WO2018215943A1

WO2018215943A1 - Copper-zinc-zirconium-based catalyst for direct hydrogenation of co2 to methanol

Info

Publication number: WO2018215943A1
Application number: PCT/IB2018/053644
Authority: WO
Inventors: Aghaddin Mamedov; Shahid Shaikh; Clark Rea; Xiankuan Zhang
Original assignee: Sabic Global Technologies B.V.
Priority date: 2017-05-24
Filing date: 2018-05-23
Publication date: 2018-11-29

Abstract

A Cu-Zn-Zr oxide catalyst for the direct hydrogenation of CO2 to methanol, and a method for producing the catalyst comprising the precipitation of copper/zinc/zirconium salts in the presence of a cesium and an alkaline salt.

Description

COPPER-ZINC-ZIRCONIUM-BASED CATALYST FOR DIRECT HYDROGENATION OF C02 TO METHANOL

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/510,704 filed May 24, 2017, the entire contents of which are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

[0002] This invention relates to a catalyst composition for the direct conversion of CO2 to methanol.

BACKGROUND [0003] Today, much effort is being put into the development of technologies for capture and conversion of carbon dioxide (CO2) in order to mitigate the greenhouse effect and earn carbon credits. Capturing CO2 and converting it to useful chemicals such as methanol reduces both pollution and dependencies on petroleum products.

[0004] Manufacturers generally produce methanol, a key chemical building block and fuel, from petroleum-derived syngas, a mixture of carbon monoxide (CO) and hydrogen (H2). Direct hydrogenation of the greenhouse gas carbon dioxide provides a more efficient and environmentally sustainable route to methanol, and is the subject of active investigation.

[0005] Much of the CO2 to methanol research has focused on the catalyst systems. CuO-ZnO-Al20₃ catalysts have been employed on an industrial scale for the conversion of syngas to methanol, however, long term deactivation, low conversion, and poor selectivity affect many of the common Cu-Zn-Al industrial catalysts. Thus, there is a need in the industry for improved catalyst systems for the direct conversion of CO2 to methanol.

SUMMARY [0006] The present disclosure addresses the need to provide an improved catalytic system for the direct conversion of CO2 to methanol. The inventors have found that a mixed metal oxide catalyst comprising copper, zinc, and zirconium provides for improved conversion of one or more oxides of carbon to methanol. A notable feature of the present disclosure is the novel catalyst preparation method which leads to the formation of the stable and active catalyst. In some aspects, the catalyst preparation method comprises using a mixture of alkaline salts to establish a buffer system. The mixture of alkaline salts establishes a precipitating agent/buffer system that affects catalyst precipitation by facilitating homogeneous distribution of copper, zinc, and zirconium components in the precipitate, thereby resulting in the formation of a stable, active mass of the catalyst oxide components. In some embodiments, the mixture of alkaline salts comprises a cesium salt and a sodium salt. In specific embodiments, the mixture of alkaline salts comprises cesium nitrate and sodium carbonate. In some aspects, the catalysts produced using the precipitating agent/buffer system mixture of salts recited above exhibit improved stability and activity in comparison with catalysts prepared using a single salt for precipitation. In particular aspects, the single salt is sodium carbonate.

[0007] In some embodiments, a mixed metal oxide catalyst comprising copper, zinc, and zirconium is disclosed. The catalyst comprises or is derived from a catalytic precursor precipitated from an aqueous solution comprising cesium nitrate and sodium carbonate. The cesium nitrate and sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate, thereby resulting in the formation of a stable, active mass of the catalyst oxide components. In some embodiments, the catalyst has a catalytic activity for production of methanol from a carbon dioxide source that is greater than a catalyst comprising a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate. In particular embodiments, the catalyst comprises 30 to 70 wt.% copper oxide, 15 to 40 wt.% zinc oxide, and 10 to 40 wt.% zirconium oxide based on the total weight of the catalyst.

[0008] In some embodiments, a method of making a mixed metal oxide catalyst in an amount of at least 1 kilograms capable of producing methanol from a carbon dioxide source is disclosed. In some aspects, the method comprises the steps of obtaining an aqueous solution comprising a copper salt, a zinc salt, a zirconium salt, and a cesium salt, precipitating a catalytic precursor with an alkaline salt, separating at least part of the catalytic precursor from the aqueous mixture, and calcining the catalytic precursor to form the mixed metal oxide catalyst in an amount of at least 1 kilograms. In particular aspects, the copper salt is copper nitrate (Cu(NCb)2), the zinc salt is zinc nitrate (Zn(NCb)2), the zirconium salt is zirconium oxynitrate (ZrO(NCb)2), and the cesium salt is cesium nitrate (Cs(NCb)2). In some aspects, the mixed metal oxide catalyst comprises less than a catalytic amount of cesium. In some embodiments, calcining the catalytic precursor comprises subjecting the catalytic precursor to a calcination temperature ranging from 400 °C to 600 °C. In some embodiments, the calcination step comprises calcining the catalytic precursor for a period of time ranging from 1 hour to 8 hours, preferably from 3 hours to 6 hours. The extrudate may be calcined in an ambient air atmosphere or an inert atmosphere, including a reduced oxygen atmosphere or an inert gas atmosphere.

[0009] In some embodiments, a method of making a mixed metal oxide catalyst in an amount of at least 1 kilograms capable of producing methanol from a carbon dioxide source comprises heating the aqueous solution at a temperature of at least 80 °C before precipitating a catalytic precursor with an alkaline salt. In some aspects, the alkaline salt is sodium carbonate. In particular aspects, the cesium salt and the sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate, thereby resulting in the formation of a stable, active mass of the catalyst oxide components.

[0010] In some aspects, method of producing methanol from a carbon dioxide source is disclosed. The method comprises the steps of obtaining a mixed metal oxide catalyst comprising copper, zinc, and zirconium, exposing a carbon dioxide source to the mixed metal oxide catalyst under conditions sufficient to produce methanol. The catalyst comprises catalytic material precipitated from an aqueous solution comprising cesium nitrate and the catalyst has a catalytic activity that is greater than a catalyst comprising a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate. In some aspects, the carbon dioxide source comprises syngas. In some embodiments, the catalyst comprises 30 to 70 wt.% copper oxide, preferably 40 to 65 wt.% copper oxide, more preferably 50 to 60 wt.% copper oxide based on the total weight of the catalyst. In some aspects, the catalyst comprises 15 to 40 wt.% zinc oxide, preferably 15 to 35 wt.% zinc oxide, more preferably 20 to 30 wt.% zinc oxide based on the total weight of the catalyst. In some aspects, the catalyst comprises 10 to 40 wt.% zirconium oxide, preferably 15 to 30 wt.% zirconium oxide, more preferably 18 to 23 wt.% zirconium oxide based on the total weight of the catalyst. In some embodiments, the catalytic activity comprises a methanol selectivity of greater than 20%, preferably greater than 25%. In further aspects, the catalytic activity comprises a methanol selectivity of greater than 30% after 100 days of time of stream (TOS). In additional embodiments, the catalytic activity comprises a methanol selectivity that increases between 50 and 150 days. In further embodiments, the catalytic activity comprises a carbon dioxide conversion to methanol of greater than 12%. In some aspects, the catalytic activity comprises a carbon monoxide selectivity of less than 85%, preferably less than 70%. [0011] In some aspects, conditions sufficient to produce methanol from a carbon dioxide source comprise a reaction temperature ranging from 200 °C to 400 °C, preferably ranging from 225 °C to 260 °C. In some aspects, conditions sufficient to produce methanol from a carbon dioxide source comprise a reaction pressure ranging from 500 psi to 1,000 psi, preferably from 600 psi to 900 psi, more preferably ranging from 700 to 800 psi. In some aspects, conditions sufficient to produce methanol from a carbon dioxide source comprise using a IfciCCh feed stream ratio ranging from 2: 1 to 5: 1, preferably ranging from 2.5: 1 to 3 : 1.

[0012] The following includes definitions of various terms and phrases used throughout this specification.

[0013] The term "coupled" is defined as connected, although not necessarily directly, and not necessarily mechanically. The terms "a" and "an" are defined as one or more unless this disclosure explicitly requires otherwise. The term "substantially" is defined as being largely but not necessarily wholly what is specified (and include wholly what is specified) as understood by one of ordinary skill in the art. In any disclosed embodiment, the term "substantially" may be substituted with "within [a percentage] of what is specified, where the percentage includes .1, 1, 5, and 10 percent.

[0014] The terms "comprise" (and any form of comprise, such as "comprises" and "comprising"), "have" (and any form of have, such as "has" and "having"), "include" (and any form of include, such as "includes" and "including") and "contain" (and any form of contain, such as "contains" and "containing") are open-ended linking verbs. As a result, a catalyst that "comprises," "has," "includes" or "contains" one or more elements possesses those one or more elements, but is not limited to possessing only those one or more elements. Likewise, an element of a system or composition that "comprises," "has," "includes" or "contains" one or more features possesses those one or more features, but is not limited to possessing only those one or more features.

[0015] The terms "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.

[0016] The terms "wt.%", "vol.%" or "mol.%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component. [0017] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification, includes any measurable decrease or complete inhibition to achieve a desired result.

[0018] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0019] In the context of the present invention at least sixteen embodiments are now described. Embodiment 1 is mixed metal oxide catalyst containing copper, zinc, and zirconium, wherein the catalyst includes a catalytic precursor precipitated from an aqueous solution comprising cesium nitrate and sodium carbonate; wherein the cesium nitrate and sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate; and the formation of a stable, active mass of the catalyst oxide components and wherein the catalyst has a catalytic activity for production of methanol from a carbon dioxide source that is greater than a catalyst containing a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate. Embodiment 2 is the catalyst of embodiment 1, wherein the copper, zinc, and zirconium comprise 30 to 70 wt.% copper oxide, 15 to 40 wt.% zinc oxide, and 10 to 40 wt.% zirconium oxide based on the total weight of the catalyst.

[0020] Embodiment 3 is a method of making a mixed metal oxide catalyst in an amount of at least 1 kilograms capable of producing methanol from a carbon dioxide source, the method including the steps of: (i) obtaining an aqueous solution including a copper salt, a zinc salt, a zirconium salt and a cesium salt; (ii) precipitating a catalytic precursor with an alkaline salt; (iii) separating at least part of the catalytic precursor from the aqueous mixture; and (iv) calcining the catalytic precursor to form the mixed metal oxide catalyst in an amount of at least 1 kilograms. Embodiment 4 is the method of embodiment 3, wherein the copper salt is copper nitrate (Cu(N0₃)₂), the zinc salt is zinc nitrate (Zn(N0₃)₂), the zirconium salt is zirconium oxynitrate (ZrO(N0₃)₂), and the cesium salt is cesium nitrate (Cs(N0₃)₂). Embodiment 5 is the method of any of embodiments 3 or 4, wherein the mixed metal oxide catalyst contains less than a catalytic amount of cesium. Embodiment 6 is the method of any of embodiments 3 to 5, further comprising heating the aqueous solution at a temperature of at least 80 °C before precipitating a catalytic precursor with an alkaline salt. Embodiment 7 is the method of any of embodiments 3 to 6, wherein the alkaline salt is sodium carbonate. Embodiment 8 is the method of embodiment 7, wherein the cesium salt and the sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate.

[0021] Embodiment 9 is a method of producing methanol from a carbon dioxide source, the method including the steps of (i) obtaining a mixed metal oxide catalyst comprising copper, zinc, and zirconium, wherein the catalyst comprises catalytic material precipitated from an aqueous solution comprising cesium nitrate; and (ii) exposing a carbon dioxide source to the mixed metal oxide catalyst under conditions sufficient to produce methanol, wherein the catalyst has a catalytic activity that is greater than a catalyst comprising a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate. Embodiment 10 is the method of embodiment 9, wherein the carbon dioxide source contains syngas. Embodiment 11 is the method of any of embodiments 9 or 10, wherein the catalyst contains 30 to 70 wt.% copper oxide, 15 to 40 wt.% zinc oxide, and 10 to 40 wt.% zirconium oxide based on the total weight of the catalyst. Embodiment 12 is the method of any of embodiments 9 to 11, wherein the catalytic activity includes a methanol selectivity of greater than 20%. Embodiment 13 is the method of any one of embodiments 9 to 12, wherein the catalytic activity comprises a methanol selectivity of greater than 30% after 100 days of time of stream (TOS). Embodiment 14 is the method of any of embodiments 9 to 13, wherein the catalytic activity comprises a methanol selectivity that increases between 50 and 150 days. Embodiment 15 is the method of any of embodiments 9 to 14, wherein the catalytic activity comprises a carbon dioxide conversion to methanol of greater than 12%. Embodiment 16 the method of any of embodiments 9 to 15, wherein the catalytic activity comprises a carbon monoxide selectivity of less than 85%.

[0022] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 is a graph depicting methanol selectivity over the course of several days using a catalyst of the present invention. The catalyst has the composition: ZnO 24.9%, CuO 55.19%, ZrC-2 19.53%.

[0024] FIG. 2 is a graph depicting CO2 conversion at a reactor space velocity of 9,720 hr^"1 using a catalyst of the present invention. The catalyst has the composition: ZnO 24.9%, CuO 55.19%, Zr02 19.53%.

[0025] FIG. 3 is a graph depicting methanol selectivity over the course of several days using an industrial methanol catalyst of the following composition: ZnO 25%, CuO 67.24%, AI2O3 11.43%. Reaction carried out at space velocity 2430 hr^-1.

[0026] FIG. 4 is a graph depicting CO2 conversion at a reactor space velocity of 2,430 hr^"1 using an industrial methanol catalyst of the following composition: ZnO 25%, CuO

DETAILED DESCRIPTION [0027] Various features and advantageous details are explained more fully with reference to the non-limiting embodiments that are illustrated in the accompanying drawings and detailed in the following description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the invention, are given by way of illustration only, and not by way of limitation. Various substitutions, modifications, additions, and/or rearrangements will become apparent to those of ordinary skill in the art from this disclosure.

[0028] In the following description, numerous specific details are provided to provide a thorough understanding of the disclosed embodiments. One of ordinary skill in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

[0029] Direct conversion of CO2 to methanol by catalytic hydrogenation is the subject of active investigation. The overall conversion of CO2 to methanol is represented by the following reaction equation:

[0030] The overall conversion reaction above involves consecutive but distinct reactions:

CO2 + 3H₂→ CO + 2H₂ + H2O (2)

[0031] The second reaction above (Equation 3) represents the commonly-employed syngas to methanol process.

[0032] Cu-Zn-Al oxide catalysts are commonly employed for CO2 hydrogenation. As is common in the field of industrial catalysis, these Cu-Zn-Al oxide catalysts become deactivated over the long term. A significant amount of research has focused on the development of improved Cu-Zn-Al oxide catalysts for CO2 hydrogenation. A number of different metals, including Cr, Ce, Zr, and Mn have been employed as promoters of the basic Cu-Zn-Al oxide catalyst system. The experiments detailed below investigate the effect of modifications to the basic Cu-Zn-Al oxide catalyst system.

[0033] Metal promoters were incorporated into catalysts by co-precipitation with the primary catalyst components. Variations to precipitation conditions were investigated, including pre-catalyst solution pH values, buffer combinations, catalyst precipitate washing conditions, and different catalyst drying and calcination conditions. Catalyst precipitation using a cesium nitrate/sodium carbonate buffer mixture produced the most active catalyst. Example 1 - Catalyst Preparation

[0034] The following salts were dissolved in 200 ml deionized water in a reaction vessel equipped with overhead stirring motor, condenser and dropping funnel: 35.73 g Cu(N0₃)₂ 3H₂0, 20.93 g Zn(N0₃)₂ 6H₂0, 11.16 g ZrO(N0₃)₂ 6H₂0, and 9.30 g Cs(N0₃)₃-6H₂0. The solution was stirred at 400 rpm and heated to 85 °C using a silicone oil-bath. The solution exhibited a blue color at pH -0.15. A Na₂C0₃ solution (30%) was added dropwise to the heated salt solution through the addition funnel under constant stirring until a pH of 8.0 was reached. The light blue slurry was stirred for two hours at 85 °C. Stirring was stopped and the slurry was allowed to cool to room temperature. The precipitate was then filtered using a filter funnel with medium porosity filter paper. The collected filter cake was grey-green in color. The filter cake was stirred in deionized water at 60 °C and re-filtered to remove excess sodium nitrate. The filter cake was then transferred to a porcelain dish and dried at 105 °C for 12 hours. The dried material was ground to 100 mesh powder, and calcined at 400 °C for 5 hours under air flow to obtain a black powder. The black material was pressed at a force of 20,000 lbs, crushed, and sieved to 20-50 mesh. The bulk density of powdered catalyst was 1.4 gm/cc. The prepared catalyst had the composition: 24.9% ZnO 55.2% CuO, 19.5% Zr0₂, and did not include Cs₂0 in an amount affecting catalytic activity.

Example 2 - MeOH Selectivity and CO2 Conversion Using Prepared Catalyst

[0035] The conversion of CO2 to methanol using a catalyst of the present invention was examined. Reaction conditions included the following parameters: catalyst loading lg, H₂ flow rate 124 cc/min, CO2 flow rate 42 cc/min, pressure 750 psi, reaction temperature 240 °C, and space velocity 9,720 hr^"1. CO2 conversion and methanol selectivity results are depicted in FIG. 1 and FIG. 2, respectively.

Example 3 - Comparative Catalyst 1

[0036] A comparative catalyst having the same elemental composition of the catalyst prepared in Example 1 was prepared. The synthetic procedure mirrors the procedure given in Example 1 above, but precipitation was performed using sodium carbonate (no cesium nitrate). Reaction conditions included the following parameters: catalyst loading lg, H₂ flow rate 32 cc/min, CO2 flow rate 8.5 cc/min, pressure 750 psi, reaction temperature 250 °C, and space velocity 2,430 hr^"1. The following conversion and selectivity results were observed:

Table 1 Comparative Catalyst 1 Results

Example 4 - Comparative Catalyst 2

[0037] A comparative catalyst having the following components was prepared: 40%CuO-30%ZnO-15%ZrO₂-15%A12O3. The synthetic procedure mirrors the procedure given in Example 1 above, but precipitation of Cu, Zr, and Zn was performed with aluminum nitrate and sodium carbonate (no cesium nitrate), which allowed for the incorporation of aluminum into the precipitated product. Reaction conditions included the following parameters: catalyst loading lg, H2 flow rate 28 cc/min, CO2 flow rate 12.2 cc/min, pressure 750 psi, reaction temperature 250 °C, and space velocity 2,430 hr^"1. The following conversion and selectivity results were observed:

Table 2 Comparative Catalyst 2 Results

Example 5 - MeOH Selectivity and CO2 Conversion Using Industrial Catalyst

[0038] The conversion of CO2 to methanol using an industrial Cu-Zn-AhCb catalyst (medium pressure catalyst 25% ZnO, 67.24%) CuO, 11.43%) AI2O3) was examined. Reaction conditions included the following parameters: catalyst loading lg, H2 flow rate 32 cc/min, CO2 flow rate 8.5 cc/min, pressure 750 psi, and reaction temperature 240 °C. CO2 conversion and methanol selectivity results are depicted in FIG. 3 and FIG. 4, respectively.

[0039] The industrial catalyst of Example 5 exhibited no change for CO2 conversion, but methanol selectivity dropped from 40 to 33%> within seven days (FIG. 4). Note that catalyst deactivation correlates with a decrease in methanol selectivity.

[0040] Comparison between the inventive catalyst (FIGS. 1 and 2) and the industrial catalyst (FIGS. 3 and 4) shows that the inventive catalyst exhibits high activity. The inventive catalyst generated comparable CO2 conversion levels at a space velocity 4 times greater than the industrial catalyst. The inventive catalyst was active for several months, with no apparent deactivation after 150 days.

[0041] Comparison between the inventive catalyst (FIGS. 1 and 2), comparative catalyst 1 (precipitation with sodium carbonate only, Table 1), and shows that the inventive catalyst exhibits significantly higher methanol selectivity. Although cesium nitrate was part of the original inventive catalyst mixture, cesium was not present in the precipitated product. The combination of cesium nitrate and sodium carbonate establish a precipitating agent/buffer system that affects catalyst precipitation by facilitating homogeneous distribution of copper, zinc, and zirconium components in the precipitate, thereby resulting in the formation of a stable, active mass of the catalyst oxide components.

[0042] The inventive catalyst (FIGS. 1 and 2) exhibits significantly higher methanol selectivity than comparative catalyst 2 (aluminum present in catalyst composition, Table 2), demonstrating that the inclusion of AI2O3 in the catalyst does not improve performance. The catalyst prepared by the method outlined in Example 1 exhibits the best with combination of activity and stability.

[0043] The feature or features of one embodiment may be applied to other embodiments, even though not described or illustrated, unless expressly prohibited by this disclosure or the nature of the embodiments. Any embodiment of any of the disclosed container assemblies and compositions can consist of or consist essentially of— rather than comprise/include/contain/have— any of the described elements and/or features and/or steps. Thus, in any of the claims, the term "consisting of or "consisting essentially of can be substituted for any of the open-ended linking verbs recited above, in order to change the scope of a given claim from what it would otherwise be using the open-ended linking verb. Details associated with the embodiments described are presented herein.

[0044] The claims are not to be interpreted as including means-plus- or step-plus- function limitations, unless such a limitation is explicitly recited in a given claim using the phrase(s) "means for" or "step for," respectively.

Claims

1. A mixed metal oxide catalyst comprising copper, zinc, and zirconium, wherein the catalyst comprises a catalytic precursor precipitated from an aqueous solution comprising cesium nitrate and sodium carbonate; wherein the cesium nitrate and sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate; and the formation of a stable, active mass of the catalyst oxide

components wherein the catalyst has a catalytic activity for production of methanol from a carbon dioxide source that is greater than a catalyst comprising a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate.

2. The catalyst of claim 1, wherein the copper, zinc, and zirconium comprise 30 to 70 wt.% copper oxide, 15 to 40 wt.% zinc oxide, and 10 to 40 wt.% zirconium oxide based on the total weight of the catalyst.

3. A method of making a mixed metal oxide catalyst in an amount of at least 1 kilograms capable of producing methanol from a carbon dioxide source, the method comprising:

(i) obtaining an aqueous solution comprising a copper salt, a zinc salt, a zirconium salt and a cesium salt;

(ii) precipitating a catalytic precursor with an alkaline salt;

(iii) separating at least part of the catalytic precursor from the aqueous mixture; and

(iv) calcining the catalytic precursor to form the mixed metal oxide catalyst in an amount of at least 1 kilograms.

4. The method of claim 3, wherein the copper salt is copper nitrate (Cu(NCb)2), the zinc salt is zinc nitrate (Zn(NCb)2), the zirconium salt is zirconium oxynitrate (ZrO(NCb)2), and the cesium salt is cesium nitrate (Cs(NCb)2).

5. The method of claim 3 or 4, wherein the mixed metal oxide catalyst comprises less than a catalytic amount of cesium.

6. The method of any of claims 3 or 4, further comprising heating the aqueous solution at a temperature of at least 80 °C before precipitating a catalytic precursor with an alkaline salt.

7. The method of any of claims 3 or 4, wherein the alkaline salt is sodium carbonate.

8. The method of claim 7, wherein the cesium salt and the sodium carbonate establish a buffer medium that facilitates homogeneous distribution of copper, zinc, and zirconium components in the precipitate.

9. A method of producing methanol from a carbon dioxide source, the method comprising

(i) obtaining a mixed metal oxide catalyst comprising copper, zinc, and zirconium,

wherein the catalyst comprises catalytic material precipitated from an aqueous solution comprising cesium nitrate; and

(ii) exposing a carbon dioxide source to the mixed metal oxide catalyst under conditions sufficient to produce methanol,

wherein the catalyst has a catalytic activity that is greater than a catalyst comprising a catalytic precursor precipitated from an aqueous solution in the absence of cesium nitrate.

10. The method of claim 9, wherein the carbon dioxide source comprises syngas.

11. The method of any of claims 9 or 10, wherein the catalyst comprises 30 to 70 wt.% copper oxide, 15 to 40 wt.% zinc oxide, and 10 to 40 wt.% zirconium oxide based on the total weight of the catalyst.

12. The method of any of claims 9 or 10, wherein the catalytic activity comprises a methanol selectivity of greater than 20%.

13. The method of any of claims 9 or 10, wherein the catalytic activity comprises a methanol selectivity of greater than 30% after 100 days of time of stream (TOS).

14. The method of any of claims 9 or 10, wherein the catalytic activity comprises a methanol selectivity that increases between 50 and 150 days.

15. The method of any of claims 9 or 10, wherein the catalytic activity comprises a carbon dioxide conversion to methanol of greater than 12%.

16. The method of any of claims 9 or 10, wherein the catalytic activity comprises a carbon monoxide selectivity of less than 85%.