range of about 1 mm to about 8 mm, preferably about 2 mm to about 5 mm. In another embodiment, the catalyst is in the form of a slurry or suspension and can have a median particle size in the range of about 10 μm to about 100 μm, preferably about 20 μm to about 80 μm.

[0019] The catalyst may further comprise at least a first element selected from the group consisting of Ni, Co, Fe, and mixtures thereof. In one embodiment, the first element is Ni. The catalyst may further comprise at least a second element selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof. In one embodiment, the second element is aluminum.

[0020] The catalyst can be a skeletal metal catalyst. Suitable skeletal metal catalysts include skeletal metal nickel, skeletal metal cobalt, skeletal metal nickel / molybdenum, skeletal metal nickel / chromium, skeletal metal nickel / chromium / iron or rhenium sponge.

[0021] Copper can be present in the catalyst in an amount in the range of about 1.0 wt% to 20.0 wt%, preferably about 1.0 wt% to about 12.0 wt%, more preferably about 2.0 wt% to about 8.0 wt% of the catalyst.

[0022] The molar ratio of hydrogen to butynediol in the reactor can be at least 3:1, preferably 4:1 to 100:1.

[0023] When a fixed-bed reactor is used in the process of the present invention, the space velocity of the solution and gas flowing through the fixed bed of the catalyst is not limited. Those skilled in the art can adjust the space velocity of the solution and gas to obtain 1,4-butanediol with an optimal yield with small amounts of products such as butanol and acetal.

[0024] The catalyst according to the present invention can comprise only one type of catalyst or a mixture of several types of catalysts. The mixture of several types of catalysts can exist as a quasi-homogeneous mixture or as a structured bed in which each individual reaction zone is composed of a quasi-homogeneous catalyst bed. For example, it is also possible to combine methods by using one type of catalyst at the start of the reaction and a mixture further downstream.

[0025] The process can produce acetal as a by-product in an amount of less than about 1.0 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.25 wt%, based on the total weight of acetal, butanol, and 1,4 - butanediol when the solution containing 1,4 - butynediol has a pH of 7.5 or higher.

[0026] In one embodiment of the process for producing 1,4 - butanediol, the catalyst is a skeletal element catalyst. The catalyst includes at least a first element selected from the group consisting of Ni, Co, Fe, and mixtures thereof, at least a second element selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof, and copper as a promoter. Copper is present in an amount in the range of about 1.0 wt% to about 12.0 wt% of the catalyst. The solution containing 1,4 - butynediol has a pH of about 4.0 to about 11.0. The process produces acetal as a by - product in an amount of less than about 1.0 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.25 wt%, based on the total weight of acetal, butanol, and 1,4 - butanediol when the solution containing 1,4 - butynediol has a pH of 7.5 or higher.

[0027] Another example of the present invention is an alloy precursor for a catalyst for producing 1,4 - butanediol. The alloy precursor may contain a first metal, a second metal, and copper in an amount in the range of about 1.0 wt% to about 10.0 wt%, preferably about 2.0 wt% to 7.0 wt% of the alloy precursor.

[0028] In one embodiment, copper is in the range of about 2.0 wt% to about 5.0 wt% of the alloy precursor.

[0029] In one embodiment, the first metal is Ni in the range of about 30 wt% to about 60 wt% of the alloy precursor, and the second metal is Al in the range of about 40 wt% to about 65 wt% of the alloy precursor. In another embodiment, the first metal is Ni in the range of about 40 wt% to about 49 wt% of the alloy precursor, and the second metal is Al in the range of about 50 wt% to about 60 wt% of the alloy precursor.

[0030] Another example of the present invention is a catalyst for making 1,4-butanediol. The catalyst can include a skeletal metal catalyst including copper as a promoter. The copper can be present in the catalyst in an amount ranging from about 1.0% to about 10.0% by weight of the catalyst, preferably from about 2.0% to about 8.0% by weight. In one embodiment including about 1.0% to about 10.0% by weight of copper, the first element of the skeletal metal is nickel and the second element of the skeletal metal is aluminum.

[0031] Another example of the present invention is a process for preparing a catalyst. The process can include melting and mixing copper, a first element, and a second element to form an alloy precursor.

[0032] The first element may be selected from the group consisting of Ni, Co, Fe, and mixtures thereof. The second element may be selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof. In one embodiment, the first element is Ni and the second element is aluminum. Ni is the most important element in the alloy precursor. The aluminum may be present in an amount ranging from about 40% to about 65% by weight, preferably about 50% to about 60% by weight, based on the total weight of the alloy precursor. The copper may be present in an amount ranging from about 1.0% to about 10.0% by weight, preferably about 2.0% to about 6.0% by weight, based on the total weight of the alloy precursor.

[0033] In one embodiment, the process of preparing the catalyst further includes activating the alloy precursor by contacting the alloy precursor with an alkaline solution. The alkaline solution can be an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration in the range of 1 wt% to 25 wt%. In one embodiment, the alkaline solution is continuously pumped through the alloy precursor bed to activate the alloy precursor. In another embodiment, the alloy precursor particles are added to the alkaline solution in batches to activate the alloy precursor. In one embodiment, the catalyst is a skeletal metal catalyst.

[0034] In one embodiment, the process of preparing the catalyst includes melting and mixing copper, a first element, and a second element to form an alloy precursor, and contacting the alloy precursor with an aqueous alkaline solution to produce the catalyst. The first element is selected from the group consisting of Ni, Co, Fe, and mixtures thereof, and the second element is selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof. Copper is present in an amount in the range of about 1.0 wt% to about 10.0 wt% based on the total weight of the catalyst. In one embodiment containing about 1.0 wt% to about 12.0 wt% of copper, the first element of the skeletal metal is nickel and the second element of the skeletal metal is aluminum.

[0035] Another example of the present invention is a catalyst produced by a process of preparing a catalyst according to an embodiment of the present invention.

[0036] The descriptions of the various embodiments of the present invention are presented for purposes of illustration and are not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terms used herein are selected to enable an understanding of the principles of the embodiments, practical applications or technical improvements by technologies found in the market, or to enable those skilled in the art to understand the embodiments disclosed herein.

[0037] Hereinafter, the present invention will be described in more detail with reference to the examples. However, the scope of the present invention is not limited to the following examples.

Example

[0038] Example 1 Catalyst Preparation By melting and mixing three components, an alloy precursor containing 58 wt% Al, 2.5 wt% Cu, and 39.5 wt% Ni was formed. The alloy precursor was then pulverized and sieved into alloy precursor particles having a diameter in the range of 8 - 12 mesh size or in the range of about 2 mm - about 3 mm.

[0039] A 390 g portion of the alloy precursor particles was placed in a beaker to form a "bed". This bed of alloy precursor particles was converted into part of the catalyst by contact with an "leaching solution", which involved continuously pumping five portions of an aqueous NaOH solution through the alloy precursor bed at a constant rate. Each portion of the NaOH aqueous solution was 18 liters, and the strength of the five portions increased during the process from 1%, then 2%, 3%, 4% to a final 5%. Each portion of the NaOH aqueous solution was delivered through the alloy precursor bed for 40 minutes, while an immersed cooling coil (having an internal water flow) was used to control the temperature of the process to the target of 38 °C.

[0040] The catalyst was then washed with 2 liters of 0.25% NaOH solution for 10 minutes and then washed with water at 45 °C until the effluent wash water reached a pH of 9.

[0041] This portion of the catalyst had the following assay (wt%) by ICP analysis: 54.6 Ni, 41.7 Al, 3.5 Cu, 0.2 Fe

[0042] Catalyst Testing When the prepared catalyst was loaded into a vertical column reactor having a bed dimension of about 0.5 inches inner diameter and about 6 inches height, it was maintained in a water-wet state. This was in a catalyst bed having a volume of 18 mL.

[0043] 1,4 - butanediol was used to prepare a reactant feed solution by dissolving 40% (representing recycled "BDO" product) in water along with 10 wt% of 2 - butyne - 1,4 - diol. The overall organic compound content was nominally 50%, and water was 50%. The pH of this newly prepared mixture varied from about 4 to about 5.5. As a further variable for subsequent catalyst testing, an additional portion of the reactant feed solution was prepared by adding a small amount of 15% NaOH solution and then adjusted to a pH in the range of about 7.0 to about 8.5.

[0044] In the catalyst test, the reaction conditions used were an inlet temperature of 100 °C, peak temperature: 150 °C (exit temperature), hydrogen pressure = about 2500 psig (16 - 17 MPa), and a controllable liquid feed flow rate. 0.25 mL / min was the default liquid flow rate, and a range of 0.10 - 2.5 was feasible. When the flow rate was changed, it was then maintained at a constant level for several days to achieve a steady - state level of the product. Co - current upward flow of H2 gas (300 mL / min) and the liquid were maintained throughout the test process.

[0045] The product assay, stated in weight % of the organic product, was determined by GC analysis using a Restek Stabilwax 30×0.32×0.5 column, 90% ethanol solvent, diglyme as the internal standard, and a flame ionization detector. The yields reported for each condition in Tables 1 and 2 are averages from samples taken after each 8 - hour continuous operation.

[0046] The main by - product of interest, n - butanol ("n - butanol, BuOH"), is in the range of 0.23 - 0.35% over a variety of pH conditions. When using a higher pH of the feed solution, the butanol yield is lower. The second by - product, 2 - (4 - hydroxybutoxy) tetrahydrofuran, a cyclic acetal formed by the reaction and dehydration of the product and the feed molecule, is listed as "acetal" in Tables 1 and 2. As shown in Table 1, the acetal varies from 0.17 - 0.38% at different pHs.

[0047] List the pH of the reactant supply solution used, the elapsed time under the pH conditions, and the outlines of the two main by-products in Table 1.

[0048] Example 2 Catalyst Preparation The same method as in Example 1 was used, except that the alloy had a composition of 58 wt% Al, 3.8 wt% Cu, and 38.2 wt% Ni. The resulting catalyst composition was 42.6% Al, 52.3% Ni, 5.0% Cu, and 0.2% Fe.

[0049] Catalyst Test The test proceeded in the same manner as in Example 1 and was conducted to show the improvement of Ce-Ni and the variation of the Cu content compared to Example 1.

[0050] Comparative Example (Ce-Ni) Catalyst Preparation The alloy precursor used had the following composition: 61.5% Al, 34.9% Ni, and 2.1% Ce. The activation and washing procedures were the same as in Example 1, except that the concentrations of the NaOH solution were 0.9, 1.75, 2.6, 3.5, and 4.35% respectively. The resulting catalyst composition was 51.5% Al, 45.2% Ni, and 3.3% Ce.

[0051] Catalyst Test The test conditions and methods were as described in Example 1. The test results are shown in Table 2. As summarized in Table 2, the butanol by-product was in the range of 0.21 - 0.55%, and the acetal was in the range of 0.40 - 0.65.

[0052] As shown in Tables 1 and 2 using the catalyst according to an embodiment of the present invention, by using copper instead of cerium as a promoter, a significant improvement is shown in reducing the amount of acetal by-products while maintaining a similar or slightly lower level of butanol by-products. These by-products have maximum allowable values in full-scale industrial applications. Therefore, these reductions in acetal by-products are very significant in industrial applications, whereby the life of the fixed-bed catalyst system is often extended in units of months, leading to a reduction in the operating costs of the user. There are also other advantages such as low cost and simpler use with Cu metal compared to CeO2.

[0053]

Table 1

[0054]

Table 2

[0055] The principles and embodiments of the present disclosure are described herein. The description of the embodiments of the present disclosure is used only to assist in understanding the method and the core idea of the present disclosure. On the other hand, for those skilled in the art, with respect to the scope of the present disclosure, the technical scheme is not limited to a specific combination of technical features, and other technical schemes formed by combining technical features or equivalent features of technical features without departing from the concept of the present invention should be covered. For example, the technical scheme can be obtained by replacing the features described above as disclosed in the present disclosure with similar features (but not limited to these). features can be obtained by replacing with similar features (but not limited to these).

Claims

1. A process for producing 1,4 - butanediol, comprising reacting a solution containing 1,4 - butynediol with hydrogen in the presence of an effective amount of a catalyst, wherein the catalyst contains copper.

2. The process according to claim 1, wherein the catalyst is in the form of a fixed bed, a suspension, or a combination thereof.

3. The process according to claim 2, wherein the catalyst is in the form of the fixed bed and has a particle size in the range of about 1 mm to about 8 mm.

4. The process according to claim 2, wherein the catalyst is in the form of the suspension and has a median particle size in the range of about 10 to about 100 μm.

5. The process according to claim 1, wherein the catalyst further contains at least a first metal selected from the group consisting of Ni, Co, Fe, and mixtures thereof.

6. The process according to claim 5, wherein the first metal is Ni.

7. The process according to claim 5, wherein the catalyst further contains at least a second metal selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof.

8. The process according to claim 7, wherein the second metal is aluminum.

9. The process according to claim 1, wherein the catalyst is a skeletal metal catalyst.

10. The process according to claim 1, wherein copper is present in an amount in the range of about 1.0 wt% to about 12.0 wt% of the catalyst.

11. The process according to claim 1, wherein copper is present in an amount in the range of about 2.0 wt% to about 8.0 wt% of the catalyst.

12. The process according to claim 1, wherein the solution containing 1,4 - butynediol has a pH in the range of about 4.0 to about 11.

0.

13. The process according to claim 1, wherein the solution containing 1,4 - butynediol has a pH in the range of about 7.5 to 10.

14. The process according to claim 1, wherein when the solution containing 1,4 - butynediol has a pH of 7.5 or higher, the process produces the acetal as a by - product in an amount in the range of less than about 0.5 wt% based on the total weight of butanol, acetal, and 1,4 - butanediol.

15. ​ The process according to claim 1, wherein when the solution containing 1,4 - butynediol has a pH of 7.5 or more, the acetal is produced as a by - product in a range of less than 0.25% by weight based on the total weight of butanol, acetal, and the 1,4 - butanediol.

16. An alloy precursor for a catalyst for producing 1,4 - butanediol, comprising a first metal, a second metal, and copper in a range of about 1.0% to about 10.0% by weight of the alloy precursor.

17. The alloy precursor according to claim 16, wherein the copper is in a range of about 2.0% to about 5.0% by weight of the alloy precursor.

18. The alloy precursor according to claim 16, wherein the first metal is Ni in a range of about 30% to about 60% by weight of the alloy precursor, and the second metal is Al in a range of about 40% to about 65% by weight of the alloy precursor.

19. The alloy precursor according to claim 16, wherein the first metal is Ni in a range of about 40% to about 49% by weight of the alloy precursor, and the second metal is Al in a range of about 50% to about 60% by weight of the alloy precursor.

20. The catalyst prepared from the alloy precursor according to claim 18, wherein the catalyst is a skeletal metal catalyst containing copper as a promoter.

21. The catalyst according to claim 20, wherein the copper is present in an amount in a range of about 1.0% to about 12.0% by weight of the catalyst.

22. The catalyst according to claim 21, wherein the copper is present in an amount in a range of about 2.0% to about 8.0% by weight of the catalyst.

23. A process for preparing a catalyst, the process comprising: melting and mixing copper, a first metal, and a second metal to form an alloy precursor; wherein the first metal is selected from the group consisting of Ni, Co, Fe, and mixtures thereof, and the second metal is selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof.

24. The process according to claim 23, wherein the first metal is Ni and the second metal is aluminum.

25. The process according to claim 24, wherein Ni is present in an amount in the range of about 40 wt% to about 49 wt% of the alloy precursor, aluminum is present in an amount in the range of about 50 wt% to about 60 wt% of the alloy precursor, and copper is present in an amount in the range of about 1.0 wt% to about 10.0 wt% of the alloy precursor. **Claim 26** The process according to claim 25, further comprising contacting the alloy precursor with an aqueous alkaline solution to produce the catalyst, wherein the catalyst contains copper in an amount in the range of about 1.0 wt% to 12.0 wt% of the catalyst. **Claim 27** The process according to claim 25, wherein the catalyst is a skeletal metal catalyst.

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