Patent Application
20240083755
The impact of ever-increasing CO2 levels on the anthropogenic induced climate change have been widely documented (Shukla et al, IPCC, 2019). During 1970 to year-end 2019, global radiative forcing increased by an average of 3.03 Watts/square meter (W/m2), due to increases in the greenhouse gases, CO2, CH4, N2O and H2O, with a concurrent, average global temperature increase of 1.18° C. (2.13° F.). Climate models predict that average global temperatures could reach +2.00° C. (+3.60° F.) sometime between 2026 and 2028, and 2.36° C. (+4.28° F.) by year end 2031 compared to the average global temperature in 1970. Since CO2 accounts for two thirds of these increases, rapid reductions in CO2 emissions and atmospheric CO2 are needed by no later than 2030 (Schuetzle, 2020).
CO2 can be captured efficiently from emissions generated by industrial processes. Since CO2 is a useful carbon source, the first priority should be to utilize this carbon source for the production of low-carbon fuels and chemicals, instead of sequestering the CO2 in geological formations (Hepburn et al, 2019). CO2 can also be captured from air (called Direct Air Capture—DAC) which allows for CO2 collection from any location globally without being tied to an industrial source (Artz et al, 2018).
Since there are very few locations where suitable geological formations are available to sequester captured CO2, it is much more suitable to produce fuels and chemical products from the CO2. Furthermore, CO2 is a valuable feedstock that can be used to produce low-carbon fuels and chemicals.
Syngas can potentially be commercially produced from the catalytic conversion of low-carbon H2 and captured CO2 mixtures. This catalytic process is referred to as CO2 Hydrogenation, or the Reverse Water-Gas Shift (RWGS) reaction (Equation 1) (Daza et al, 2016; Vogt et al, 2019; Chen et al, 2020).
CO2+H2=CO+H2O Eq. 1
The reaction is endothermic and requires heat to proceed. Elevated temperatures and efficient catalysts are required for significant CO2 conversion to CO with minimal or no coking (carbon formation) or degradation in catalyst performance with time.
Since no commercially viable catalysts have been developed to date for the efficient production of syngas from H2 and CO2 mixtures, an improved catalyst and process has been developed and is described herein for the efficient commercial production of low-carbon syngas from mixtures of low-carbon H2 and captured CO2.
This low-carbon syngas is an excellent feedstock for producing a wide range of other chemical products, including liquid and gaseous hydrocarbon fuels, alcohols, acetic acid, dimethyl ether, and many other chemical products (Olah et al, 2009; Centi et al, 2009; Jiang et al, 2010; Schuetzle et al, 2010-2020; Fischer et al, 2016; Gumber et al, 2018; Tan et al, 2018; Li et al, 2019; NAS, 2019).
Many patent applications, patents and publications have described the development of RWGS catalysts for the conversion of H2 and CO2 mixtures to syngas (Bahmanpour et al, 2021). There is a second emerging approach that encompasses electrolysis processes for the conversion of mixtures of CO2 and H2O to syngas (Wang et al, 2016). However, this electrolysis approach is in the early research and development stages, and it is not considered as a viable commercial scale method at this time.
Most of the RWGS catalysts described in the current art operate at conditions that are not relevant to industrial relevant process conditions, or have significant limitations such as high costs, not amenable to large-scale manufacturing, or they have limited operational lifetime. We therefore have developed catalysts per the invention that are commercially viable and meet the following specifications outlined in Table 1.
The field of the invention is the application of improved catalysts for the conversion of renewable H2 and captured CO2 to syngas, which is then used concurrently to produce low-carbon fuels and chemicals. The improved catalysts use low-cost metals, they can be produced economically in commercial quantities, and they are chemically and physically stable up to 2,100° F. CO2 conversion efficiencies are between 80% and 100% with CO selectivity of greater than 99%. The catalysts don't sinter or form coke when converting H2:CO2 mixtures to syngas at 1,300-1,800° F., 75-450 psi and space velocities of 2,000-100,000 hr−1. The catalysts are robust, exhibiting a reduction in CO2 conversion of between 0 and 1.0% per 1000 hours.
Iwanani et al (1995) developed a catalyst comprised of transition metals with rare metals (such as Ni, Fe, Ru, Rh, Pt, W, Pd, Mo) on a ZnO/Al2O3 substrate for the conversion of CO2 and H2 mixtures to CO, targeting specifically catalytic performance with feeds containing H2S. They achieved relatively low conversions of CO2 of up to 37% at 1,100° F. at 3,000 hr−1 for a 12.4% Ni/21.2% Zn catalyst without significant loss of catalyst activity after 150 hours but testing for longer periods was not carried out. This catalyst doesn't meet any of the specifications in Table 1.
Dupont et al (2003) developed a catalyst consisting of 0.78% ZnO/0.21% Cr2O3/0.01% NiO for the conversion of an H2/CO2 (3.5/1.0 v/v) mixture to CO. The CO2 conversion efficiency was 36% with a 92% CO and 8% CH4 selectivity at 950° F., a pressure of 580 psi, and a space velocity of 5.0 hr−1. No data was presented on the efficiency of the catalyst with time. This catalyst does not meet all of the criteria outlined in Table 1.
Kim et al (2014) determined the CO2 hydrogenation efficiency for a BaZr0.8Y0.16Zn0.04O3 perovskite catalyst with a 1/1 H2/CO2 blend at 1,110° F. and 15 psi. They achieved a low 38% conversion of CO2 with a CO selectivity of 97%. The long-term catalyst durability was not determined since the catalyst was only run for 5 hours.
Chen et al (2015) reported the synthesis of a nano,intermetallic catalyst (InNi3Co0.5) that proved to be active and selective for the RWGS reaction. The catalyst was fabricated by carburizing the In—Ni intermetallic base which produced dual active sites on the catalyst surface. They achieved a moderate 52-53% CO2 conversion for 150 hours at 1125° F. at high gas hourly velocities of 30,000 hr−1. As based upon its structure, this catalyst may meet criteria #3 and #7. It would be difficult and costly to manufacture this catalyst in multiple ton quantities (criteria #1 and #2) and it is not known if can be used commercially in traditional catalytic reactors (criteria #5 and #6). This catalyst does not meet CO2 to CO conversion efficiency requirements (criteria #8) and CO production selectivity. Since this catalyst was only tested for 150 hours, its stability and lifetime are not known.
Daza and Kuhn (2016) developed a La/Sr (3.0/1.0 w/w) catalyst impregnated on an FeO3 substrate. They observed a 16% conversion of H2/CO2 (1.0/1.0 v/v) to CO with a 95% selectivity at 1,300° F. and 15 psi. The CO2 conversion efficiency and CO selectivity were relatively constant over the period of a 150-hr. test. This catalyst meets criteria #1, #7 and #9 presented in Table 1. Since this catalyst was only run for 150 hrs. its long-term lifetime is not known.
Daza et al (2016) determined the CO2 hydrogenation efficiency for a La0.75Sr0.25FeO3 perovskite catalyst with a 1/1 H2/CO2 (v/v) blend at 1,020° F. and 15 psi. They achieved a very low 15% conversion of CO2 with a CO selectivity of 95%. The long-term catalyst durability was not determined since the catalyst was only run for less than 24 hours. In summary, no data has been published to date that indicates perovskites could be acceptable catalysts for CO2 hydrogenation.
Alumina has been widely studied as a catalyst support for both CO2 hydrogenation and dry reforming of methane (DRM). The benefits of alumina lay primarily in its high surface area, low cost and stability at high temperatures. It is also relatively cheap compared to other support materials. Yang et al (2018) synthesized a 10% Ni/20% CeO2 catalyst on γ-Al2O3. They tested this catalyst with a 4/1 H2/CO2 (v/v) blend at 1,300° F., 15 psi and a space velocity of 400 k hr−1. They observed a CO2 conversion of 67%, a CO selectivity of 90% and a CH4 selectivity of 10%. The catalyst efficiency dropped by 37% after 50 hrs. due to carbon formation and Ni sintering. Therefore, this is not a viable commercial catalyst.
While a Ni catalyst on Al2O3 substrate is a potential RWGS catalyst, the spinel nickel aluminate NiAl2O4 is easily formed, which can result in at least some loss of activity (Ryu et al, 2021). However, the resistance to coke formation of Ni/Al2O3 is highly dependent on the catalyst structure and composition. At high temperatures, the formation of the spinel phase NiAl2O4 results in increased resistance to coke formation. This is a result of the strengthening of the Ni—O bond in NiAl2O4 with respect to NiO crystal, thus increasing the difficulty of Ni2+ reduction to elemental nickel (Hu et al, 2004).
Magnesia is a promising support for due to its enhanced chemisorption of CO2 and high basicity. The benefits of magnesia and alumina can also be combined in mixed MgO—Al2O3 supports. The effect of the increased basicity and specific surface area has been reported by Jun et al using a catalyst for dry reforming of methane (Jun et al, 2015). The influence of the Mg/Al on the catalytic activity and catalyst lifetime remains unclear. Also, none of the catalysts reported fully meets the requirements stated in Table 1.
Depending on the reaction conditions and preparation methods of the catalysts, mixed MgO—Al2O3 systems doped with nickel both form spinels from the respective components. Based on a systematic study with varying nickel content in NixMg1−xAl2O4, Park et al reported that RWGS conversion was preferred at high magnesium atomic ratios (2021). The results which were supported by DFT calculations, indicating that CO selectivity increased with increasing magnesium content. Zhang et al (2021) described a 0.43% Ni on MgAl2O4 catalyst for CO2 hydrogenation of a 1/1 H2/CO2 blend at 1,472° F. They observed a modest 46% CO2 conversion efficiency with no discernable loss in conversion efficiently after 75 hours. However, this efficiency doesn't meet the CO2 conversion efficiency of between 70% and 100% above 1,300° F. and above 50 psi as outlined in Table 1. They didn't report CO production selectivity and the long-term deactivation rate of the catalyst is unknown.
The preparation of mixed Ni—Mg—Al—O phases has also been reported for the dry reforming of methane (DRM), where hydrotalcite-like mixed layered hydroxides were thermally decomposed, showing high activity and enhanced stability (Bhattacharyya et al.). Bhattacharyya et al. also compared the catalytic activity to commercial NiO supported catalyst. Hydrotalcite is a naturally occurring layered mineral, discovered in Sweden in 1842, with the chemical formula: Mg6Al2(OH)16CO3.4H2O, a name stemming from the high-water content of the material as well as its resemblance to talc. It can also easily be synthesized by co-precipitation methods (Cavani et al, 1991). Many minerals with different molecular compositions but with similar empirical elemental structures have been reported. The term hydrotalcite (hydrotalcite-like compounds—HTs, layered double hydroxides—LDHs) is used to describe a large group of naturally occurring minerals and synthetic materials that possess the typical layered structure of hydrotalcite. The general formula of hydrotalcites can be summarized as: [M2+1−xM3+x(OH)2][(An−x/n)·mH2O] where M2+, M3+ are di- and tri-valent cations; A are interlayer anions; and x is the mole fraction of trivalent cations. The part [M2+1−xM3+x(OH)]2 describes the composition of brucite-like layers and [(An−x/n)·mH2O] describes the composition of interlayer spaces.
For the DRM catalyst synthesis, nickel was introduced using various methods including incipient wetness impregnation, ion-exchange, as well as co-precipitation. Nickel based hydrotalcite based catalysts have been considered for DRM and are well investigated.
Ni-Hydrotalcite catalysts with low nickel content are highly active towards CO2 conversion, pointing at a simultaneous occurrence of reverse water gas shift (RWGS) (Lin et al, 2021). Numerous heterogeneous catalysts have been developed based on the cation-exchange ability of the Brucite layer, the anion-exchange ability of the interlayer, the surface tunable basicity, as well as the adsorption capacity (Debek et al, 2017; U.S. Pat. No. 8,388,987B2, 2013). Hydrotalcites have also been found for the production and processing of polymers, as neutralizing additives, or as part of building materials (Figueras et al, 2010; Sikander et al, 2017). However, to our knowledge there are no reports on the application of hydrotalcites in commercial RWGS catalysts, either with or without the additional metal active sites such as for example Ni.
Hydrotalcite based materials were also reported as possible solid sorbents for pressure swing CO2 adsorption, a technology known as sorption-enhanced water-gas shift (SEWGS). Hydrotalcites showed high thermal and mechanical stability with sufficiently high cyclic working capacity and fast adsorption kinetics. The regeneration step (desorption of CO2 by feeding steam to the adsorbent) is slower and limits the cyclic working capacity of the adsorbent. It was found that a higher operating temperature is beneficial because of enhanced desorption kinetics. Steam induces the desorption of a second adsorption site available for CO2 which cannot be desorbed with N2 (Boon et al, 2014). Calcination of hydrotalcites leads to dehydration, dihydroxylation and decarbonation, and eventual formation of the spinel. While the formation of the spinel phase from alumina and magnesia precursors is performed at temperatures above 1500° C., spinel phase forms at significantly lower temperatures during the calcination of hydrotalcites. When applying hydrotalcite precursors for the synthesis of commercial RWGS catalysts, the spinel phase can form as low as 700° C. (Jatav et al, 2016).
Bahmanpour et al (2019) studied an in situ formed Cu—Al spinel as an active substrate for the hydrogenation of CO2 with H2 into syngas. They used co-precipitation followed by hydrogen treatment to form the Cu—Al spinel with excess Cu in different weight ratios. A 4% Cu catalyst on the Cu—Al spinel was found to be the most efficient for CO2 conversion. A low CO2 conversion rate of 47% at 1,110° F. was achieved at relatively high space velocities with no detectable deactivation after a 40-hr. test. In comparison, a 4% Cu on gamma-alumina converted 33% of the CO2 at 1,110° F. This catalyst meets criteria #1 and it possibly meets criteria #2, #3, #5, #6 and #7. However, copper containing catalysts tend to deactivate over time by sintering at high temperatures, which is problematic especially for the Cu excess formulation. In addition, this catalyst formulation needs to be tested for 1,000 hrs. or longer to assess long-term lifetime (criteria #10).
Table 2 summarizes the above catalytic systems and other potential catalysts for the catalytic CO2 hydrogenation to CO. Most of these catalysts were tested for less than 48 hrs. which is not a sufficient length of time to assess catalyst durability. Since the lifetime of a commercial catalyst needs to be 2 years or longer, the reduction in CO2 conversion must be between 0% and 1.0% conversion decline per 1000 hours.
Since these catalysts will be run in commercial reactors, they need to operate efficiency at pressures above 50 psi, and preferably above 150 psi. All the catalysts listed in Table 2 have been evaluated at 15 psi, except for Dupont et al, 2003; Kharaji et al, 2012; and Chen et al, 2019 who tested their catalyst at 300, 150 and 145 psi, respectively.
The present invention is generally directed to the production of low-carbon syngas from captured CO2 and renewable H2. The H2 is generated from water using an electrolyzer powered by renewable electricity, or from any other method of low-carbon H2 production. The improved catalysts use low-cost metals, they can be produced economically in commercial quantities, and they are chemically and physically stable up to 2,100° F. CO2 conversion efficiencies are between 80% and 100% with CO selectivity of greater than 99%. The catalysts don't sinter or form coke when converting H2:CO2 mixtures to syngas in the operating ranges of 1,300-1,800° F., pressures of 75-450 psi, and space velocities of 2,000-100,000 hr−1. The catalysts are stable, exhibiting between 0 and 1.0% reduction in conversion or selectivity per 1,000 hrs. The syngas can be used for the synthesis of low-carbon fuels and chemicals, or for the production of purified H2. The H2 can be used at the production site for the synthesis of low-carbon chemical products or compressed for transportation use.
In this section we describe our improved catalyst formulations which has been demonstrated to meet the performance and quality requirements presented in Table 1.
Four types of improved CO2 hydrogenation or Reverse Water Gas Shift (RWGS) catalysts are described in these embodiments.
Type A. Metal-Spinel Catalysts - Pure alumina is an amphoteric substance, as it can react with both acids and bases. Depending on the morphology and crystal structure present the basicity of alumina can be complex. Acidic alumina catalyzes reactions that are typically acid catalyzed (Pines et al, 1960). However, several spinels produced from the high-temperature calcination of alumina with the Group 1 metals (Li, Cs, Rb) and Group 2 metals (Mg, Ca, Sr, Ba and Be) form metal aluminates that have defined and usually basic surface properties, also due to the increased surface concentrations of the hydroxy (—OH) groups.
Formates are formed when H2/CO2 mixtures react with these hydroxy groups according to Equation 2.
H2+CO2=HCOO-Metal Aluminate+H2O (Eq. 2)
These formates decompose rapidly at high temperatures in the presence of H2 to form CO (Equation 3) with a high selectivity. Therefore, some of these spinels are excellent CO2 hydrogenation catalysts.
2HCOO-Metal Aluminate+H2=2CO+2H2O (Eq. 3)
A spinel of the invention is any class of minerals or synthetically produced minerals with the general chemical form of AB2X4. For the invention, X is oxygen, B can be chosen from the group comprising aluminum, iron, chromium, cobalt, and vanadium. A is chosen from a group comprising Mg, Zn, Fe, Mn, Cu, Ni, Li, Cs, Rb, Mg, Ca, Sr, Ba, Be, and Ti. In one embodiment of the invention, the catalyst is a metal aluminate such that B is Aluminum, and X is Oxygen.
Type B. Metal Impregnated Metal-Spinel Catalysts—When selected Group 1 (alkali metals such as Li, Cs, Rb) and/or Group 2 (alkaline earth metals such as Mg, Ca, Sr, Ba, and Be) are impregnated on selected spinels in the appropriate levels, the surface abundance of hydroxy groups increases, resulting in their improved efficiency for CO2 hydrogenation. The addition of these elements is believed to enhance the chemisorption of CO2 due to their impact on basicity, total pore volume and surface are. Dopants may be Ni, Cu, Ce, Zr, Ti, La, or the early Lanthanides. When two or more impregnated metals on the metal aluminate spinel are calcined up to a temperature of 2,100° F., a solid solution is formed. This solid solution represents excellent catalyst for CO2 hydrogenation. Ni and Mg form a solid solution, Ni2Mg, at 2,050° F. on Mg-Aluminate since Ni and Mg both crystallize in a face-centered cubic structure, and they have similar electronegativities and valences. Ni also forms a solid solution with Cu, NiCu3, at 2,050° F. since Ni and Cu both crystallize in a face-centered cubic structure, and they have similar atomic radii, electronegativities and valences. Solid solutions are formed when two of the metals impregnated on the metal aluminate spinel have similar crystal structures, atomic radii, electronegativities and valences. Dopants may be present as extra framework and unincorporated into the spinel or may be supported on the Metal-Spinel Catalyst, or especially at higher concentrations be both supported by spinel or be present in close proximity inside a physical mixture.
The RWGS catalyst is operated in the 1,300-1,800° F. range in order to achieve CO2 conversion efficiencies above 70%, which is a temperature range where many materials sinter at increased rates as they approach their melting point. The solid solution used in the catalyst should be a solid at these temperatures. Therefore, viable solid solutions are those that are formed in the 1,850-2,100° F. range. Ni2Mg and NiCu3 are stable solids at these catalyst operating temperatures, and they have excellent performance as CO2 hydrogenation catalysts. The solid solution, Cu2Mg, is formed from 2 moles of Cu and 1 mole of Mg at 1,300° F. and it doesn't qualify as a candidate since the solution is a liquid at the catalyst operating temperatures.
Type C. Enjineered Layered Solids—Hydrotalcite based materials are used as catalysts for RWGS. These materials include natural hydrotalcite as well as synthetic highly engineered anionic clays or layered double hydroxides (LDH). Natural hydrotalcites may be used as additives, or as precursors for further synthesis. Synthetic Hydrotalcites are commercially available or may be prepared by coprecipitation methods.
Hydrotalcite is a layered double hydroxide (LDH)—Mg6Al2CO3(OH)16.4H2O. Multiple structures containing loosely bound carbonate ions exist, which are known for their ion exchange capabilities as well as their ability to adsorb CO2. Upon calcination the material decomposes to high surface area spinel, that can easily be rehydroxylated or recarboxylated. Full thermal decomposition will lead to a spinel that is known for its hardness and durability.
LDH's are structurally derived from the brucite (Mg(OH)2) structure by the isomorphous substitution of M2+ ions by M3+ ions. The LDH layers are positively charged and charge neutrality is realized by the presence of interlamellar anions. When M3+ is Al3+ the mineral hydrotalcite is obtained. The uniquely high surface area of LHD as well as their surface basicity significantly improve the performance of RWGS. The surface area, chemical composition as well as basicity of the layered solid is engineered to optimize the performance of the commercial RWGS catalyst.
Type D. Perovskite Catalysts.—Similar to the materials of Type A, perovskite materials can be used as improved RWGS catalysts. Perovskite materials have the general chemical form of ABX3. For the invention, X is Oxygen. A and B are cations. Perovskite materials can be chosen from simple perovskites such where A is chosen from the group comprising Sr, Ca, Ba, Mg, Fe, La, Ca, Pb, or Bi and B is chosen from the group comprising Al, Ti, Rb, Si, Fe, Yb or Mn. In addition, solid solution perovskite materials can also be used such as lanthanum strontium manganite, lanthanum aluminate-strontium aluminum tantalate (LSAT), lead scandium tantalate, or lead zirconate tantalate. These catalysts comprise perovskites or mixtures of various perovskites.
In the following embodiments that described the preferred catalyst compositions and catalyst performance, certain specific details provide a thorough understanding of various embodiments. Unless the context requires otherwise, throughout the specification and claims which follow, the word “comprise” and variations thereof, are to be construed in an open, inclusive sense, that is, as “including, but not limited to.”
1. A reverse water gas shift (RWGS) catalyst for the conversion of H2 and CO2 mixtures into syngas comprising the process steps of: a) introducing a H2 and CO2 mixture, or b) a mixture of H2 and CO2 and light hydrocarbons, into a catalytic reactor in a catalytic conversion system to produce syngas or carbon monoxide. The product of the catalytic reactor is further reacted to produce at least one of the following products chosen from the list consisting of liquid fuels, methanol, propane, naphtha, and chemicals
2. A reverse water gas shift (RWGS) catalyst of embodiment 1 (Type A) which comprises: a) a metal-aluminate spinel having a surface area between 10 m2/g and 1000 m2/g, wherein the metal spinel is selected from a group consisting of:
3. A reverse water gas shift (RWGS) catalyst (Type B) which employs one of the metal-alumina spinels described in embodiment 2 with an impregnated metal dopant such but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce. The metal dopant may not be chemically bond to the spinel. In some embodiments only one of the above elements may be added, while in other embodiments catalyst formulations may comprise complex mixtures of several of the above elements.
Metal dopants may be introduced by impregnation, or in some cases also by physical mixing of solid precursors with the spinel. The amount of metal precursor may range from 0 to 35 wt. % of a metal salt (e.g. nitrates, acetates, carbonates, etc.) or metal hydroxides, or a metal oxide. The formed material is then calcined at a temperature up to 2,100° F., thereby synthesizing a catalyst that is a metal-impregnated, metal-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
4. A reverse water gas shift (RWGS) catalyst of embodiment 1 (Type C), which contains an engineered layered solid in which the engineered layered solid may embody 100% of the solid catalyst without any additional additives. A reverse water gas shift (RWGS) catalyst (Type C) which employs the use of engineered layered solids with an impregnated metal dopant such but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce. The metal precursor may be a metal salt (e.g., nitrates, acetates, carbonates, etc.), or metal hydroxides, or a metal oxide. The engineered layered solid may embody 0-10% of catalyst formulation, 20-30% of catalyst formulation, 40-50% of catalyst formulation, 50-60% of catalyst formulation, 50-60% of catalyst formulation, 60-70% of catalyst formulation, 70-80% of catalyst formulation, or 80-90% of catalyst formulation. The remaining part of the formulation may be dopants or other additives needed to form a commercial catalyst. The metal dopant may not be chemically bond to the engineered layered solid. In some embodiments only one of the above elements may be added, while in other embodiments catalyst formulations may comprise complex mixtures of several of the above elements.
Metal dopants may be introduced by impregnation, or in some cases also by physical mixing of solid precursors with the engineered layered solid. The formed material is then calcined at a temperature up to 2,100° F. This reverse water gas shift (RWGS) catalyst (Type C) employs the use of natural occurring layered solid with an impregnated metal dopant such but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce. The metal precursor may be a metal salt (e.g. nitrates, acetates, carbonates, etc.), or metal hydroxides, or a metal oxide. The natural occurring layered solid may embody 0-10% of catalyst formulation, 20-30% of catalyst formulation, 40-50% of catalyst formulation, 50-60% of catalyst formulation, 50-60% of catalyst formulation, 60-70% of catalyst formulation, 70-80% of catalyst formulation, or 80-90% of catalyst formulation. The remaining part of the formulation may be dopants or other additives needed to form a commercial catalyst. The metal dopant may not be chemically bond to the engineered layered solid. In some embodiments only one of the above elements may be added, while in other embodiments catalyst formulations may comprise complex mixtures of several of the above elements. Metal dopants may be introduced by impregnation, or in some cases also by physical mixing of solid precursors with the engineered layered solid. The formed material is then calcined at a temperature up to 2,100° F.
5. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Mg salt; b) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of a CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Mg-alumina spinel according to embodiment 2 having a surface area between 5 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce. d) Ca-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary; ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g. e) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100 ° F., resulting in a metal-impregnated, Mg-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
6. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Ca salt; b) Ca-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of a CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ca-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d). Ca-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Ca-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Ca-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
7. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Sr salt; b) Sr-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of a CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Sr-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Sr-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Sr-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Sr-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
8. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Ba salt; b) Ba-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ba-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Ba-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Ba-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Ba-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
9. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Li salt; b) Li-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Li-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Li-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Li-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Li-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
10. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Rb salt; b) Rb-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Rb-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Rb-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Rb-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Rb-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
11. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Cs salt; b) Cs-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Cs-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Cs-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Cs-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
12. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Fe salt; b) Fe-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Fe-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Fe-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Fe-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Fe-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
13. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Co salt; b) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Co-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Co-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Co-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
14. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Ni salt; b) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, and a different metal spinel of embodiment 2 of at least 10 m2/g; e) Ni-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Ni-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
15. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Cu salt; b) Cu-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) a Cu-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Cu-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as a different metal spinel of at least 10 m2/g; e) Cu-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Cu-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
16. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Zn salt; b) Zn-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Zn-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Zn-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as a different metal spinel of at least 10 m2/g; e) Zn-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The.resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Zn-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
17. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a La salt; b) La-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) La-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) La-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as a different metal spinel of at least 10 m2/g; e) a La-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, La-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
18. A reverse water gas shift (RWGS) catalyst of embodiment 3 wherein the catalyst is comprises the following components: a) Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35 wt. % of a Ce salt; b) Ce-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; mixed with up to 35 wt. % of CaCO3, MgCO3, SrCO3, CaO, MgO, or SrO; c) Ce-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce; d) Ce-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as a different metal spinel of at least 10 m2/g; e) a Zn-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; impregnated with up to 35% of mixtures of primary, secondary, ternary, or more mixtures of salt mixtures including but not limited to Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, as well as a natural or engineered layered solid comprising 5-10% of the catalyst formulation, 20-30% of the catalyst formulation, 40-50% of the catalyst formulation, 50-60% of the catalyst formulation, 60-70% of the catalyst formulation, 70-80% of the catalyst formulation. The resulting formulation is calcined to up 2,100° F., resulting in a metal-impregnated, Ce-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
19. Although the embodiments 5-18 cover the formulations of a CO2 hydrogenation catalyst that focuses on the impregnation of a specific metal on a metal-alumina spinel synthesized from the same metal, the various permutations of the other metals in embodiment 3 on the other metal-spinels in embodiment 2 are covered (e.g., Ni on Mg-aluminate; Ni on Ba-aluminate, etc.).
20. This embodiment comprises a reverse water gas shift (RWGS) catalyst (Type C) which employs one of the metal-alumina spinels described in embodiment 2 with a) the impregnation of up to 35 wt. % of two metal salts (e.g. nitrates, acetates, carbonates, etc.) or metal hydroxides selected from a group comprising Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, which don't chemically bond to the spinel; b) calcining the metal-alumina spinel impregnated with the two or more metals at a temperature up to 2,100° F., thereby synthesizing a solid-solution of the two metals on the metal-alumina spinel.
21. The reverse water gas shift (RWGS) catalyst of embodiment 20 wherein the catalyst is produced by a process comprising the steps of: a) synthesizing a Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; b) impregnating the spinel with up to 35 wt. % of a mixture of Ni and Mg; c) calcining the Ni- and Mg-impregnated, Mg-alumina spinel at a temperature up to 2,100° F.; d) thereby producing a solid-solution of the two metals that has the composition Ni2Mg. Ni and Mg form a solid solution at 2,100° F. since Ni and Mg both crystallize in a face-centered cubic structure, have similar electronegativities and valences.
22. The reverse water gas shift (RWGS) catalyst of embodiment 20 wherein the catalyst is produced by a process comprising the steps of: a) synthesizing a Mg-alumina spinel according to embodiment 2 having a surface area between 10 m2/g and 1000 m2/g; b) impregnating the spinel with up to 35 wt. % of a mixture of Ni and Cu; c) calcining the Ni- and Mg-impregnated, Mg-alumina spinel at a temperature up to 2,100° F.; d) thereby producing a solid-solution of the two metals that has the composition NiCu3. Ni and Cu form a solid solution at 2,100° F. since Ni and Cu both crystallize in a face-centered cubic structure, have similar atomic radii, electronegativities and valences.
Most of the improved CO2 hydrogenation catalysts described above in the Catalyst Composition Embodiments meet the commercial quality and performance specifications summarized in Table 1.
1. Low-Cost Constituents—The catalysts are formulated primarily using low-cost Group 1 elements (Alkali Metals) comprising Na, K, Li, Cs and Rb; the Group 2 elements (Alkaline Earth Metals): Mg, Ca, Sr, Ba and Be; the Transition Metals comprising Ni, Co, Fe and Cu; and the Rare-Earth elements comprising Ce, Y, La. It has been found that the addition of small quantities of precious metals (such as Au, Ag, Pt, Pd, Ir) do not improve the performance of these improved CO2 hydrogenation catalysts.
2. Commercial Production—The substrates and catalysts are economically produced in multiple ton quantities using well established commercial-scale production processes. The metal alumina spinel substrates may be prepared by a) coprecipitation methods or b) by mixing appropriate molar quantities of a metal precursors and alumina particles to form a slurry, drying the slurry, and then calcining the mixture up to 2,600° F. The catalysts are prepared by the impregnation of the metal(s) on the metal-alumina spinel substrates followed by calcination up to 2,100° F.
3. Physically Robust—The disclosed catalysts have hardness of between 4 Mohs and 10 Mohs, or an equivalent Rockwell hardness. This high level of hardness eliminates the potential problem of catalyst breakage, cracking and ablation.
4. Chemically and Physically Stable—These a). metal-alumina spinels, b). metal impregnated metal metal-alumina spinels and c). solid solutions impregnated on the metal metal-alumina spinels maintain their chemical and physical properties (such as not melt) up to 2,100° F.
5. Compatible with Commercial Catalytic Reactors—The catalyst pellets, tablets, or hollow tablets are easy to load into catalytic reactors (tubular, or packed bed reactors). The pressure drop from the top to the bottom of the catalytic reactors is between 0 and 50 psi and usually between 0 and 25 psi. The activation of the catalyst (e.g., reduction with H2) is carried out in-situ if required.
6. High CO2 Conversion Efficiency—The CO2 to CO conversion efficiency for H2/CO2 blends with ratios higher than 3.0/1.0 is between 70% and 100%, preferably between 75% and 100%, and more preferably between 80% and 100% at space velocities between 2,000 hr−1 and 1,000,000 hr−1 and temperatures between 1,300° F. and 1,800° F.
7. High CO Production Selectivity—The disclosed catalyst formulations have CO of at least 90%. Some of the preferred catalyst formulations have CO selectivities greater than 99% with methane selectivities below 1%, and CO selectivities as low as 0.1% in some cases.
8. Doesn't Coke or Change Composition—These improved catalyst formulations do not coke or change chemical composition during operation.
9. Long-Term Performance—Several of the improved CO2 hydrogenation catalysts have been tested for more than 1,500 hrs. on stream and it has been determined that the reduction in CO2 conversion is between 0 and 0.50% per 1000 hours.
Example 1: Improved RWGS Catalyst Formulation A—A stream comprising CO2 is produced by an industrial process or captured from ambient air. This CO2 stream is fed to a CO2 capture facility. The CO2 capture facility uses methyl diethanolamine (MDEA) in an absorber tower to capture the CO2. Relatively pure CO2 is regenerated from the MDEA by heating. Low-carbon electricity from a wind farm, a solar farm, a nuclear power plant, or other low-carbon power sources is available at the site of the carbon capture facility. High-purity water is produced from locally available water. Low-carbon H2 is produced from the purified water via electrolysis.
This reaction uses the low-carbon electricity to split the water into H2 and O2. The electrolyzer in this example is a PEM Electrolyzer. The electrolyzer produces two streams, H2 and O2.
This improved catalyst formulation A of embodiment 2 (above) is manufactured by a method comprising the steps of: a) synthesizing a metal-aluminate spinel having a surface area between 10 m2/g and 1000 m2/g, wherein the metal spinel is selected from a group comprising:
The improved catalyst is used to convert the captured CO2 and renewable H2 stream into syngas. Example 1 provides the relationship between temperature and % CO2 conversion to CO for the improved CO2 hydrogenation catalyst. In this example, the H2 to CO2 ratio is 3.4/1.0, the pressure is 300 psig, and the space velocity is 20,000 hr−1. The conversion of CO2 varies from 75% to 83.5% from 1,250-1,650° F. with between 0 and 0.5% conversion reduction after 1,000 hrs. on stream. Since the catalysts at these relevant temperature ranges exhibits very little sintering, their lifetime is excellent. The CO selectivity is >99.5% with between 0 and 0.5% CH4 selectivity. The dotted line is the trendline which shows that the relationship between CO2 conversion and temperature is nearly linear.
Example 1—The Typical Relationship between Temperature and % CO2 Conversion to CO for the Improved RWGS Catalysts.
Example 2: Improved RWGS Catalyst Formulation B—This improved catalyst formulation B is described in embodiment #3 (above) as a metal on a metal aluminate. This type B CO2 hydrogenation catalyst employs one of the metal-alumina spinels described in embodiment 2 with a) the impregnation of up to 35 wt. % of a metal salt (e.g. nitrates, acetates, carbonates, etc.) or metal hydroxide selected from a group comprising Mg, Ca, Sr, Ba, Li, Rb, Cs, Fe, Co, Ni, Cu, Zn, La and Ce, which don't chemically bond to the spinel; b) calcining the impregnated, metal-coated metal-alumina spinel at a temperature up to 2,100° F., thereby synthesizing a catalyst that is an metal-impregnated, metal-alumina spinel that has a surface area between 5 m2/g and 1000 m2/g.
In this example the catalyst is MgO or Mg(OH)2 impregnated on a Mg-Alumina Spinel. The MgO or Mg(OH)2 is reduced in-situ with H2, producing Mg, MgO and Mg(OH)2 on the surface of the spinel.
The improved catalyst is used to convert the captured CO2 and renewable H2 stream into syngas. In this example, the H2 to CO2 ratio is 3.4/1.0, the temperature is 1,650° F., the pressure is 300 psig, and the space velocity is 20,000 hr−1. The conversion of CO2 is 82% at 1,650° F. with between 0 and 0.5% conversion reduction after 1,000 hrs. on stream. The CO selectivity is greater than 99%.
Example 3: Improved RWGS Catalyst Formulation C—This improved RWGS catalyst C is described in embodiments 20-23 for the efficient conversion of CO2 and H2 into syngas by a process comprising the steps of: a) synthesizing a Mg-aluminate spinel having a surface area between 10 m2/g and 1000 m2/g; b) coating the spinel with up to 20 wt. % of Mg to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising water soluble nickel salts and either nitrate or acetate salts of rare-earth metals; d) calcining the impregnated, metal-coated spinel at a temperature up to 2,100° F., thereby synthesizing a catalyst that is an impregnated spinel that is comprised with up to 35 wt. % nickel and of 0.1 wt. % to 5.0 wt. % of the rare earth metals. The catalyst may contain 0.1 to 5 parts-by-weight of cerium, ruthenium, lanthanum, platinum, or rhenium, and 2 wt. % to 20 wt. % nickel per 100 parts-by-weight of the spinel support. As described in embodiment #21, the solid solution catalyst is Ni2Mg.
Another improved catalyst type C for the efficient conversion of CO2 and H2 into syngas is produced by a process comprising the steps of a) synthesizing a Cu impregnated Cu-aluminate spinel having a surface area between 10 m2/g and 1000 m2/g; b) coating the spinel with up to 20 wt. % of Cu to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising water soluble Ni salts and either nitrate or acetate salts of rare-earth metals; d) calcining the impregnated, metal-coated spinel at a temperature up to 2,100° F., thereby synthesizing a catalyst that is an impregnated spinel that is comprised with up to 20 wt. % nickel and of 0.1 wt. % to 5.0 wt. % of the rare earth metals. As described in embodiment #22, the primary solid solution catalysts are NiCu3.
The relationship between temperature and CO2 conversion efficiency (Example #1) is similar for catalyst #1 and catalyst #2. The difference is that catalyst #1 has between 0 and 0.5% CH4 selectivity compared to up to 7.0% CH4 selectivity (depending upon temperature and pressure) for catalyst #2. However, catalyst #2 is more efficient at higher space velocities.
This application is a division of U.S. patent application Ser. No. 17/300,820, filed Nov. 16, 2021, which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17300820 | Nov 2021 | US |
| Child | 18445227 | US |
