High-temperature methanol steam reforming catalyst

Abstract

The present disclosure generally relates to a methanol reforming catalyst composition. The composition includes a ZnO phase in an amount of 20 to 75 wt% in the composition, a zinc-aluminum spinel phase in an amount of 20 to 60 wt% in the composition, and a Cu dopant phase in an amount of 0.1 to 20 wt% in the composition. In various embodiments, the methanol reforming catalyst can obtain a high methanol conversion rate and a high hydrogen production rate that are stable even at high temperatures (>300 °C).

Description

Technical Field

[0001] The present disclosure generally relates to a methanol steam reforming catalyst. More specifically, the present disclosure relates to a spinel-based catalyst useful for high-temperature methanol steam reforming reaction, a method for producing the catalyst, and a method for producing hydrogen from methanol using the catalyst.

Background Art

[0002] Hydrogen fuel cells are one of the most promising new clean technologies for producing electricity. This technology is attracting increasing attention currently due to its energy efficiency and environmental advantages. However, the storage and transportation of hydrogen remain a problem due to insufficient storage capacity and safety concerns. Therefore, an alternative hydrogen source is needed to overcome these storage and transportation problems. One such alternative is to use methanol to produce hydrogen on-site by methanol steam reforming. Methanol steam reforming can reduce or even eliminate the need for hydrogen storage and transportation. Compared with hydrogen, the storage and transportation of methanol are much more cost-effective and safe. Methanol is also a desirable precursor candidate for hydrogen production compared with methane and other alcohols. Methanol has a high hydrogen content, and theoretically, 3 moles of hydrogen are produced from 1 mole of methanol during steam reforming. Furthermore, methanol can be obtained from biomass, which can significantly reduce carbon emissions and make the methanol steam reforming process more environmentally sustainable. Therefore, methanol steam reforming is a desirable alternative for supplying hydrogen to fuel cells used in stationary power systems and mobile applications.

[0003] Methanol steam reforming has conventionally been carried out either at low temperature (less than 300 °C) or at high temperature (at least 300 °C). Since the reaction is an endothermic reaction (Equation 1), the reforming reaction is preferably carried out at a higher temperature to achieve a higher H 2 yield. CH 3 OH + H2 O → 3H 2 + CO 2 , ΔH 298K = 49.3 kJ / mol (1) According to the report, under favorable conditions, the H 2 selectivity can reach 75%. Therefore, it is desirable to have a methanol steam reforming catalyst that can withstand high-temperature conditions in order to achieve a high methanol conversion rate. Naturally, the steam reforming process requires a catalyst suitable for specific conditions, which can be a particularly stringent requirement for high-temperature processes.

[0004] To cope with the methanol steam reforming reaction conditions, various catalysts have been developed. Conventionally, the most commonly used catalysts for methanol steam reforming and methanol synthesis are based on copper and Group VIIIB metals. For example, Non-Patent Document 1 (Chem. Rev. 2007, 107, 3992~4021) can be referred to. Copper-based catalysts are not only active and selective for H 2 but also stable at reaction temperatures below 300°C. However, copper catalysts, such as commercially available CuO-ZnO / Al 2 O 3 catalysts tend to sinter rapidly above 280°C and are susceptible to the effects of condensed steam, sulfur, chlorides, and coke deposition. Also, the pyrophoricity when exposed to air is a problem. To address these issues, rare earth oxides, Cr 2 O 3 and ZrO 2 have been used as carriers or supports. Another common method to improve the CuO-ZnO catalyst formulation is to add promoters such as Ce, La, Ba, Mg, Co, Fe, etc. For example, Patent Document 1 (EP1077081A2), Patent Document 2 (CN104741128), and Patent Document 3 (JP2003-265961A) can be referred to.

[0005] Unlike copper-based catalysts, palladium / zinc or platinum / zinc alloy catalysts are more stable at high temperatures, such as 350 °C or higher, but exhibit relatively low activity. Coupled with the high price of precious metals, the commercial viability of palladium / zinc or platinum / zinc catalysts is very low (see, for example, Patent Document 4 (WO2010-138483A2)). Patent Documents 5 (US2001-0021469A1) and 6 (US2002-0039965A1) report that PdZnZr and Pd / Pt-CuZn catalysts also deactivate at high temperatures, and zinc elution was observed in the PdZnZr catalyst during reforming. There are also chromium / zinc catalysts for high-temperature methanol steam reforming. These exhibit excellent activity, selectivity, and stability at high temperatures. However, due to the toxicity and carcinogenicity of chromium, as countries around the world strengthen their environmental protection efforts, these catalysts are not industrially desirable. Other catalysts such as CuZr, NiZr, AgY, NiZn, AuHf, etc. have been used at low temperatures but are not suitable for high-temperature reforming reactions. See, for example, Patent Document 7 (US5635439A).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Non-Patent Documents

[0007]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, a methanol steam reforming catalyst that is active, sustainable, cost - effective, and environmentally friendly at high temperatures is still desired. The inventors of the present invention have developed a methanol reforming catalyst that maintains catalytic activity even at high temperatures.

Means for Solving the Problems

[0009] The inventors of the present invention have found that a catalyst based on a zinc - aluminum spinel phase containing a small amount of copper dopant has activity and stability even at high temperatures, is low - cost, and can be provided without causing adverse environmental effects by using a large amount of chromium.

[0010] One aspect of the present disclosure provides a methanol reforming catalyst composition comprising a ZnO phase in an amount of 20 - 75 wt% in the composition, a zinc - aluminum spinel phase in an amount of 20 - 60 wt% in the composition, and a Cu dopant in an amount of 0.1 - 20 wt% in the composition. In various embodiments, the catalyst composition contains little or no crystalline Al 2 O 3 phase.

[0011] Another aspect of the present disclosure is a fired methanol reforming catalyst composition comprising oxides of Zn, Al, and Cu, wherein Zn has a total amount in the composition, calculated as ZnO, of 40 - 80 wt% (for example, 60 - 80 wt%), Al has a total amount in the composition, calculated as Al 2 O 3 of 20 - 50 wt% (for example, 20 - 40 wt%), and Cu has a total amount in the composition, calculated as CuO, of 0.5 - 25 wt% (for example, 1 - 15 wt%). Here, the catalyst, measured by XRD, has ZnAl 2 O 4Calculated as, it contains at least 20 wt% (e.g., at least 30 wt%, or at least 40 wt%) of zinc-aluminum spinel.

[0012] Another aspect of the present disclosure is a method for manufacturing the methanol reforming catalyst composition described herein. The method includes the steps of preparing an aqueous precursor solution containing zinc ions, aluminum ions, and copper ions; precipitating a solid catalyst precursor containing salts of zinc, aluminum, and copper from the aqueous precursor solution; and then firing the solid catalyst precursor to obtain a catalyst composition. Another aspect of the present disclosure is a method for performing a methanol reforming reaction. The method includes the step of contacting a feed containing water and methanol with the methanol reforming catalyst composition described herein at a temperature of at least 300 °C to produce hydrogen and carbon dioxide.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0014] The present disclosure relates to a methanol reforming catalyst composition containing zinc, aluminum, oxygen, and copper. The present disclosure demonstrates that the catalyst preferably contains little chromium and can exhibit activity equivalent to or higher than that of conventional methanol reforming catalysts. The present disclosure demonstrates that the catalyst can be used at a higher temperature compared to catalysts manufactured by conventional methods in various embodiments.

[0015] In various preferred aspects and embodiments of the compositions described separately herein, zinc is present in the form of ZnO. In various advantageous aspects and embodiments of the compositions described separately herein, zinc, aluminum, and oxygen form a zinc aluminum spinel crystal structure. Preferably, the inventors have found that adding copper to the methanol reforming catalyst improves the catalytic activity. Accordingly, in various embodiments described separately herein, the disclosed materials include a Cu dopant. The inventors have found that including copper provides good catalytic activity and stability at high temperatures.

[0016] Accordingly, one aspect of the present disclosure is a methanol reforming catalyst composition. The catalyst composition includes a ZnO phase in an amount of 20 to 75 wt%, a zinc-aluminum spinel phase in an amount of 20 to 60 wt% in the composition, and a Cu dopant in an amount of 0.1 to 20 wt% in the composition. The amounts of such phases are measured using X-ray diffraction with the Rietveld refinement method.

[0017] As described above, the ZnO phase is 20 to 75% by weight in the composition of this embodiment. In the catalyst composition of the present disclosure, the content of the ZnO phase can be varied within this range. For example, in various embodiments described separately herein, the ZnO phase is 20 to 70% by weight, for example, 20 to 65% by weight, or 20 to 60% by weight, or 20 to 55% by weight, or 20 to 50% by weight, or 20 to 45% by weight, or 20 to 40% by weight. In various embodiments described separately herein, the ZnO phase is 25 to 75% by weight (e.g., 25 to 70% by weight or 25 to 65% by weight or 25 to 60% by weight or 25 to 55% by weight or 25 to 50% by weight or 25 to 45% by weight or 25 to 40% by weight) in the composition. In various embodiments described separately herein, the ZnO phase is 30 to 75% by weight or 30 to 70% by weight or 30 to 65% by weight or 30 to 60% by weight or 30 to 55% by weight or 30 to 50% by weight or 30 to 45% by weight or 30 to 40% by weight in the composition. In various embodiments described separately herein, the ZnO phase is 35 to 75% by weight (e.g., 35 to 70% by weight or 35 to 65% by weight or 35 to 60% by weight or 35 to 55% by weight or 35 to 50% by weight or 35 to 45% by weight or 35 to 40% by weight) in the composition. In various embodiments described separately herein, the ZnO phase is 40 to 75% by weight (e.g., 40 to 70% by weight or 40 to 65% by weight or 40 to 60% by weight or 40 to 55% by weight or 40 to 50% by weight) in the composition.

[0018] In various embodiments described separately herein, in the composition described separately herein, the ZnO phase has an average crystallite size of 1 to 50 nm. For example, in various embodiments, the ZnO phase has an average crystallite size of 1 to 45 nm (e.g., 1 to 40 nm or 1 to 35 nm or 1 to 30 nm). In various embodiments, the ZnO phase has an average crystallite size of 2 to 50 nm (e.g., 2 to 45 nm or 2 to 40 nm or 2 to 35 nm or 2 to 30 nm).

[0019] In various embodiments, the ZnO phase has an average crystallite size of 5 to 50 nm, for example, 5 to 45 nm, or 5 to 40 nm, or 5 to 35 nm, or 5 to 30 nm. As those skilled in the art will understand, the smaller the crystallite size, the larger the surface area. By having a larger surface area, the total catalytic surface area for the methanol steam reforming reaction increases, resulting in higher overall catalytic activity.

[0020] As described above, in the composition of this aspect, the zinc-aluminum spinel phase is present in an amount of 20 to 60% by weight. In various embodiments described herein, the zinc-aluminum spinel phase is 20 to 55% by weight (for example, 20 to 50% by weight, 20 to 45% by weight, 20 to 40% by weight, or 20 to 35% by weight) in the composition. In various embodiments described herein, the zinc-aluminum spinel phase is 25 to 60% by weight (for example, 25 to 55% by weight, 25 to 50% by weight, 25 to 45% by weight, 25 to 40% by weight, or 25 to 35% by weight) in the composition.

[0021] In various embodiments, the average crystallite size of the zinc-aluminum spinel phase of the composition described herein is 1 to 100 nm. The average crystallite size of the zinc-aluminum spinel phase of the composition described herein can vary. For example, in various embodiments, the average crystallite size of the zinc-aluminum spinel phase is 1 to 75 nm (for example, 1 to 50 nm). In various embodiments, the average crystallite size of the zinc-aluminum spinel phase is 2.5 to 100 nm (for example, 2.5 to 75 nm or 2.5 to 50 nm). In various embodiments, the average crystallite size of the zinc-aluminum spinel phase is 5 to 100 nm (for example, 5 to 75 nm or 5 to 50 nm). Similar to the crystallite size of the ZnO phase, the smaller the crystallite size of the zinc-aluminum spinel phase, the more it correlates with a higher surface area and provides higher catalytic activity.

[0022] Zinc-aluminum spinel itself typically has the idealized chemical formula ZnAl 2 O 4Since it has, it may be desirable to select a ratio of zinc to aluminum that provides a desired amount of spinel structure together with other elemental components. In various embodiments of the compositions described herein, zinc is present in an amount exceeding that required to form the spinel structure, i.e., it provides a substantial amount of ZnO as described herein.

[0023] As described above, in the compositions according to this aspect of the present disclosure, the Cu dopant is from 0.1 to 20 wt%. The amount of the Cu dopant in the compositions described herein can also vary. In various embodiments, the Cu dopant is from 0.1 to 15 wt% (e.g., from 0.1 to 10 wt%) in the composition. In various embodiments, the Cu dopant is from 0.5 to 20 wt% (e.g., from 0.5 to 15 wt% or from 0.5 to 10 wt%) in the composition. In various embodiments, the Cu dopant is from 1 to 20 wt% (e.g., from 1 to 15 wt% or from 1 to 10 wt%) in the composition. The inventors have determined that the amount of copper required for the desired activity and stability is very small. Therefore, in various embodiments, the Cu dopant in the composition does not exceed 15 wt% (e.g., 10 wt%).

[0024] In various embodiments, the catalyst composition of the present disclosure is substantially free of or completely free of crystalline Al 2 O 3 phase. For example, in various embodiments, the amount of crystalline Al 2 O 3 phase in the catalyst composition is 5 wt% or less. For example, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less. In various embodiments, the catalyst composition contains Al 2 O 3 phase in an amount in the range of 1 to 6 wt%, 1 to 4 wt%, 1 to 3 wt%, or 1 to 2 wt%. In various embodiments, the catalyst composition is substantially free of crystalline Al 2 O 3 phase, e.g., 0.5 wt% or less.

[0025] In another definition of the useful catalyst composition of the present disclosure, the catalyst composition is a calcined methanol reforming catalyst composition containing oxides of Zn, Al, and Cu, where the total amount of Zn in the composition is 40 to 80 wt% calculated as ZnO (e.g., 60 to 80 wt%), Al has a total amount in the composition of 20 to 50 wt% calculated as 2 O 3 (e.g., 20 to 40 wt%), and Cu has a total amount in the composition of 0.5 to 20 wt% calculated as CuO (e.g., 1 to 15 wt%, or 1 to 10 wt%). Here, the catalyst composition, measured by XRD, contains at least 20 wt% (e.g., at least 30 wt%, or at least 40 wt%) of zinc-aluminum spinel calculated as ZnAl 2 O 4 . The catalyst composition according to this aspect of the present disclosure can have the features generally described with respect to the foregoing aspects in various embodiments.

[0026] In various embodiments of the catalyst composition of the present disclosure, zinc, as calculated as ZnO, is 40 to 80 wt% in total in the composition. The amount of zinc in the catalyst composition of the present disclosure can vary within this range. For example, in various embodiments described herein, zinc, as calculated as ZnO, is 40 to 75 wt% (e.g., 40 to 70 wt% or 40 to 65 wt% or 40 to 60 wt%) in total in the composition. In various embodiments described herein, zinc, as calculated as ZnO, is 45 to 80 wt% (e.g., 45 to 75 wt% or 45 to 70 wt% or 45 to 65 wt% or 45 to 60 wt%) in total in the composition. In various embodiments described herein, zinc, as calculated as ZnO, is 50 to 80 wt% (e.g., 50 to 75 wt% or 50 to 70 wt% or 50 to 65 wt% or 50 to 60 wt%) in total in the composition. In various embodiments described herein, zinc, as calculated as ZnO, is 55 to 80 wt% (e.g., 55 to 75 wt% or 55 to 70 wt% or 55 to 65 wt% or 55 to 60 wt%) in total in the composition. In various embodiments described herein, zinc, as calculated as ZnO, is 60 to 80 wt% (e.g., 60 to 75 wt% or 60 to 70 wt% or 60 to 65 wt%) in total in the composition.

[0027] In various embodiments described herein, aluminum is Al 2 O 3 and is 20 to 50 wt% in total in the composition as calculated. The amount of aluminum in the catalyst composition of the present disclosure can vary within this range. For example, in various embodiments described herein, aluminum, as calculated as Al2O3, is 20 to 45 wt% (e.g., 20 to 40 wt% or 20 to 35 wt% or 20 to 30 wt%) in total in the composition. In various embodiments described herein, aluminum is Al 2 O 3Calculated as, in the composition, it is 25 to 50% by weight in total (for example, 25 to 45% by weight, 25 to 40% by weight, 25 to 35% by weight or 25 to 30% by weight in total). In various embodiments described herein, aluminum is Al 2 O 3 Calculated as, in the composition, it is 30 to 50% by weight in total (for example, 30 to 45% by weight, 30 to 40% by weight or 30 to 35% by weight in total).

[0028] In various embodiments described herein, copper is present in the composition in an amount of 0.5 to 20% by weight in total calculated as CuO. The amount of copper in the catalyst composition of the present disclosure can vary within this range. For example, in various embodiments described herein, copper is 0.5 to 15% by weight in total (for example, 0.5 to 10% by weight or 0.5 to 5% by weight) in the composition calculated as CuO. In various embodiments described herein, copper is 1 to 20% by weight in total (for example, 1 to 15% by weight, 1 to 10% by weight or 1 to 5% by weight) in the composition calculated as CuO. In various embodiments described herein, copper is 2 to 20% by weight in total (for example, 2 to 15% by weight, 2 to 10% by weight or 2 to 5% by weight) in the composition calculated as CuO.

[0029] In various embodiments described herein, the composition can further include one or more metal species. For example, in such various embodiments, the composition can include one or more of sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium; these generally do not form part of a crystalline spinel. The metal can be added as any compound that imparts the metal (e.g., as an oxide) to the catalyst composition (e.g., by impregnation) (e.g., prior to the calcination step). For example, in various embodiments, the metal is added as a salt selected from carbonates, nitrates, acetates, formates, oxalates, molybdates, and citrates. In various embodiments described herein, potassium is added as a salt. For example, as potassium acetate, introduced by impregnation prior to the calcination step. In various embodiments described herein, magnesium is added as a salt. For example, as magnesium acetate, introduced by impregnation prior to the calcination step. Generally, such metals are present in the catalyst composition in the form of oxides and generally exist separately from the crystalline spinel structure.

[0030] In various embodiments described herein, the composition additionally comprises only one metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium. One of ordinary skill in the art can select one or more suitable metal species based on the description herein. For example, in various embodiments of the compositions described herein, the composition comprises one or more (e.g., one) metal species selected from sodium, potassium, magnesium, and calcium. In another example, in various embodiments of the compositions described herein, the composition comprises one or more (e.g., one) metal species selected from potassium and magnesium. In various embodiments described herein, the composition comprises a first metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium and zirconium (e.g., sodium, potassium, magnesium and calcium) and a second metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium and zirconium (e.g., sodium, potassium, magnesium, and calcium). For example, in various embodiments, the composition comprises a first metal species selected from sodium and potassium and a second metal species selected from magnesium and calcium. In yet another example, in various embodiments of the compositions described herein, the composition comprises potassium as the first metal species and magnesium as the second metal species.

[0031] Without being bound by theory, the metal species described herein are thought to act as promoters that modify the reactivity in a desirable manner.

[0032] The metal species can be added in various amounts. For example, in various embodiments of the catalyst composition described herein, the catalyst composition can contain one or more metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium in an amount of 0.05 to 20 wt% in total. For example, in various embodiments described herein, the catalyst composition described herein can further contain one or more metal species of sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium in an amount of 0.05 to 15 wt% or 0.05 to 10 wt% or 0.05 to 5 wt% or 0.1 to 20 wt% or 0.1 to 15 wt% or 0.1 to 10 wt% or 0.1 to 5 wt% or 0.5 to 20 wt% or 0.5 to 15 wt% or 0.5 to 10 wt% or 0.5 to 5 wt% in total. In various desirable embodiments, the total amount of these metal species is 10 wt% or less, for example 5 wt% or less.

[0033] In certain embodiments described herein, the catalyst composition further contains at least one of magnesium and potassium. For example, in various embodiments described herein, the catalyst further contains 0.1 to 2 wt% of magnesium calculated as MgO and K 2Calculated as O, it contains at least one of potassium in an amount of 0.25 to 3% by weight. In various embodiments described herein, the catalyst further contains magnesium in an amount of 0.1 to 1.5% by weight (for example, 0.1 to 1.0% by weight or 0.1 to 0.75% by weight or 0.1 to 0.5% by weight) calculated as MgO. In various embodiments described herein, the catalyst further contains magnesium in an amount of 0.25 to 2.0% by weight (for example, 0.25 to 1.5% by weight or 0.25 to 0.75% by weight or 0.25 to 0.5% by weight) calculated as MgO. In various embodiments described herein, the catalyst further contains magnesium in an amount of 0.5 to 2.0% by weight (for example, 0.5 to 1.5% by weight or 0.5 to 1.0% by weight or 0.5 to 0.75% by weight) calculated as MgO. In various embodiments described herein, the catalyst further contains K 2 Calculated as K 2 O, it contains potassium in an amount of 0.25 to 2.75% by weight (for example, 0.25 to 2.5% by weight, 0.25 to 2.25% by weight, or 0.25 to 2% by weight). In various embodiments described herein, the catalyst further contains K 2 Calculated as K 2 O, it contains potassium in an amount of 0.5 to 3% by weight (for example, 0.5 to 2.75% by weight or 0.5 to 2.5% by weight or 0.5 to 2.25% by weight or 0.5 to 2% by weight).

[0034] The inventors have surprisingly found that it is possible to provide good catalytic activity and stability at high temperatures while using a relatively small amount of copper. In various embodiments described herein, the catalyst composition does not contain more than 20% by weight of copper calculated as CuO. For example, in various embodiments described herein, the catalyst composition does not contain more than 15% by weight of copper calculated as CuO. Also, in various embodiments, the catalyst composition does not contain more than 10% by weight of copper calculated as CuO. The inventors have found that by limiting the amount of copper in the methanol reforming catalyst, the catalyst can maintain its activity without deteriorating at high temperatures. Furthermore, the inventors have found that even when the abundance of copper is low, the catalyst exhibits a high methanol conversion rate and hydrogen selectivity.

[0035] As described above, chromium has conventionally been used in methanol shift catalysts with excellent activity, selectivity, and stability at high temperatures. However, since chromium is toxic and carcinogenic, it is desirable to avoid its use as much as possible. The inventors have found that the catalysts of the present disclosure exhibit good activity and stability at high temperatures even without chromium. Accordingly, in various embodiments described herein, the catalyst composition does not contain more than 1 wt% chromium, calculated as Cr 2 O 3 For example, in various embodiments described herein, the catalyst composition does not contain more than 0.5 wt%, or more than 0.1 wt%, or more than 0.01 wt% chromium, calculated as Cr 2 O 3

[0036] The catalyst compositions described herein can be substantially composed of oxides of copper, aluminum, and zinc. For example, in various embodiments of the catalyst compositions described herein, the total amount of oxides of Cu (calculated as CuO), Al (calculated as Al 2 O 3 ), and Zn (calculated as ZnO) is 90 wt% or more (e.g., 95 wt% or more) of the catalyst composition.

[0037] The inventors have also noted that the addition of certain metal species (e.g., as promoters) may be desirable. Accordingly, in various embodiments of the catalyst compositions described herein, the total amount of oxides of Cu (calculated as CuO), Al (calculated as Al 2 O 3 ), and Zn (calculated as ZnO), and the total amount of oxides of metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium (all calculated as the most common oxides) is at least 95 wt% (e.g., at least 98 wt%) of the catalyst composition.

[0038] ​In various embodiments described herein, the catalyst composition has a BET specific surface area in the range of 20 to 500 m 2 / g. For example, in various embodiments described herein, the catalyst composition has a BET specific surface area of 20 to 500 m 2 / g (e.g., 20 to 400 m 2 / g or 20 to 300 m 2 / g or 20 to 200 m 2 / g or 30 to 500 m 2 / g or 30 to 400 m 2 / g or 30 to 300 m 2 / g or 30 to 200 m 2 / g or 40 to 500 m 2 / g or 40 to 400 m 2 / g or 40 to 300 m 2 / g or 40 to 200 m 2 / g or 50 to 500 m 2 / g or 50 to 400 m 2 / g or 50 to 300 m 2 / g or 50 to 200 m 2 / g). One skilled in the art can use conventional techniques in conjunction with the synthesis techniques described herein to provide a catalyst having the desired surface area.

[0039] In various embodiments described herein, the catalyst composition has an N2 accessible pore volume of 0.05 to 1 cc / g. For example, in various embodiments described herein, the catalyst composition has an N2 accessible pore volume of 0.05 to 1.0 cc / g (e.g., 0.05 to 0.8 cc / g or 0.05 to 0.6 cc / g or 0.05 to 0.4 cc / g or 0.05 to 0.35 cc / g or 0.1 to 0.8 cc / g or 0.1 to 0.6 cc / g or 0.1 to 0.4 cc / g or 0.1 to 0.35 cc / g or 0.2 to 0.8 cc / g or 0.2 to 0.6 cc / g or 0.2 to 0.4 cc / g or 0.2 to 0.25 cc / g) of N 2 accessible pore volume. One skilled in the art can use conventional techniques in conjunction with the synthesis techniques described herein to provide a catalyst having the desired pore volume.

[0040] The inventors have found that the mixed oxide catalysts of copper, zinc, and aluminum of the present disclosure can be produced using the coprecipitation method. For example, other techniques such as the impregnation method can optionally be used to add additional species that are not suitable for the coprecipitation method. Another aspect of the present disclosure is a method for producing a methanol reforming catalyst composition. The method includes the steps of preparing an aqueous precursor solution containing zinc ions, aluminum ions, and copper ions; precipitating a solid catalyst precursor containing salts of zinc, aluminum, and copper from the aqueous precursor solution; and then firing the solid catalyst precursor to obtain a catalyst composition.

[0041] As described above, the production method includes the step of preparing an aqueous precursor solution containing zinc ions, aluminum ions, and copper ions. In various embodiments described herein, the step of preparing the aqueous precursor solution includes the step of dissolving one or more salts containing zinc ions, aluminum ions, and copper ions in water. For example, in various embodiments described herein, the one or more salts can be selected from the group consisting of zinc nitrate, zinc sulfate, zinc carbonate, zinc acetate, zinc chloride, zinc bromide, zinc iodide, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum acetate, aluminum chloride, aluminum bromide, aluminum iodide, copper nitrate, copper sulfate, copper carbonate, copper acetate, copper chloride, copper iodide, and copper bromide. In various embodiments of the present disclosure, the one or more salts containing zinc ions, aluminum ions, and copper ions have the same counter ion. In other embodiments described herein, the one or more salts containing zinc ions, aluminum ions, and copper ions have different counter ions. In a specific embodiment described herein, the step of preparing the precursor solution includes the step of dissolving one or more of zinc nitrate, aluminum nitrate, and copper nitrate in water.

[0042] As described above, the manufacturing method includes a step of precipitating a solid catalyst precursor containing salts of zinc, aluminum, and copper from the solution. In this precipitation, the pH of the solution can be adjusted to the range of 5 to 7.5. For example, in various embodiments of the manufacturing method described in this specification, the pH of the precursor solution is adjusted to, for example, 5 to 7.2, 5 to 7, 5 to 6.8, 5 to 6.5, 5 to 6.2, 5 to 6, 5.5 to 7.5, 5.5 to 7.2, 5.5 to 7, 5.5 to 6.8, 5.5 to 6.5, 6 to 7.5, 6 to 7.2, 6 to 7, 6.5 to 7.5, or 6.5 to 7.2. Such a pH range can be preferably maintained during precipitation.

[0043] In some embodiments of the method described in this specification, the precipitation step includes a step of adding a basic solution containing carbonate ions and hydroxide ions to the aqueous precursor solution. In an embodiment of the manufacturing method described in this specification, the basic solution contains sodium carbonate (for example, 15 to 35 wt% or 20 to 30 wt%) and sodium hydroxide (for example, 5 to 15 wt%). Of course, other basic solutions can also be used. For example, potassium carbonate and / or potassium hydroxide can be used instead of sodium analogs.

[0044] In an embodiment of the method described in this specification, the temperature of the precursor solution is maintained between 30°C and 100°C during precipitation. For example, in an embodiment of the method described in this specification, the temperature of the precursor solution is maintained in the range of 30 to 100°C (for example, 30 to 90°C, 30 to 80°C, 40 to 100°C, 40 to 90°C, 40 to 80°C, 50 to 100°C, 50 to 90°C, or 50 to 80°C) during precipitation.

[0045] A person skilled in the art can select a desirable time period for precipitation. In an embodiment of the method described in this specification, the precipitation is carried out in the range of 0.5 to 2 hours (for example, 0.5 to 1.5 hours, 0.5 to 1 hour, 1 to 2 hours, 1 to 1.5 hours, or 1.5 to 2 hours). For example, in one embodiment, the time taken for precipitation is 1 hour. However, other times may also be acceptable.

[0046] As described above, the manufacturing method includes a step of firing the solid catalyst precursor to obtain a catalyst composition. In one embodiment of the manufacturing method described in this specification, the manufacturing method further includes a step of separating and washing the solid catalyst precursor before firing the solid catalyst precursor. Conventional methods can be used without particular limitation. The separation can be performed by any desired method for separating the solid precipitate from the solution. For example, filtration, centrifugation, etc. The washing can be performed by rinsing with deionized water.

[0047] In one embodiment of the manufacturing method described in this specification, the solid catalyst precursor is aged before firing. For example, it is aged after separation and before drying. In one embodiment of the manufacturing method described in this specification, the solid catalyst precursor is aged in the range of 5 minutes to 1 hour (for example, in the range of 5 minutes to 45 minutes or in the range of 5 minutes to 30 minutes or in the range of 5 minutes to 15 minutes or in the range of 15 minutes to 1 hour or in the range of 15 minutes to 45 minutes or in the range of 15 minutes to 30 minutes or in the range of 30 minutes to 1 hour or in the range of 30 minutes to 45 minutes or in the range of 45 minutes to 1 hour).

[0048] In one embodiment of the manufacturing method described in this specification, the solid catalyst precursor is dried before firing. Conventional methods can be used without particular limitation. In one embodiment of the manufacturing method described in this specification, the solid catalyst precursor is dried at a temperature within the range of 40°C to 200°C for a time within the range of 15 minutes to 36 hours. However, those skilled in the art can understand that other conditions (for example, drying the material under normal temperature conditions) can also be used. Also, in some samples, since water is removed at the initial stage of heating for firing, a separate drying step may not be required.

[0049] The catalyst is calcined by treating it at a high temperature with oxygen (usually in air) to substantially convert the zinc, aluminum, and copper salts of the precipitate into oxides. In one embodiment of the production method described herein, the calcination temperature ranges from 200 to 600 °C. For example, in one embodiment of the production method described herein, the calcination temperature is 300 to 700 °C (e.g., 300 to 650 °C or 300 to 600 °C or 300 to 550 °C or 300 to 500 °C or 350 to 700 °C or 350 to 650 °C or 350 to 600 °C or 350 to 550 °C or 400 to 700 °C or 400 to 650 °C or 400 to 600 °C or 450 to 700 °C or 450 to 650 °C or 500 to 700 °C).

[0050] One skilled in the art can select a calcination time sufficient to substantially convert the precipitated salts into oxides as described above. In one embodiment of the production method described herein, the solid catalyst precursor is calcined for 5 minutes to 24 hours. For example, in one embodiment of the production method described herein, the solid catalyst precursor is calcined for 5 minutes to 12 hours or 5 minutes to 8 hours or 1 hour to 24 hours or 1 to 12 hours or 1 to 8 hours or 2 to 24 hours or 2 to 12 hours or 2 to 8 hours.

[0051] As described above with respect to various aspects and embodiments of the catalyst composition of the present disclosure, metal sources other than Zn, Al, or Cu (e.g., Na, K, Mg, Ca, La, Ce, Ge, Ba, or Zr sources) may be, for example, carbonates, nitrates, acetates, formates, oxalates, molybdates, or citrates, or any compound capable of adding alkali metals and / or alkaline earth metals to the calcined catalyst composition.

[0052] Some of these compounds can be precipitated together with salts of zinc, aluminum, and copper. In other embodiments of the manufacturing method described herein, the manufacturing method further includes a step of adding one or more of sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium to the composition by an impregnation step. In one embodiment, the manufacturing method described herein includes a step of adding one or more of potassium and magnesium to the composition by an impregnation step.

[0053] In an embodiment of the method described herein, the method includes impregnating the calcined composition by the incipient wetness impregnation method. For example, in an embodiment of the method described herein, the manufacturing method includes a step of impregnating the calcined composition with an aqueous solution of potassium acetate, and a step of calcining the impregnated composition. For example, in various embodiments of the manufacturing method described herein, the manufacturing method includes a step of impregnating the calcined composition with an aqueous solution of magnesium acetate, and a step of calcining the impregnated composition. For example, in various embodiments of the manufacturing method described herein, the manufacturing method includes a step of impregnating the calcined composition with an aqueous solution of potassium acetate and magnesium acetate, and a step of calcining the impregnated composition.

[0054] In various embodiments of the manufacturing method described herein, a calcination step is performed before the impregnation step. In various embodiments of the manufacturing method described herein, a calcination step is performed after the impregnation step. In various embodiments of the manufacturing method described herein, a calcination step is performed both before and after the impregnation step. Drying and calcination after impregnation can be carried out, for example, within the temperature and time ranges described above for the calcination of the precipitate.

[0055] Another aspect of the present disclosure provides a catalyst composition (e.g., a methanol reforming catalyst composition) produced by the manufacturing method described herein.

[0056] The inventors have advantageously found that the catalyst compositions disclosed herein can catalyze the high-temperature methanol reforming reaction with an efficiency comparable to that of conventional chromium-containing and copper-containing catalysts, and in various embodiments, can be produced over a wider range of water-to-methanol ratios and at a wider range of elevated temperatures compared to conventional catalyst materials. Further, the inventors have confirmed that the use of such catalyst compositions can catalyze the high-temperature methanol reforming reaction with high efficiency comparable to that of conventional high-copper-containing catalysts.

[0057] The compositions described herein are particularly useful for methanol reforming reactions (e.g., reactions carried out at relatively high temperatures). As will be appreciated by those skilled in the art, methanol reforming reactions generally produce hydrogen from methanol, e.g., by converting water and methanol to hydrogen and carbon oxides (preferably mainly carbon dioxide). Thus, another aspect of the present disclosure is a method of performing a methanol reforming reaction that includes contacting a feed comprising water and methanol with a catalyst composition described herein under conditions that produce hydrogen and carbon dioxide. The feed can be formed, for example, by gasifying an organic feedstock such as coal or biomass.

[0058] Accordingly, one embodiment of the present disclosure is a method of performing a methanol reforming reaction that includes contacting a feed comprising water and methanol with a catalyst composition described herein at at least 300 °C.

[0059] The feed preferably contains a substantial amount of methanol. For example, in various embodiments described herein, the feed contains at least 10 mol% (e.g., at least 20 mol%) methanol. This can provide a substantial amount of hydrogen for use, e.g., in a fuel cell. However, in other embodiments, a feed with a low methanol content can be used, e.g., to remove a small amount of methanol from the feed stream for other purposes.

[0060] As described above, the method includes the step of contacting a feed comprising water and methanol with a methanol reforming catalyst composition. In an embodiment of the method described herein, the molar ratio of water to methanol in the feed is at most 2.5. For example, in such an embodiment, the molar ratio of water to methanol in the feed is at most 2.4 or at most 2.3 or at most 2.2 or at most 2.1 or at most 2.0. The inventors have noted that as the water to methanol ratio increases, the hydrogen yield may decrease. Also, in an embodiment of the method described herein, the molar ratio of water to methanol in the feed is at least 0.5 (e.g., at least 0.6 or at least 0.8 or at least 1). The inventors have noted that when the steam:methanol ratio is low, coke formation and related pressure drop in the catalyst bed can be problematic. Thus, in an embodiment of the method described herein, the steam:methanol ratio of the feed is in the range of 0.5 to 2.5 (e.g., 0.5 to 2.3 or 0.5 to 2 or 0.5 to 1.8 or 0.5 to 1.5 or 0.7 to 2.5 or 0.7 to 2.3 or 0.7 to 2 or 0.7 to 1.8 or 0.7 to 1.5 or 1 to 2.5, or 1 to 2.3, or 1 to 2, or 1 to 1.8, or 1 to 1.5).

[0061] As described above, the method includes a step of contacting the feed at a temperature of at least 300 °C. The inventors have found that the catalysts described herein are particularly useful in such high-temperature methanol reforming processes. In embodiments of the method described herein, the feed is contacted with the catalyst composition at a temperature of 300-550 °C, or 325-550 °C, or 350-550 °C, or 375-550 °C, or 400-550 °C, or 425-550 °C, or 450-550 °C, or 300-525 °C, or 325-525 °C, or 350-525 °C, or 375-525 °C, or 400-525 °C, or 425-525 °C, or 300-500 °C, or 325-500 °C, or 350-500 °C, or 375-500 °C, or 400-500 °C, or 300-475 °C, or 325-475 °C, or 350-475 °C, or 375-475 °C, or 300-450 °C, or 325-450 °C, or 350-450 °C, or 300-425 °C, or 325-425 °C, or 300-400 °C.

[0062] The step of contacting the feed with the catalyst composition described herein can be carried out in a variety of ways well known to those skilled in the art. Conventional devices and processes can be used in combination with the catalyst compositions of the present disclosure to provide beneficial performance. Thus, the catalyst bed in the reactor vessel can be single or divided into multiple ones. The reaction system can include one or more reaction vessels arranged in parallel. The feed to the reaction zone can flow through the catalyst bed vertically upward or downward in a conventional plug flow reactor, or horizontally across the catalyst bed in a radial flow reactor.

[0063] The space velocity depends on various factors, as will be apparent to those skilled in the art. In embodiments of the method described herein, the feed is contacted with the catalyst composition at a gas hourly space velocity (GHSV) of 200-30,000 h -1 . For example, in embodiments of the method described herein, the feed is contacted with the catalyst composition at a GHSV of 1000-30,000 h -1 , or 5,000-30,000 h-1 or 10,000 - 30,000 h -1 or 200 - 20,000 h -1 or 1,000 - 20,000 h -1 or 5,000 - 20,000 h -1 or 10,000 - 20,000 h -1 at a gas hourly space velocity of and contact with the catalyst composition.

[0064] In various embodiments of the methods described herein, the feed is contacted with the catalyst composition at a pressure between atmospheric pressure and 600 psi (e.g., between atmospheric pressure and 550 psi, or between atmospheric pressure and 500 psi, or between atmospheric pressure and 450 psi, or between atmospheric pressure and 400 psi, or between atmospheric pressure and 350 psi). For example, in various embodiments, the pressure of the feed contacting the catalyst composition is between 50 psi and 600 psi, or between 50 psi and 550 psi, or between 50 psi and 500 psi, or between 50 psi and 450 psi, or between 50 psi and 400 psi, or between 50 psi and 350 psi, or between 100 psi and 600 psi, or between 100 psi and 550 psi, or between 100 psi and 500 psi, or between 100 psi and 450 psi, or between 100 psi and 400 psi, or between 100 psi and 350 psi, or between 150 psi and 600 psi, or between 150 psi and 550 psi, or between 150 psi and 500 psi, or between 150 psi and 450 psi, or between 150 psi and 400 psi, or between 150 psi and 350 psi, or between 200 psi and 600 psi, or between 200 psi and 550 psi, or between 200 psi and 500 psi, or between 200 psi and 450 psi, or between 200 psi and 400 psi, or between 200 psi and 350 psi, or between 250 psi and 600 psi, or between 250 psi and 550 psi, or between 250 psi and 500 psi, or between 250 psi and 450 psi, or between 250 psi and 400 psi, or between 250 psi and 350 psi.

[0065] One of ordinary skill in the art will, of course, understand that, for example, H 2Generally, reaction conditions are selected considering factors such as achieving a balance among yield, catalyst performance, thermal durability, and coke formation. For example, when the steam:methanol ratio is high, the hydrogen yield decreases, which may reduce the performance in a hydrogen fuel cell. On the other hand, when the steam:methanol ratio is low, coke formation may be induced, leading to a significant pressure drop in the catalyst bed. Similarly, when the operating pressure is lower than atmospheric pressure, the hydrogen yield may decrease, while when it is high, the power requirement increases and the cost efficiency decreases. Temperature, if too low, results in an undesirable decrease in conversion rate, and if too high, may damage the catalyst over time and plays an important role in catalysis as is well known. Based on the teachings of the present disclosure, those skilled in the art can balance these considerations and provide an effective industrial process.

[0066] Desirably, the hydrogen-containing product by contact with the catalyst can be introduced into a fuel cell. The hydrogen-containing product mainly contains H 2, CO, and CO 2 . In embodiments of the present disclosure, H 2 ranges from 60 to 90% by volume (e.g., 65 to 90% by volume, or 65 to 85% by volume, or 65 to 80% by volume, or 70 to 90% by volume, or 70 to 85% by volume, or 70 to 80% by volume, or 75 to 90% by volume, or 75 to 85% by volume, or 75 to 80% by volume) in the hydrogen-containing product. In embodiments of the present disclosure, CO ranges from 1 to 20% by volume (e.g., 1 to 15% by volume, or 1 to 10% by volume, or 1 to 5% by volume, or 5 to 20% by volume, or 5 to 15% by volume, or 5 to 10% by volume) in the hydrogen-containing product. In embodiments of the present disclosure, CO 2 ranges from 10 to 40% by volume (e.g., 15 to 35% by volume, or 15 to 30% by volume, or 15 to 25% by volume, or 20 to 40% by volume, or 20 to 35% by volume, or 20 to 30% by volume, or 25 to 40% by volume, or 25 to 35% by volume, or 25 to 30% by volume) in the hydrogen-containing product.

Examples

[0067] The following examples illustrate embodiments of the method of the present disclosure and its various applications. These are described for illustrative purposes only and do not limit the scope of the present disclosure.

[0068] Example 1. Preparation of Catalyst A mixed metal solution was prepared as follows. 0.723 mol of Zn(NO 3 ) 2 solution, 0.478 mol of Al(NO 3 ) 3 and 0.048 mol of Cu(NO 3 ) 2 solution were dissolved in 500 mL of deionized water, and the temperature of the resulting aqueous solution was set to 50°C. A base solution was prepared as follows. 240 mL of 10% NaOH solution and 960 mL of 25% Na 2 CO 3 solution were mixed, and the temperature of the resulting aqueous solution was set to 50°C. The metal solution and the base solution were mixed at 60°C and a constant pH of 6.8 to obtain a precipitate over one hour. The resulting precipitate was aged for 30 minutes. Then, the precipitate was filtered, washed with deionized water, and dried at 120°C. The resulting dried product was calcined at 450°C for 2 hours to obtain Catalyst E1.

[0069] A mixed metal solution was prepared as follows. 0.723 mol of Zn(NO 3 ) 2 solution, 0.478 mol of Al(NO 3 ) 3 solution and 0.109 mol of Cu(NO 3 ) 2 solution were dissolved in 500 mL of deionized water, and the temperature of the resulting aqueous solution was set to 50°C. A base solution was prepared as follows. 240 mL of 10% NaOH solution and 960 mL of 25% Na 2 CO 3The solutions were mixed and the temperature of the resulting aqueous solution was set to 50 °C. The metal solution and the base solution were mixed at 60 °C under a constant pH of 6.8 to obtain a precipitate over the course of one hour. The resulting precipitate was aged for 30 minutes. Thereafter, the precipitate was filtered, washed with deionized water, and then dried at 120 °C. The obtained dried product was calcined at 450 °C for 2 hours to obtain Catalyst E2.

[0070] A mixed metal solution was prepared as follows. 0.723 mol of Zn(NO 3 ) 2 solution, 0.478 mol of Al(NO 3 ) 3 solution, and 0.048 mol of Cu(NO 3 ) 2 solution were dissolved in 500 mL of deionized water, and the temperature of the resulting aqueous solution was set to 50 °C. The base solution was prepared as follows. 240 mL of 10% NaOH solution and 960 mL of 25% Na 2 CO 3 solution were mixed, and the temperature of the resulting aqueous solution was set to 50 °C. The metal solution and the base solution were mixed at 60 °C under a constant pH of 6.8 to obtain a precipitate over the course of one hour. The resulting precipitate was aged for 30 minutes. Thereafter, the precipitate was filtered, washed with deionized water, and then dried at 120 °C. The obtained dried product was calcined at 450 °C for 2 hours. An aqueous mixed solution of magnesium acetate and potassium acetate was added by an impregnation method, K and Mg were added as promoters, and then it was dried at 120 °C and calcined at 450 °C for 2 hours to obtain Catalyst E3.

[0071] A mixed metal solution was prepared as follows. 0.723 mol of Zn(NO 3 ) 2 solution, 0.478 mol of Al(NO 3 ) 3 solution were dissolved in 500 mL of deionized water, and the temperature of the resulting aqueous solution was set to 50 °C. The base solution was prepared as follows. 240 mL of 10% NaOH solution and 960 mL of 25% Na 2 CO 3The solutions were mixed and the temperature of the resulting aqueous solution was set to 50 °C. The metal solution and the base solution were mixed under the conditions of 60 °C and a constant pH of 6.8 to obtain a precipitate over the course of one hour. The resulting precipitate was aged for 30 minutes. Then, the precipitate was filtered, washed with deionized water, and dried at 120 °C. The resulting dried product was calcined at 450 °C for 2 hours to obtain Catalyst C1.

[0072] A mixed metal solution was prepared as follows. 0.723 mol of Zn(NO 3 ) 2 solution, 0.478 mol of Al(NO 3 ) 3 solution, 0.048 mol of Cu(NO 3 ) 2 solution, and 0.017 mol of Mg(NO 3 ) 2 solution were dissolved in 500 mL of deionized water, and the temperature of the resulting aqueous solution was set to 50 °C. The base solution was prepared as follows. 240 mL of 10% NaOH solution and 960 mL of 25% Na 2 CO 3 solution were mixed, and the temperature of the resulting aqueous solution was set to 50 °C. The metal solution and the base solution were mixed under the conditions of 60 °C and a constant pH of 9 to obtain a precipitate over the course of one hour. The resulting precipitate was aged for 30 minutes. Then, the precipitate was filtered, washed with deionized water, and dried at 120 °C. The resulting dried product was calcined at 450 °C for 2 hours, then dried at 120 °C, calcined at 450 °C for 2 hours to obtain Catalyst C2.

[0073] A mixed powder was prepared as follows. 80.0 g of Al 2 O 3 , 100 g of ZrCO 3 and 38 g of deionized water were mixed for 10 minutes and then dried at 110 °C for 3 hours. Next, the powder was mixed with 4% graphite to form pellets, which were calcined at 350 °C to 550 °C for 6 hours. Ni(NO 3 )2·6H 2O nitrate was dissolved in deionized water to prepare a 14% Ni impregnation solution. The pellets were immersed in the Ni solution for 0.5 h, and then dried in an oven at 110 °C for 2 h, calcined at 300 °C for 2 h, heated to 500 °C at a heating rate of 5 °C / min for 4 h. The Ni impregnation process was repeated 3 - 4 times until the target Ni concentration was reached (25 wt% Ni supported on the ZrO 2 and Al 2 O 3 oxide mixture). The obtained product was used as the comparative catalyst C3.

[0074] The compositions of commercially available reference samples were also analyzed by XRD and used as comparative catalysts C4 - C7. Table 1. Catalyst Compositions

[0075]

Table 1

[0076] Example 2. Methanol Conversion Rate and Hydrogen Selectivity The catalyst sample prepared in Example 1 was made into tablets and 7.25 mL was filled into a tubular reactor (inner diameter 19 mm) for high-temperature methanol steam reforming. In the test, a reaction gas containing steam and methanol in a molar ratio of (S / M, molar ratio) 1:1 was supplied at 300 °C and GHSV 3650 h -1 . GHSV was calculated based on the flow rate of the methanol / H 2 O feed under the conditions of 1 atm and 25 °C. The gas was brought into contact with the catalyst bed at 250 psi and >300 °C to form a hydrogen-containing gas. Two reaction temperatures, 400 °C and 450 °C, were tested at a reaction pressure of 250 psi. All tests were completed in 72 h. The methanol conversion rate was calculated from the difference between the inlet and outlet of methanol. The results of the methanol conversion rate and hydrogen selectivity are shown in Table 2. Table 2. Methanol Conversion Rate and Hydrogen Selectivity

[0077]

Table 2

[0078] ZnO and ZnAl with Cu as the promoter 2 O 4 The spinel-based catalysts (E1 and E2) showed better performance than the corresponding Cu-free counterparts (C1). E1 and E2 had the same trend in activity and selectivity at 450 °C, indicating that the addition of an additional 5.5% Cu did not result in a significant difference under high-temperature reaction conditions. However, due to the higher Cu content in E2, at a lower temperature (e.g., 400 °C), it showed slightly higher activity than E1. The methanol conversion rate of E3 was slightly improved by adding promoters of 0.8% MgO and 1.2% K 2 O. Similar to E3, C2 has the same active composition, but during precipitation, in a basic environment with a pH of 9, the resulting catalyst showed a 32% and 26% decrease in methanol conversion rate at 400 °C and 450 °C, respectively, showing much lower activity than the corresponding E3. The Ni-based catalyst C3 was also prepared and tested for methanol steam reforming. Despite showing good activity under the same test conditions, the selectivity of C3 for H 2 was as low as 35%, which was unacceptable compared to the selectivity of ~75% for the spinel-based catalysts. 2 O 4 The reference C4 is a Zn / Cr catalyst that has been commonly used for high-temperature methanol steam reforming. Its activity and H

[0079] selectivity are very close to those of the ZnO-ZnAl 2 O catalyst with Cu as the promoter. The reference samples C6 and C7 are both CuO / ZnO / Al catalysts containing a large amount of CuO. Under the above test conditions, they showed significant activity at 400 °C and 450 °C, but during the long-term test, the activity decreased very quickly due to the sintering of Cu. 2 O 4 Example 3. Influence of reaction temperature and steam / methanol (S / M) ratio 2 O 3 catalyst. Under the above test conditions, they showed significant activity at 400 °C and 450 °C, but during the long-term test, the activity decreased very quickly due to the sintering of Cu.

[0080] Example 3. Influence of reaction temperature and steam / methanol (S / M) ratio The effects of reaction temperature and steam / methanol (S / M) ratio on the catalyst were investigated. The reaction temperature was in the range of 330 °C to 500 °C, and the reaction pressure was 250 psi. In this test, a reaction gas containing steam and methanol was supplied at 300 °C and GHSV 3650 h -1 . All tests were completed in 72 hours. The details of the tests are described in Table 3. Table 3. Effects of Reaction Temperature and S / M Ratio on Methanol Conversion Rate

[0081]

Table 3

[0082] The ZnO-ZnAl 2 O 4 catalyst of E1 showed a higher MeOH conversion rate at 330 °C compared to the reference sample C4 containing chromium. For example, at S / M = 1, the conversion rates were 83% and 51% respectively. At higher temperatures of 400 °C or 450 °C, the difference in conversion rates between the two catalysts was very small. In fact, E1 showed a methanol conversion rate with the same trend at all temperatures tested. Usually, the MeOH conversion rate has a positive correlation with the S / M ratio. This is true for E1. However, C4 showed a higher MeOH conversion rate when the S / M ratio was 0.6 than when it was 1 or 2. Therefore, E1 can obtain a more stable and consistent methanol conversion rate at all S / M ratios and temperatures tested, and shows better performance than the chromium-containing catalyst C4.

[0083] Example 4. Methanol Conversion Rate over Time For catalyst E1, a test of methanol steam reforming was conducted as a function of time, and the results are shown in Figure 1. The reaction was carried out continuously for 175 hours under the conditions of 330 °C, 250 psi, and GHSV 3650 h -1 . Figure 1 shows that during the 175-hour continuous operation, the deactivation in methanol conversion rate, hydrogen selectivity, carbon monoxide selectivity, and carbon dioxide selectivity is negligible, indicating the long-term stability of catalyst E1.

[0084] Catalyst E1 showed excellent activity, stability, and a certain H 2 selectivity. Although not theoretically binding, its high activity is due to the following two reasons. One is the oxygen vacancies generated by the incorporation of extra Zn 2 O 4 into the lattice, and the other is due to the free high-activity ZnO phase. ZnO tends to show higher methanol steam reforming activity than ZnAl 2+ O 2 O 4 , while the spinel structure of ZnAl 2 O 4 is known to be thermally stable. Therefore, the long-term stability and high methanol conversion rate of catalyst E1 shown in Figure 1 are due to both ZnO and ZnAl 2 O 4 present in the catalyst.

[0085] Regarding the product selectivity, the dry exhaust gas contained 73 - 74% H 2 , 1 - 3% CO, and 23 - 25% CO 2 , and CH 4 was not detected. Furthermore, as shown by the XRD data and Rietveld analysis in Figure 2, the used sample E1 contained a high proportion of ZnAl 2 O 4 at 46.5%, while it was 42.9% in the unused sample. Although not theoretically binding, a hypothesis is put forward that during the reaction, the phase changes from ZnO to ZnAl 2 O 4 , making it possible to maintain the high activity of the catalyst at a stable level. Note that the used catalyst was used in an operation of 160 hours (24 hours at 400 °C and 136 hours at 450 °C) at GHSV 3650 h -1 .

[0086] Example 5 Influence of Reaction Pressure and Space Velocity Table 4 shows the results of investigating the influence of various reaction pressures and gas space velocities on the methanol conversion rate and H 2 selectivity. C5 and C6 were at 3650 h -1Under specific test conditions of an S / M ratio of 1, even when the pressure was changed from 30 psi to 250 psi, it was shown that the effect on the catalytic activity was small. At a high space velocity of 20,000 h -1 −1, the methanol conversion rates of both catalysts decreased significantly. For example, C5 showed a MeOH conversion rate of 26% at 20,000 h -1 −1, but it was 68% at 3650 h -1 −1. C6 was similarly 61% and 95% respectively. It should be noted that the MeOH conversion rates of 61% and 65% for C6 are the average conversion rates for the first 24 hours. Due to the high CuO content, the activity of this catalyst dropped very rapidly, especially under high space velocity and high temperature conditions.

[0087] Generally, at a higher space velocity, it is well known that usually the H 2 2 selectivity remains unchanged while the MeOH conversion rate decreases. Other catalysts such as the ZnO-ZnAl 2 2 4 3 catalyst, as shown in Table 5, at 400 °C and 450 °C, 3650 h -1 −1, and under the condition of an S / M ratio of 1, even when the pressure changed, the MeOH conversion rate and the H 2 2 selectivity hardly changed. Furthermore, it was found that this activity was consistent without a decrease in activity during a 72-hour test under each condition described in Table 5. Tables 4 and 5 show that the ZnO-ZnAl 2 2 4 3 catalyst with substantially less CuO can maintain its activity without deteriorating at high temperatures. Furthermore, the ZnO-ZnAl 2 2 4 3 catalyst (E1, Table 5) shows a higher methanol conversion rate and hydrogen selectivity than the catalysts with more CuO (C1 and C2, Table 4). Table 4 Influence of reaction conditions on methanol conversion rate and hydrogen selectivity

[0088]

Table 4

[0089] *For C6 at 20,000 h-1 The MeOH conversion rate at -1 is the average value of the 24-hour operation. The activity decreased by 8% and 18% at 400 °C and 450 °C, respectively, after 24 hours. Table 5. ZnO-ZnAl 2 O 4 Methanol conversion rate and hydrogen selectivity of the catalyst with respect to reaction conditions

[0090] [Table 5]

[0091] Additional aspects of the present disclosure are the following listed embodiments, which can be combined in any number and any combination as long as they are not logically or technically contradictory.

[0092] Embodiment 1. A methanol reforming catalyst composition comprising a ZnO phase in an amount of 20 to 75% by weight in the composition, a zinc-aluminum spinel phase in an amount of 20 to 60% by weight in the composition, and a Cu dopant in an amount of 0.1 to 20% by weight in the composition.

[0093] Embodiment 2. The catalyst composition according to Embodiment 1, wherein the ZnO phase is in an amount of 20 to 75% by weight, or 40 to 60% by weight, or 30 to 50% by weight.

[0094] Embodiment 3. The catalyst composition according to Embodiment 1 or 2, wherein the ZnO phase has a crystallite size of 1 to 50 nm (for example, 2.5 to 40 nm or 5 to 39 nm).

[0095] Embodiment 4. The catalyst composition according to any one of Embodiments 1 to 3, wherein the zinc-aluminum spinel phase is in an amount of 30 to 60% by weight, or 40 to 60% by weight, or 30 to 50% by weight in the composition.

[0096] Embodiment 5. The catalyst composition according to any one of Embodiments 1 to 4, wherein the zinc-aluminum spinel phase has a crystallite size of 1 to 100 nm (for example, 2.5 to 75 nm or 5 to 50 nm).

[0097] Embodiment 6. The catalyst composition according to any one of Embodiments 1 to 5, wherein the Cu dopant is in an amount of 0.5 to 15% by weight (for example, 1 to 10% by weight) in the composition, calculated as CuO.

[0098] Embodiment 7. Further, the catalyst composition according to any one of Embodiments 1 to 6, containing crystalline Al of 5% by weight or less, for example, 4% by weight or less, or 3% by weight or less, or 2% by weight or less, or 1% by weight or less. 2 O 3

[0099] Embodiment 8. The catalyst composition according to any one of Embodiments 1 to 7, wherein Zn in the composition is 40 to 80% by weight (for example, 50 to 80% by weight or 60 to 80% by weight) in total, calculated as ZnO.

[0100] Embodiment 9. The catalyst composition according to any one of Embodiments 1 to 8, wherein Al in the composition is 20 to 50% by weight (for example, 20 to 40% by weight) in total, calculated as Al 2 O 3

[0101] Embodiment 10. The catalyst composition according to any one of Embodiments 1 to 9, wherein Cu in the composition is 0.5 to 20% by weight (for example, 1 to 15% by weight or 1 to 10% by weight) in total, calculated as CuO.

[0102] Embodiment 11. A calcined methanol reforming catalyst composition containing oxides of Zn, Al, and Cu, wherein Zn is 40 to 80% by weight (for example, 60 to 80% by weight) in total in the composition, calculated as ZnO, Al is 20 to 50% by weight (for example, 20 to 40% by weight) in total in the composition, calculated as Al 2 O 3 and Cu is 0.5 to 25% by weight (for example, 1 to 15% by weight) in total in the composition, calculated as CuO. Here, the catalyst is measured by XRD, and ZnAl 2 O 4 ​​Calculated as such, a calcined methanol reforming catalyst composition containing at least 20% by weight (e.g., at least 30% by weight or at least 40% by weight) of zinc-aluminum spinel.

[0103] Embodiment 12. Any of the calcined methanol reforming catalyst compositions of Embodiment 11, further characterized by any of the explicit limitations of Embodiments 1 to 10.

[0104] Embodiment 13. Any of the catalyst compositions of Embodiments 1 to 12, further containing one or more of Na, K, Mg, Ca, La, Ce, Ga, Ba, and Zr in a total amount of 0.05 to 20% by weight (e.g., 0.1 to 10% by weight or 0.5 to 5% by weight).

[0105] Embodiment 14. Further containing at least one of Mg and K, where Mg is 0.1 to 2% by weight (e.g., 0.5 to 1.5% by weight) calculated as MgO, and K is, K 2 O is 0.25 to 3% by weight (e.g., 0.5 to 2% by weight) calculated as such, any of the catalyst compositions of Embodiments 1 to 13.

[0106] Embodiment 15. Any of the catalyst compositions of Embodiments 1 to 14, where the catalyst composition does not contain more than 15% by weight (e.g., 10% by weight) of copper calculated as CuO.

[0107] Embodiment 16. The catalyst composition does not contain more than 1% by weight (e.g., 0.5% by weight or 0.1% by weight or 0.01% by weight) of chromium calculated as Cr 2 O 3 as such, any of the catalyst compositions of Embodiments 1 to 15.

[0108] Embodiment 17. The total amount of the oxides of Cu (calculated as CuO), Al (calculated as Al 2 O 3 as such) and Zn (calculated as ZnO) is at least 90% by weight of the catalyst composition, any of the catalyst compositions of Embodiments 1 to 16.

[0109] Embodiment 18. The total amount of oxides of Cu (calculated as CuO), Al (calculated as Al 2 O 3 calculated as), and Zn (calculated as ZnO), and the total amount of oxides of metal species selected from sodium, potassium, magnesium, calcium, lanthanum, cesium, gallium, barium, and zirconium (all calculated as the most common oxides) are at least 95% by weight of the catalyst composition, the catalyst composition according to any one of Embodiments 1 to 17.

[0110] Embodiment 19. The BET specific surface area is 20 to 500 m 2 / g (for example, 30 to 400 m 2 / g or 50 to 200 m 2 / g), the catalyst composition according to any one of Embodiments 1 to 18.

[0111] Embodiment 20. The N 2 accessible pore volume is 0.05 to 1 cc / g (for example, 0.1 to 0.6 cc / g or 0.2 to 0.35 cc / g), the catalyst composition according to any one of Embodiments 1 to 19.

[0112] Embodiment 21. A method for producing a methanol reforming catalyst composition according to any one of Embodiments 1 to 20, comprising the steps of: preparing an aqueous precursor solution containing zinc ions, aluminum ions, and copper ions; precipitating a solid catalyst precursor containing salts of zinc, aluminum, and copper from the aqueous precursor solution; and calcining the solid catalyst precursor to obtain a catalyst composition.

[0113] Embodiment 22. The step of preparing the precursor solution includes the step of dissolving one or more of Zn(NO 3 ) 2 , Al(NO 3 ) 3 and Cu(NO 3 ) 2 in water, the production method of Embodiment 21.

[0114] Embodiment 23. The method for producing the solid catalyst precursor according to Embodiment 21 or Embodiment 22, wherein the step of precipitating the solid catalyst precursor includes a step of adjusting the pH of the solution to a range of 5 to 7.5 (for example, 6.5 to 7.2).

[0115] Embodiment 24. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 23, wherein the step of precipitating the solid catalyst precursor includes a step of adding a basic solution containing carbonate ions and hydroxide ions to the precursor solution.

[0116] Embodiment 25. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 24, wherein the temperature of the precursor solution is maintained between 30°C and 100°C (for example, between 50°C and 80°C) during precipitation.

[0117] Embodiment 26. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 25, further including an aging step, a washing step, and a drying step of the solid catalyst precursor before firing the solid catalyst precursor.

[0118] Embodiment 27. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 26, wherein the firing temperature is 300 to 700°C (for example, 400 to 600°C).

[0119] Embodiment 28. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 27, further including adding one or more of Na, K, Mg, Ca, La, Ce, Ga, Ba, and Zr to the composition by an impregnation step, and performing firing after the impregnation step.

[0120] Embodiment 29. The method for producing the solid catalyst precursor according to any one of Embodiments 21 to 27, further including adding one or more of K and Mg to the composition by an impregnation step, and performing firing after the impregnation step.

[0121] Embodiment 30. A catalyst composition produced by the production method according to any one of Embodiments 21 to 29.

[0122] Embodiment 31. A method for performing a methanol reforming reaction, comprising a step of bringing a feed containing water and methanol into contact with a catalyst composition according to any one of Embodiments 1 to 20 or 30 at a temperature of at least 300°C to produce hydrogen and carbon dioxide.

[0123] Embodiment 32. The method according to Embodiment 31, wherein the feed contains at least 10% by volume (for example, at least 20% by volume) of methanol.

[0124] Embodiment 33. The method according to Embodiment 31, wherein the feed contains at least 10% by volume (for example, at least 20% by volume) of methanol.

[0125] Embodiment 34. The method according to any one of Embodiments 31 to 33, wherein the molar ratio of water to methanol in the feed is 2.5 or less (for example, 2 or less).

[0126] Embodiment 35. The method according to any one of Embodiments 31 to 32, wherein the molar ratio of water to methanol in the feed is 0.5 to 2.5 (for example, 0.5 to 2.3 or 0.5 to 2 or 0.5 to 1.8 or 0.5 to 1.5 or 0.7 to 2.5 or 0.7 to 2.3 or 0.7 to 2 or 0.7 to 1.8 or 0.7 to 1.5 or 1 to 2.5 or 1 to 2.3 or 1 to 2 or 1 to 1.8 or 1 to 1.5).

[0127] Embodiment 36. The method according to any one of Embodiments 31 to 35, wherein the feed is brought into contact with the catalyst composition at a temperature of 300 to 550°C (for example, 325 to 500°C).

[0128] Embodiment 37. The method according to any one of Embodiments 31 to 36, wherein the feed is brought into contact with the catalyst composition at a gas hourly space velocity of 200 to 30,000 h -1 .

[0129] Embodiment 38. The method according to any one of Embodiments 31 to 37, wherein the feed is contacted with the catalyst composition at a pressure between atmospheric pressure and 600 psi (for example, atmospheric pressure and 350 psi).

[0130] Embodiment 39. The method according to any one of Embodiments 31 to 38, further comprising the step of supplying the hydrogen-containing product produced by the contacting step to a fuel cell.

[0131] The details presented herein are for illustrative discussion of preferred embodiments of the invention and are set forth for the purpose of providing what is believed to be the most useful and readily understood description of the principles of the invention and the conceptual aspects of the various embodiments. In this regard, no attempt is made to show the structural details of the invention in more detail than is necessary for a fundamental understanding of the invention. The description, together with the drawings and / or examples, makes apparent to those skilled in the art how some forms of the invention may be actually embodied. Accordingly, it is understood that the aspects described herein are not limited to a particular embodiment, apparatus, or configuration prior to the description of the disclosed processes and devices, and are thus of course subject to change. Also, it is understood that the terms used herein are for the purpose of describing particular aspects and are not intended to be limiting unless specifically defined herein.

[0132] As used in the context of the description of the present invention, the terms "a", "an", "the", and similar designations (especially in the context of the following claims) are to be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. The recitation of a range of values herein is merely intended to provide a concise method of referring individually to each separate value within the range. Unless otherwise indicated herein, each separate value is incorporated into the specification as if it were individually recited herein. Further, it is understood that the endpoints of each range are significant both in relation to the other endpoint and independently of the other endpoint.

[0133] All of the methods described in this specification can be executed in any suitable order of any appropriate procedures, unless otherwise indicated herein or unless clearly inconsistent with the context. The use of any examples provided herein or of exemplary language (e.g., "such as") is merely intended to more clearly illustrate the invention and does not limit the scope of the invention as otherwise claimed. No description in the specification should be construed as indicating an essential element for the practice of the invention that is not claimed.

[0134] Unless the context clearly requires otherwise, throughout the specification and the claims, words such as "comprise", "comprising", etc. should be construed in an inclusive sense rather than an exclusive or exhaustive sense; that is, in the sense of "including, but not limited to". Words using the singular or plural number also include the plural and the singular respectively. Additionally, as used herein, the words "this specification", "above", "below", and words of similar meaning, when used in this application, refer to the entire application and not to any particular part of the application.

[0135] As will be understood by those skilled in the art, each embodiment disclosed herein can include, consist essentially of, or consist of its particular described elements, steps, components, or ingredients. As used herein, the transitional term "comprise" or "comprising" is not limiting, but means allowing for the inclusion of elements, steps, components, or ingredients not specified, even in major amounts. The transitional phrase "consisting of" excludes any unspecified element, step, component, or ingredient. The transitional phrase "consisting essentially of" limits the scope of the embodiment to the specified elements, steps, components, or ingredients, and those that do not materially affect the embodiment.

[0136] Unless otherwise indicated, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant figures and by applying ordinary rounding techniques.

[0137] Although the broad numerical ranges and parameters set forth by the present invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements.

[0138] The grouping of alternative elements or embodiments of the invention disclosed herein is not to be construed as a limitation. Elements within each group may be referred to individually, or in any combination with other elements in the group, or other elements described herein, and may be claimed. For convenience and / or reasons of patentability, one or more elements of a group may be included in, or deleted from, the group. When such inclusion or deletion occurs, the specification is to be regarded as including the modified group, thereby fulfilling the written description requirements of all Markush groups used in the appended claims.

[0139] Some embodiments of the invention are described herein, including what the inventors believe to be the best mode for practicing the invention. It will of course be apparent to those of ordinary skill in the art from the foregoing detailed description that modifications may be made to the described embodiments. The inventors expect skilled artisans to employ such modifications as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Further, unless otherwise indicated herein or otherwise clearly contradicted by context, any combination of the above-described elements in all possible variations thereof is included within the scope of the invention.

[0140] Throughout this specification, numerous patents and publications are referenced. Each of these cited references and publications is hereby incorporated by reference in its entirety into this specification.

[0141] Furthermore, it should be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the invention. Other modifications that may be employed are within the scope of the invention, and thus, although exemplary and not limiting, alternative configurations of the invention can be utilized in accordance with the teachings of this specification. Accordingly, the invention is not limited to exactly what is shown and described.

Claims

1. A ZnO phase in an amount of 20 to 75% by weight in the composition, a zinc-aluminum spinel phase in an amount of 20 to 60% by weight in the composition, and a Cu dopant in an amount of 0.1 to 20% by weight in the composition, a methanol reforming catalyst composition containing the same.

2. The catalyst composition according to Claim 1, wherein the ZnO phase is in an amount of 30 to 70% by weight, or 40 to 60% by weight, or 30 to 50% by weight.

3. The catalyst composition according to Claim 1 or 2, wherein the ZnO phase has a crystallite size of 1 to 50 nm (for example, 2.5 to 40 nm, or 5 to 30 nm).

4. The catalyst composition according to any one of Claims 1 to 3, wherein the zinc-aluminum spinel phase is in an amount of 30 to 60% by weight, or 40 to 60% by weight, or 30 to 50% by weight in the composition.

5. The catalyst composition according to any one of Claims 1 to 4, wherein the zinc-aluminum spinel phase has a crystallite size of 1 to 100 nm (for example, 2.5 to 75 nm, or 5 to 50 nm).

6. The catalyst composition according to any one of Claims 1 to 5, wherein the Cu dopant is in an amount of 0.5 to 15% by weight (for example, 1 to 10% by weight) in the composition, calculated as CuO.

7. Crystalline Al ２ O ３ The catalyst composition according to any one of claims 1 to 6, wherein the content of ２ is 5% by weight or less (for example, 4% by weight or less, or 3% by weight or less, or 2% by weight or less, or 1% by weight or less).

8. A calcined methanol reforming catalyst composition containing oxides of Zn, Al, and Cu, wherein Zn, calculated as ZnO, has a total amount in the composition of 40 to 80% by weight (for example, 60 to 80% by weight), Al is calculated as Al ２ O ３ such that the total amount in the composition is 20 to 50 wt% (e.g., 20 to 40 wt%), and and Cu, calculated as CuO, has a total amount in the composition of 0.5 to 25% by weight (for example, 1 to 15% by weight). Here, the catalyst is measured by XRD and calculated as ZnAl ２ O ４ to obtain a calcined methanol reforming catalyst composition containing at least 20% by weight (e.g., at least 30% by weight, or at least 40% by weight) of zinc-aluminum spinel.

9. Further comprising at least one of Mg and K, Mg is calculated as MgO and is 0.1 to 2% by weight (for example, 0.5 to 1.5% by weight), and K is K ２ is calculated as O and is 0.25 to 3% by weight (for example, 0.5 to 2% by weight), the catalyst composition according to any one of claims 1 to 8.

10. The catalyst composition does not contain copper in an amount exceeding 15% by weight (for example, exceeding 10% by weight) calculated as CuO, and does not contain chromium in an amount exceeding 1% by weight (for example, exceeding 0.5% by weight, or exceeding 0.1% by weight, or exceeding 0.01% by weight) calculated as Cr ２ O ３ The catalyst composition according to any one of claims 1 to 9.

11. Cu (calculated as CuO), Al (calculated as ２ O ３ calculated as) and the total amount of oxides of Zn (calculated as ZnO) is 90% by weight or more (for example, 95% by weight or more) of the catalyst composition, the catalyst composition according to any one of claims 1 to 10.

12. A step of preparing an aqueous precursor solution containing zinc ions, aluminum ions, and copper ions; a step of precipitating a solid catalyst precursor containing salts of zinc, aluminum, and copper from the aqueous precursor solution; and then, a step of calcining the solid catalyst precursor to obtain a catalyst composition, a method for producing a methanol reforming catalyst composition according to any one of Claims 1 to 11.

13. A method for performing a methanol reforming reaction, comprising a step of contacting a feed containing water and methanol with the catalyst composition according to Claims 1 to 20 or 30 at a temperature of at least 300 °C to produce hydrogen and carbon dioxide.

14. The method according to claim 13, wherein the feed comprises at least 10% by volume of methanol (for example, at least 20% by volume of methanol), and the molar ratio of water to methanol in the feed ranges from 0.5 to 2.5 (for example, 0.5 to 2.3, or 0.5 to 2, or 0.5 to 1.8, or 0.5 to 1.5, or 0.7 to 2.5, or 0.7 to 2.3, or 0.7 to 2, or 0.7 to 1.8, or 0.7 to 1.5, or 1 to 2.5, or 1 to 2.3, or 1 to 2, or 1 to 1.8, or 1 to 1.5).

15. The method according to any one of claims 13 or 14, further comprising introducing the hydrogen-containing product generated by the contacting step into a fuel cell.

Images