Catalyst, preparation method thereof and selective hydrogenation method

Abstract

The invention relates to a method for preparing 1, 4-butanediol. The method can include reacting a solution comprising 1, 4-butynediol with hydrogen in the presence of an effective amount of a catalyst. The catalyst may comprise copper.

Description

[0001] This application is a divisional application of the invention application with application number "202180038880.X" and invention title "Catalyst, Preparation Method Thereof and Selective Hydrogenation Method". Technical Field

[0002] This invention relates to catalysts, and more specifically, to catalysts for the preparation of 1,4-butanediol, methods for their preparation, selective hydrogenation methods using said catalysts, and alloy precursors for the preparation of said catalysts. Background Technology

[0003] Skeletal nickel catalysts in granular fixed-bed form are commonly used industrially to prepare butanediol (BDO) from the unsaturated compound 1,4-butynediol (BYD), a component in the preparation of polyesters. One form of skeletal nickel catalyst is produced by the Raney process, starting with an alloy containing at least two metals, such as nickel and aluminum. Optionally, other metals or compounds are added in small amounts as "promoters" to enhance the catalyst's activity, selectivity, or durability.

[0004] US 6,262,317 discloses a method for the continuous catalytic hydrogenation of 1,4-butynediol to 1,4-butanediol. The method comprises reacting 1,4-butynediol with hydrogen in a liquid continuous phase in the presence of a heterogeneous hydrogenation catalyst. The catalyst typically contains one or more elements from transition groups I, VI, VII, and VIII of the periodic table. Preferably, the catalyst also contains at least one element selected from groups II, III, IV, and VI of the periodic table, transition group II, III, IV, and V, and a lanthanide element as a promoter to increase activity. The promoter content of the catalyst is typically up to 5% by weight. The catalyst can be a precipitated, supported, or framework catalyst.

[0005] CN 201210212109.2 discloses a method for preparing and activating a framework metal nickel-aluminum-X catalyst, which is specifically used for the hydrogenation of 1,4-butynediol to 1,4-butanediol. X represents Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo, or Fe.

[0006] U.S. Patent Application No. 62 / 715,926 discloses a method for preparing 1,4-butanediol. The method involves reacting a solution containing 1,4-butynediol with hydrogen in the presence of a catalyst containing cerium as a promoter. This method can significantly reduce the formation of butanol byproducts.

[0007] Current catalysts typically have predictable finite lifetimes. Current methods produce n-butanol, acetals (e.g., 2-(4-hydroxybutoxy)tetrahydrofuran), and other byproducts at gradually increasing rates until a maximum specification limit is reached, which defines the end of the catalyst's lifespan. Acidic Al substances present in framework metal catalysts, such as hydrated alumina residues from leaching processes, are considered a major cause of byproducts containing butanol and acetals. Framework metal catalysts can often contain small amounts of added elements as promoters, whose function includes improving the catalyst's activity, selectivity, and stability in the chemical environment of a given hydrogenation process. Some promoters used with framework metals (such as conventional Mo, Cr, or Fe) can actually increase the formation of butanol byproducts due to increased surface acidity. Operating conditions, such as relatively low temperatures, relatively high pressures, and feed pH control, have been previously optimized, but their combinations still fail to adequately suppress the formation of butanol and acetals. Butanediol is a major component in the preparation of polyesters. Because downstream applications impose impurity restrictions on butanediol, reducing contaminants in butanediol during its preparation can significantly reduce costs, such as those associated with subsequent separation of impurities and butanediol (e.g., distillation). Summary of the Invention

[0008] This invention provides a method for preparing 1,4-butanediol from a 1,4-butynediol solution in the presence of a catalyst comprising copper. In addition to maintaining a desired low level of another key byproduct, n-butanol, in the final 1,4-butanediol product, the method significantly and unexpectedly reduces the amount of the major byproduct acetal (2-(4-hydroxybutoxy)tetrahydrofuran).

[0009] Therefore, one example of the present invention is a method for preparing 1,4-butanediol. This method may include reacting a solution containing 1,4-butynediol with hydrogen in the presence of a catalyst comprising copper as a promoter.

[0010] Another example of the invention is an alloy precursor for a catalyst used to prepare 1,4-butanediol. The alloy precursor may comprise a first metal, a second metal, and copper ranging from about 1% to about 10% by weight in the alloy precursor.

[0011] Another example of the invention is a catalyst for the preparation of 1,4-butanediol. The catalyst may be a skeletal metal catalyst containing copper as a promoter.

[0012] Another example of the invention is a method for preparing a catalyst. This method may include melting and mixing copper, a first element, and a second element to form an alloy precursor, followed by activation with an alkaline solution to form a catalyst. The first element may be Ni, and the second element may be aluminum.

[0013] The present invention discloses the following technical solutions: Option 1. A method for preparing 1,4-butanediol, the method comprising: A solution containing 1,4-butynediol is reacted with hydrogen in the presence of an effective amount of catalyst. The catalyst contains copper.

[0014] Option 2. The method according to Option 1, wherein the catalyst is in the form of a fixed bed, a suspension, or a combination thereof.

[0015] Option 3. The method according to Option 2, wherein the catalyst is in the form of a fixed bed and has a particle size in the range of about 1 mm to about 8 mm.

[0016] Option 4. The method according to Option 2, wherein the catalyst is in the form of a suspension and has a median particle size in the range of about 10 µm to about 100 µm.

[0017] Option 5. The method according to Option 1, wherein the catalyst further comprises at least a first metal selected from the group consisting of Ni, Co, Fe, and mixtures thereof.

[0018] Option 6. The method according to Option 5, wherein the first metal is Ni.

[0019] Option 7. The method according to Option 5, wherein the catalyst further comprises at least a second metal selected from the group consisting of: aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium, and mixtures thereof.

[0020] Option 8. The method according to Option 7, wherein the second metal is aluminum.

[0021] Option 9. The method according to Option 1, wherein the catalyst is a framework metal catalyst.

[0022] Option 10. The method according to Option 1, wherein copper is present in an amount ranging from about 1.0 wt% to about 12.0 wt% of the catalyst.

[0023] Option 11. The method according to Option 1, wherein copper is present in an amount ranging from about 2.0 wt% to about 8.0 wt% of the catalyst.

[0024] Option 12. The method according to Option 1, wherein the solution containing 1,4-butynediol has a pH in the range of about 4.0 to about 11.0.

[0025] Option 13. The method according to Option 1, wherein the solution containing 1,4-butynediol has a pH of about 7.5 to 10.

[0026] Option 14. The method according to Option 1, wherein, since the solution containing 1,4-butynediol has a pH of 7.5 or higher, the method produces an acetal as a byproduct in a range of less than about 0.5% by weight based on the total weight of butanol, acetal, and 1,4-butanediol.

[0027] Option 15. The method according to Option 1, wherein, since the solution containing 1,4-butynediol has a pH of 7.5 or higher, the method produces an acetal as a byproduct in the range of less than 0.25% by weight of the total weight of butanol, acetal, and 1,4-butanediol.

[0028] Scheme 16. An alloy precursor for a catalyst used to prepare 1,4-butanediol, said alloy precursor comprising a first metal, a second metal, and copper in the range of about 1.0 wt% to about 10.0 wt% of said alloy precursor.

[0029] Option 17. The alloy precursor according to Option 16, wherein copper is in the range of about 2.0% by weight to about 5.0% by weight in the alloy precursor.

[0030] Option 18. The alloy precursor according to Option 16, wherein the first metal is Ni in the range of about 30% to about 60% by weight of the alloy precursor, and the second metal is Al in the range of about 40% to about 65% by weight of the alloy precursor.

[0031] Option 19. The alloy precursor according to Option 16, wherein the first metal is Ni in the range of about 40% to about 49% by weight of the alloy precursor, and the second metal is Al in the range of about 50% to about 60% by weight of the alloy precursor.

[0032] Scheme 20. A catalyst prepared from an alloy precursor according to Scheme 18, wherein the catalyst is A framework metal catalyst, wherein the framework metal catalyst contains copper as a promoter.

[0033] Option 21. The catalyst according to Option 20, wherein copper is present in an amount ranging from about 1.0% by weight to about 12.0% by weight of the catalyst.

[0034] Option 22. The catalyst according to Option 21, wherein copper is present in an amount ranging from about 2.0 wt% to about 8.0 wt% of the catalyst.

[0035] Option 23. A method for preparing a catalyst, the method comprising: Copper, a first metal, and a second metal are melted and mixed to form an alloy precursor. 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.

[0036] Option 24. The method according to Option 23, wherein the first metal is Ni and the second metal is aluminum.

[0037] Option 25. The method according to Option 24, wherein Ni is present in an amount ranging from about 40 wt% to about 49 wt% of the alloy precursor, aluminum is present in an amount ranging from about 50 wt% to about 60 wt% of the alloy precursor, and copper is present in an amount ranging from about 1.0 wt% to about 10.0 wt% of the alloy precursor.

[0038] Option 26. The method according to Option 25 further includes: The alloy precursor is contacted with an alkaline aqueous solution to produce the catalyst. The catalyst contains copper in an amount ranging from about 1.0% to 12.0% by weight.

[0039] Option 27. The method according to Option 25, wherein the catalyst is a skeletal metal catalyst. Detailed Implementation

[0040] The present invention is described with reference to embodiments thereof in order to provide those skilled in the art with a better understanding of the technical solutions disclosed herein.

[0041] In this article, numbers modified by “approximately” mean that the number can vary by 10%. A range of values ​​modified by “approximately” means that the upper and lower limits of the range can vary by 10%. Butanol, n-butanol, and 1-butanol are all synonyms used for our purposes and are interchangeable.

[0042] One example of the present invention is a method for preparing 1,4-butanediol. This method may include reacting a solution containing 1,4-butynediol with hydrogen in the presence of an effective amount of catalyst comprising copper as a promoter. "Effective amount of catalyst" as used herein refers to a process that achieves a total conversion of at least about 95%, preferably at least about 99%, of the starting butynediol, exhibiting good selectivity for 1,4-butanediol. A promoter is a minor component in the catalyst compared to other major components (such as nickel and aluminum) to enhance the catalyst's activity, selectivity, or durability.

[0043] Solutions containing 1,4-butynediol can be technical-grade 1,4-butynediol in aqueous solution form and may additionally contain components from butynediol synthesis, such as bismuth, aluminum, or silicon compounds, as insoluble or soluble components. The primary solvent for solutions containing 1,4-butynediol is typically water. Solutions containing 1,4-butynediol may also contain other solvents, such as methanol, ethanol, propanol, butanol, or recycled 1,4-butanediol products. Solutions containing recycled 1,4-butanediol products may contain lower amounts of 1,4-butynediol than those containing only water as a solvent. The 1,4-butynediol content in the solution is typically from 5% to 90% by weight, preferably from 10% to 80% by weight, and particularly preferably from 10% to 50% by weight. In one embodiment, the solution containing 1,4-butynediol is 100% pure butynediol.

[0044] The pH of the solution containing 1,4-butynediol can be 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 the process conditions such as the mass of butynediol, temperature, pressure, etc., or optionally adjusted by using a small amount of diluent (such as NaOH solution).

[0045] The hydrogen required for the reaction is preferably used in pure form. However, it may also contain other components such as methane and carbon monoxide. The hydrogen pressure applied to the fixed-bed reactor for this method can range from about 15 MPa to about 30 MPa. The inlet temperature of the fixed-bed reactor can range from about 80 °C to about 120 °C. Those skilled in the art can select the combination of the feed solution flow rate and the effective amount of catalyst to allow for selection of the conversion rate, thereby achieving the desired overall conversion level of butynediol, i.e., reacting with hydrogen to form the product. The selected conversion rate of butynediol then depends on whether the process stream is partially recycled to the reactor inlet. For non-recycled process streams, the selected conversion rate produces a high gross conversion percentage, for example, above 98 wt% of 1,4-butynediol in a “single pass”. Similar high levels of gross conversion can also be achieved at variable rates, for example using a partially recycled process stream, where 10% to 20% of the process stream is removed as the final product at the reactor outlet, and another 80% to 90% is returned to the inlet.

[0046] According to the present invention, the catalyst used is one capable of hydrogenating C≡C triple and double bonds into single bonds. The catalyst can be in the form of a fixed bed, a slurry, a suspension, or a combination thereof. In one embodiment, the catalyst is in the form of a fixed bed and can have a particle size ranging from about 1 mm to about 8 mm, preferably from 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 ranging from about 10 µm to about 100 µm, preferably from about 20 µm to about 80 µm.

[0047] 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.

[0048] The catalyst can be a framework metal catalyst. Suitable framework metal catalysts include framework nickel, framework cobalt, framework nickel / molybdenum, framework nickel / chromium, framework nickel / chromium / iron, or rhenium sponge.

[0049] Copper may be present in the catalyst in an amount ranging from about 1.0% to 20.0% by weight, preferably from about 1.0% to about 12.0% by weight, and more preferably from about 2.0% to about 8.0% by weight.

[0050] The molar ratio of hydrogen to butynediol in the reactor can be at least 3:1, preferably 4:1 to 100:1.

[0051] When a fixed-bed reactor is used in the method of the present invention, the space velocities of the solution and gas flowing through the catalyst fixed bed are not limited. Those skilled in the art can adjust the space velocities of the solution and gas to obtain the optimal yield of 1,4-butanediol, with small amounts of byproducts such as butanol and acetal.

[0052] The catalyst according to the invention may contain only one type of catalyst or a mixture of several types of catalysts. The mixture of several types of catalysts may exist as a pseudo-homogeneous mixture or as a structured bed, wherein each individual reaction zone is composed of a pseudo-homogeneous catalyst bed. Methods may also be combined, for example, using one type of catalyst at the start of the reaction and using another downstream mixture.

[0053] Since the solution containing 1,4-butynediol has a pH of 7.5 or higher, the method can produce acetals as byproducts in a range of less than about 1.0% by weight, preferably less than about 0.5% by weight, and more preferably less than about 0.25% by weight, based on the total weight of acetal, butanol, and 1,4-butanediol.

[0054] In one embodiment of the method for preparing 1,4-butanediol, the catalyst is a skeletal element catalyst. The catalyst comprises 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 ranging from 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. Because the solution containing 1,4-butynediol has a pH of 7.5 or higher, the method produces an acetal as a byproduct in a range of less than about 1.0 wt%, preferably less than about 0.5 wt%, and more preferably less than about 0.25 wt% based on the total weight of the acetal, butanol, and 1,4-butanediol.

[0055] Another example of the invention is an alloy precursor for a catalyst used to prepare 1,4-butanediol. The alloy precursor may comprise a first metal, a second metal, and copper in the range of about 1.0 wt% to about 10.0 wt%, preferably about 2.0 wt% to 7.0 wt%.

[0056] In one embodiment, copper is in the range of about 2.0 wt% to about 5.0 wt% of the alloy precursor.

[0057] 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.

[0058] Another example of the invention is a catalyst for the preparation of 1,4-butanediol. The catalyst may comprise a framework metal catalyst containing copper as a promoter. Copper may be present in the catalyst in an amount ranging from about 1.0 wt% to about 10.0 wt%, preferably from about 2.0 wt% to about 8.0 wt%. In one embodiment, the framework metal comprises about 1.0 wt% to about 10.0 wt% copper, with nickel as the first element and aluminum as the second element.

[0059] Another example of the invention is a method for preparing a catalyst. This method may include melting and mixing copper, a first element, and a second element to form an alloy precursor.

[0060] 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. Based on the total weight of the alloy precursor, Ni may be present in an amount ranging from about 30 wt% to about 60 wt%, preferably from about 40 wt% to about 49 wt%. Based on the total weight of the alloy precursor, aluminum may be present in an amount ranging from about 40 wt% to about 65 wt%, preferably from about 50 wt% to 60 wt%. Based on the total weight of the alloy precursor, copper may be present in an amount ranging from about 1.0 wt% to about 10.0 wt%, preferably from about 2.0 wt% to about 6.0 wt%.

[0061] In one embodiment, the method of preparing the catalyst further includes activating the alloy precursor by contacting it with an alkaline solution. The alkaline solution may be an aqueous solution of sodium hydroxide or potassium hydroxide with a concentration ranging from 1% to 25% by weight. In one embodiment, the alkaline solution is continuously pumped through an alloy precursor bed to activate the alloy precursor. In another embodiment, alloy precursor particles are added batchwise to the alkaline solution to activate the alloy precursor. In one embodiment, the catalyst is a framework metal catalyst.

[0062] In one embodiment, the method 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. Based on the total weight of the catalyst, copper is present in an amount ranging from about 1.0 wt% to about 10.0 wt%. In one embodiment, the first element of the framework metal is nickel, and the second element of the framework metal is aluminum, comprising about 1.0 wt% to about 12.0 wt% copper.

[0063] Another example of the present invention is a catalyst produced by a method for preparing a catalyst according to an embodiment of the present invention.

[0064] Various embodiments of the invention have been described for illustrative purposes, but are not intended to be exhaustive or limiting. 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 terminology used herein has been chosen to best explain the principles of the embodiments, practical applications of technology found in the market, or technical improvements, or to enable others skilled in the art to understand the embodiments disclosed herein.

[0065] The invention will be described in more detail below with reference to embodiments. However, the scope of the invention is not limited to the following embodiments. Example

[0066] Example 1 Catalyst preparation. An alloy precursor containing 58 wt% Al, 2.5 wt% Cu, and 39.5 wt% Ni was formed by melting and mixing the three components. The alloy precursor was then crushed and sieved into alloy precursor particles in the size range of 8-12 mesh, or alloy precursor particles with a diameter in the range of about 2 mm to about 3 mm.

[0067] A 390g portion of the alloy precursor particles was placed in a beaker to form a "bed". This bed of alloy precursor particles was converted into a catalyst by contact with a 'leaching agent', which involved continuously pumping five portions of NaOH aqueous 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 from 1% during the process, then increased by 2%, 3%, 4%, and finally 5%, respectively. Each portion of the NaOH aqueous solution was delivered through the alloy precursor bed over 40 minutes, while the process temperature, targeted at 38°C, was controlled using an immersed cooling coil (with internal water flow).

[0068] The catalyst was then washed with 2 liters of 0.25% NaOH solution for 10 minutes, followed by washing with water at 45°C until the effluent wash water reached a pH of 9.

[0069] The catalyst, as determined by ICP analysis, contained the following components (wt%): 54.6 Ni, 41.7 Al, 3.5 Cu, and 0.2 Fe. Catalysis test The prepared catalyst was kept in a water-wetted state as it was loaded into a vertical column reactor with a bed size of approximately 0.5 inches in inner diameter and approximately 6 inches in height. The quantity was 18 mL of catalyst bed.

[0070] A reactant feed solution was prepared by dissolving 1,4-butanediol at 40 wt% (representing recycled 'BDO' product) and 2-butyn-1,4-diol at 10 wt% in water. The total organic compound content was nominally 50%, and water at 50%. When freshly prepared, the pH of this mixture varied from about 4 to about 5.5. As another variable for subsequent catalyst testing, an additional portion of the reactant feed solution was prepared, and this additional portion was then adjusted to a pH ranging from about 7.0 to about 8.5 by adding a small amount of 15% NaOH solution.

[0071] In the catalyst testing, the reaction conditions used were: inlet temperature 100°C, peak temperature 150°C (outlet temperature), hydrogen pressure approximately 2500 psig (16 MPa to 17 MPa), and a controllable liquid feed rate. 0.25 mL / min was the default liquid flow rate; a range of 0.10–2.5 was feasible. When the flow rate was varied, it was then maintained at a constant level for several days to achieve a stable product level. The co-current upward flow of H2 gas (300 mL / min) and liquid was maintained throughout the testing process.

[0072] Product determinations, expressed as weight percent of organic product, were performed by GC analysis using a Restek Stabilwax 30 x 0.32 x 0.5 column, 90% ethanol solvent, diethylene glycol dimethyl ether as an internal standard, and a flame ionization detector. The reported yields for each condition in Tables 1 and 2 are averages of samples collected after each 8-hour continuous operation.

[0073] The main byproduct of interest, n-butanol (“BuOH”), ranged from 0.23% to 0.35% under various pH conditions. Butanol yields were lower when using feed solutions with higher pH values. The second byproduct, 2-(4-hydroxybutoxy)tetrahydrofuran, a cyclized acetal formed from the reaction and dehydration of the product and feed molecules, is listed as “acetal” in Tables 1 and 2. As shown in Table 1, the acetal content varied from 0.17% to 0.38% at different pH values.

[0074] Table 1 lists the pH of the reactant feed solution used, the time elapsed under the specified pH conditions, and a summary of the two key byproducts.

[0075] Example 2 Catalyst preparation: The method used was similar to that of Example 1, except that the alloy composition was: 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.

[0076] Catalyst testing The tests were conducted similarly to those in Example 1 to demonstrate the improvement on Ce-Ni and to show the effect of Cu content compared to Example 1.

[0077] 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 similar to those 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 had a composition of 51.5% Al, 45.2% Ni, and 3.3% Ce.

[0078] Catalyst testing The test conditions and methods were as described in Example 1. The test results are shown in Table 2. As summarized in Table 2, butanol byproducts in the range of 0.21% to 0.55% and acetals in the range of 0.40% to 0.65% were obtained.

[0079] As shown in Tables 1 and 2, the catalyst employing one embodiment of the invention demonstrates a significant improvement in acetal byproduct levels by using copper instead of cerium as a promoter, while maintaining similar or slightly lower butanol byproduct levels. These byproducts have maximum permissible levels in full-scale industrial use. Therefore, these reductions in acetal byproducts are particularly significant in industrial applications, thereby extending the lifespan of fixed-bed catalyst systems by increments typically of several months, translating to lower operating costs for users. The use of Cu metal also offers other benefits compared to CeO2, such as lower cost and simpler operation.

[0080] Table 1

[0081] Table 2

[0082] The principles and embodiments of this disclosure are set forth in the specification. The description of the embodiments of this disclosure is only for the purpose of aiding understanding the methods and core concepts of this disclosure. Furthermore, for those skilled in the art, this disclosure covers a wide range of possibilities, and the technical solutions are not limited to specific combinations of technical features, but should also cover other technical solutions formed by combining technical features or equivalent features, without departing from the inventive concept. For example, a technical solution can be obtained by replacing the features described above with features disclosed in this disclosure (but not limited to) that have similar features.

Claims

1. A method for preparing a catalyst, the method comprising: Copper, a first metal, and a second metal are melted and mixed to form an alloy precursor. 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.

2. The method according to claim 1, wherein the first metal is Ni and the second metal is aluminum.

3. The method of claim 2, wherein Ni is present in an amount ranging from about 30% to about 60% by weight of the alloy precursor, aluminum is present in an amount ranging from about 40% to about 65% by weight of the alloy precursor, and copper is present in an amount ranging from about 1.0% to about 12.0% by weight of the alloy precursor.

4. The method of claim 2, wherein Ni is present in an amount ranging from about 40% to about 49% by weight of the alloy precursor, aluminum is present in an amount ranging from about 50% to about 60% by weight of the alloy precursor, and copper is present in an amount ranging from about 1.0% to about 10.0% by weight of the alloy precursor.

5. The method according to claim 3, further comprising: The alloy precursor is contacted with an alkaline aqueous solution to produce the catalyst. The catalyst contains copper in an amount ranging from about 1.0% to 12.0% by weight.

6. The method according to claim 3, wherein the catalyst is a skeletal metal catalyst.

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