An efficient two-step process for the direct production of liquid fuels from carbon dioxide and hydrogen

Abstract

An embodiment of the present invention relates to two improved catalysts and associated processes for the direct conversion of carbon dioxide and hydrogen to liquid fuel. The catalyst system includes two catalysts in series operating in concert to directly produce synthetic liquid fuel. The carbon conversion efficiency of carbon dioxide to liquid fuel is greater than 45%. The fuel is distilled to premium diesel fuel (about 70% by volume) and naphtha (about 30% by volume) that are used directly as "drop-in" fuels without any further processing. Any light hydrocarbons present with the carbon dioxide are also directly converted to fuel. This process is directly applicable to the conversion of carbon dioxide / hydrocarbon mixtures from ethanol plants, cement plants, power plants, biogas, secondary oil recovery, and carbon dioxide collected from other carbon dioxide / hydrocarbon streams. The catalyst system is durable, efficient, and maintains a relatively constant level of fuel productivity over time without the need for reactivation or replacement.

Description

[Technical Field]

[0001] This innovation describes an efficient two-step process for the direct production of liquid fuels from captured carbon dioxide and green hydrogen. The green hydrogen is produced by water electrolysis, where power is derived from a low-carbon source. The first step in the two-step process is the production of green syngas from the captured carbon dioxide and the green hydrogen using an improved catalyst. The improved catalyst is a catalyst that is produced by impregnating a metallic alumina spinel consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate with one or more of the following elements (barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc) to a concentration of about 35 parts by weight, and then heating the catalyst to 2150°F. (1,177℃) The improved catalyst has a carbon dioxide to carbon monoxide conversion efficiency of greater than 65% and a pressure of 135-350 psi (931~2,413kPa) and 1650°F (899℃) The second catalyst converts a mixture of hydrogen and carbon dioxide to synthesis gas with carbon monoxide selectivity of better than 98% under these conditions. The second catalyst produces liquid fuel directly from the synthesis gas. The liquid fuel is primarily composed of a small concentration of wax (C 24+ hydrocarbons) along with C5-C 23 This second catalyst is composed of aliphatic hydrocarbons. (1,724~2,413kPa)The first and second catalysts can operate at the same pressure because they operate efficiently at high pressures. The tail gas (C1-C5 hydrocarbons, hydrogen, carbon monoxide, and carbon dioxide) from the catalytic process is partially oxidized with oxygen from the electrolysis (autothermal reforming (ATR)) to produce additional synthesis gas, carbon dioxide, and heat. This commercial-scale process is applicable to the conversion of carbon dioxide recovered from conventional blast furnace power plants, gasification plants, oxyfuel combustion power plants, cement plants, grain fermentation plants, natural gas wellheads, chemical refineries, oil refineries, secondary oil recovery processes, and other plants that produce carbon dioxide emissions, as well as carbon dioxide recovered from ambient air. The liquid fuels produced include premium kerosene, diesel, jet fuel, and gasoline, and can be further processed to produce specialty chemicals including normal alkanes, normal 1-olefins, normal 1-hydroxyalkanes, solvents, lubricants, and high-performance waxes. Greenhouse gas emission reductions for the production of these liquid fuels and chemicals range from approximately 50 to 130%, depending on the carbon dioxide source and the power source used for hydrogen production. In addition to reducing greenhouse gas emissions, the synthetic fuels also reduce criteria pollutant emissions. The simplified two-stage catalytic process is durable, efficient, and maintains relatively constant fuel productivity levels over long periods of time without the need for catalyst regeneration or replacement. [Background technology]

[0002] The present invention is primarily focused on improved catalysts and related processes that efficiently and economically convert mixtures of carbon dioxide and hydrogen directly into liquid fuels that reduce greenhouse gas emissions. These liquid fuels are often referred to as low carbon liquid fuels (LCLFs), net zero carbon fuels, zero carbon fuels, ultra low carbon fuels, or green fuels.

[0003] There are several reasons why fossil fuels remain so common (Fulkerson et al., 1990): 1. Fossil fuels are available in one form or another in virtually every region of the globe because of the widespread infrastructure for the distribution of gaseous and liquid fuels. 2. Fossil fuels can be used efficiently to provide energy for a wide variety of uses at all scales. 3. Chemical fuels are unrivaled as transportation fuels because they are portable and contain significant amounts of stored chemical energy. Liquid fuels will therefore continue to be the predominant energy source for transportation.

[0004] However, the production and combustion of fossil fuels produces significant amounts of greenhouse gases, namely carbon dioxide and methane, and therefore the global objective has become to replace fossil fuels with low-carbon liquid fuels (LCLF) and / or low-carbon natural gas (LCNG) ( Schuetzle, 2018 ).

[0005] Although carbon dioxide can be converted to low-carbon natural gas (LCNG) (Marti et al., 2016; Hill, 2018), converting carbon dioxide to LCLF rather than LCNG has several advantages: 1. The energy densities of diesel and gasoline fuels are approximately 38.6 MJ / liter and 34.2 MJ / liter, respectively. These energy densities are much higher than those of methane (9.0 MJ / liter at 250 bar); hydrogen (5.3 MJ / liter at 690 bar); dimethyl ether (21.2 MJ / liter at 5 bar); methanol (15.6 MJ / liter); lithium-ion batteries (1.76 MJ / liter); and lead-acid batteries (0.56 MJ / liter) (Wikipedia, 2019). 2. Producing methane from carbon dioxide requires nearly twice as much hydrogen as producing liquid fuel from carbon dioxide. 3. Diesel and gasoline fuels can be stored at or near atmospheric pressure, compared to 200-400 bar for methane and 340-690 bar for hydrogen. 4. The global distribution infrastructure for liquid fuels is extensive, and the liquid fuels can be easily transported to almost any location on the planet. 5. Producing synthetic methane that can meet natural gas pipeline standards is challenging (Zhou et al., 2010; Melaina et al., 2013; Zaki et al., 2016; SocalGas, 2019).

[0006] As a result, there has been increasing interest in developing efficient and economical technologies for converting carbon dioxide into liquid fuels ( Arakawa et al., 2001 ; Olah et al., 2005 ; Sakakura et al., 2007 ; Centi et al., 2009 ; Olah et al., 2009 ; Mikkelsen et al., 2010 ; Artz et al., 2018 ; Li et al., 2018 ).

[0007] This improved catalyst and process offers the intriguing possibility of using primary energy from renewable, carbon-free sources (such as electricity derived from sunlight, wind, waves / tides, hydrogen, or nuclear power) to convert carbon dioxide, along with hydrogen, into a high-density vehicle fuel compatible with current transportation infrastructure. In addition, this next-generation technology will aid in the development of more efficient power plants that produce little or no emissions, such as oxyfuel plants. Oxyfuel plants refer to power plants that generate power (electricity) from natural gas and oxygen, and whose emissions are an almost pure carbon dioxide stream (instead of a dilute carbon dioxide stream as produced by traditional power plants).

[0008] Its real appeal is that it offers the promise of significant reductions in carbon emissions from transport systems without the policy changes in infrastructure required by the electrification of the vehicle fleet or the transition to a hydrogen economy (Pearson et al., 2009).

[0009] Most of the prior art on the advancement of carbon dioxide into liquid fuels has focused on the production of gasoline and diesel fuels as a "drop-in" fuel. Dimethyl ether (DME), although a potential low-emission fuel for diesel engines, is not a "drop-in" fuel because diesel engines must be modified for use with dimethyl ether and the fuel infrastructure has not been developed (Semelsberger, 2006).

[0010] Although methanol has been proposed for many years as a potential liquid fuel for engines, it has not been accepted as a fuel because it is highly flammable, toxic, and its combustion produces toxic and carcinogenic formaldehyde emissions. Instead, methanol is primarily used as a liquid fuel or as an intermediate chemical for the production of chemicals.

[0011] The production of "drop-in" liquid fuel from a mixture of hydrogen and carbon dioxide generally involves the following process. 1. Conversion of hydrogen / carbon dioxide mixture to synthesis gas 2. Conversion of the syngas to fuels that meet ASTM and other fuel specifications (Global Fuels Charter, 2019). This process typically requires two or more major conversion steps.

[0012] For a commercially viable carbon dioxide to liquid fuels process, it is important that the catalyst produced for the conversion of a hydrogen and carbon dioxide mixture to synthesis gas meet one or more of the quality and performance specifications listed below in Table 1.

[0013] Table 1. Quality and performance specifications established for the catalytic conversion of hydrogen / carbon dioxide mixtures to synthesis gas [Table 1]

[0014] Two approaches for the conversion of carbon dioxide to synthesis gas have been described in the prior art. The first, and most widely described, approach employs a catalytic process for the conversion of a mixture of carbon dioxide and hydrogen to synthesis gas. This method is also commonly referred to as "carbon dioxide hydrogenation" or "reverse water gas shift (RWGS)" (Senderens et al., 1902; Daza et al., 2016; Vogt et al., 2019). The second approach involves an electrolysis process for the conversion of a mixture of carbon dioxide and water to synthesis gas (Wang et al., 2016).

[0015] (Catalytic conversion of hydrogen / carbon dioxide mixtures to synthesis gas) Many patent applications, patents, and publications describe the conversion of hydrogen and carbon dioxide mixtures to synthesis gas. The prior art describes the development of catalysts for the conversion of ethylenediamine to propylene glycol. This prior art is summarized in Table 1. It is evaluated against the quality and performance specifications set forth above.

[0016] (1993) developed catalysts composed of transition metals, including rare metals (such as nickel, iron, ruthenium, rhodium, platinum, tungsten, palladium, and molybdenum), on zinc oxide for the reduction of carbon dioxide and hydrogen mixtures to carbon monoxide. They achieved relatively low conversions of up to 37% after 150 hours without significant loss of catalytic activity, but longer-term tests were not performed.

[0017] Chen et al. (2015) demonstrated the activity and selectivity of a nano-intermetallic catalyst (InNiCO) for the RWGS reaction. 0.5 reported the synthesis of a catalyst called 'CuO'. The catalyst was prepared by carbonizing an indium-nickel intermetallic base, which resulted in two active sites on the catalyst surface. They achieved a modest carbon dioxide conversion of 52-53% after 150 hours at 600°C and a gas rate of 300,000 mL / g catalyst / hr. Longer-term testing of this catalyst was not performed.

[0018] Bahmanpour et al. (2019) tested copper-impregnated copper-aluminum spinel as a potential catalyst for the hydrogenation of carbon dioxide to synthesis gas using hydrogen. They employed coprecipitation followed by hydrogen treatment to form copper-aluminum spinel with various copper / aluminum mass ratios. A copper to aluminum ratio of 4 to 1 was found to be most efficient for carbon dioxide conversion. However, they observed a relatively low carbon dioxide conversion rate of approximately 45% after a 40-hour test at 600 °C. Because copper-containing catalysts tend to become deactivated by sintering at high temperatures, such catalyst formulations need to be tested for more than 1,000 hours to evaluate their potential commercial viability. This is the only published study to explore the synthesis and performance of metal-impregnated and calcined metal-alumina spinel.

[0019] (Electrochemical Conversion of Carbon Dioxide / Water Mixtures to Syngas) The electrochemical conversion of carbon dioxide has been a dynamic field of research ( Zhu, 2019 ), with much of the research and development effort focused on fuel cell modifications ( Sunfire, 2016 ) and on PEM (proton exchange membrane) and alkaline electrolysis systems ( Messias et al., 2019 ).

[0020] (PEM and alkaline electrolysis) Opus 12 has developed a PEM electrolyzer that converts a mixture of carbon dioxide and water into a mixture of 16 oxygenated C1-C3 hydrocarbons (alcohols, ketones, aldehydes, and acids) (Kuhl et al., U.S. Patent Application Publication No. 2017 / 0321333). Separation of this complex mixture into specific chemicals requires expensive purification methods. Even if such separation were successful, ethanol would be the only suitable product that could be used as a fuel (e.g., blended into gasoline).

[0021] (fuel cell) Sunfire has developed a high-temperature co-electrolysis process for carbon dioxide and water using a solid oxide electrolysis cell (SOEC) to produce syngas. The SOEC operates at high pressure (>1 MPa) and high temperature (>800°C). The syngas is then converted to long-chain hydrocarbons using a traditional Fischer-Tropsch process. The wax is converted to gasoline and diesel fuels using a two-stage catalytic refining process. Thus, three stages are required to produce Sunfire's "drop-in" fuel, and the process requires complex wax upgrading or refining.

[0022] Current technology allows for four main processes for the conversion of carbon dioxide into "drop-in" liquid fuels.

[0023] (One-step process) 1. Carbon dioxide is converted directly into liquid fuel using a catalytic or electrochemical process.

[0024] (Two-step process) 1. Carbon dioxide is converted into synthesis gas using a catalytic or electrochemical process. 2. The synthesis gas is converted directly to liquid fuel using a second catalyst.

[0025] (Two-step process) 1. Carbon dioxide is converted primarily to chemical intermediates using catalytic or electrochemical processes. 2. The chemical intermediate is converted directly into a liquid fuel using a second catalyst.

[0026] (3-step process) 1. Carbon dioxide is converted into synthesis gas using a catalytic or electrochemical process. 2. The synthesis gas is converted primarily into chemical intermediates (e.g., wax; methanol, etc.). 3. The refined intermediate is converted directly into liquid fuel.

[0027] (4-step process) 1. Carbon dioxide is converted into synthesis gas using a catalytic or electrochemical process. 2. The synthesis gas is converted primarily into chemical intermediates (e.g., wax; methanol, etc.). 3. The refined intermediates are converted into liquid fuels using two main chemical processes.

[0028] (4-step process) 1. Carbon dioxide is converted into synthesis gas using a catalytic or electrochemical process. 2. The synthesis gas is converted into a mixture of organic intermediates (e.g., wax; methanol, etc.). 3. A separation process is used to produce the desired purified intermediate. 4. The refined intermediate is converted into a liquid fuel.

[0029] Prior art for one-stage, two-stage, three-stage, and four-stage processes is summarized and evaluated with respect to the quality and performance specifications outlined in Table 1.

[0030] (One-step process) Much of the effort to convert carbon dioxide to liquid hydrocarbon fuels in a single reactor has focused on developing catalysts that first generate carbon monoxide from carbon dioxide via hydrogenation. Carbon monoxide then reacts with hydrogen over the same catalyst through a mechanism based on the well-known Fischer-Tropsch (FT) catalytic reaction to form liquid fuel. One of the challenges associated with this FT process using carbon dioxide is the negligible concentration of carbon monoxide present during the reaction. This limits chain propagation, resulting in a product distribution that is typically enriched in light hydrocarbons, which are unsuitable for liquid fuels. To date, most research has focused on the use of iron-based catalysts, which are active in the reverse water-gas shift reaction and FT chemistry (National Academy of Sciences, 2019).

[0031] Landau et al. (Australian Patent Application Publication No. 2015 / 203898) described an iron spinel catalyst with 20% Fe2O3 deposited thereon. The catalyst particle size was varied from 100 μm to 3.0 mm. This catalyst was used in a synthesis gas reactor with a hydrogen / carbon dioxide ratio of 2.0-3.0 / 1.0 for approximately 2.0 hours. -1 The conditions tested were very low space velocities of 325-350°C, temperatures of 325-350°C, and pressures of 20-40 atmospheres. The maximum carbon dioxide conversion was 36%. Product selectivities were carbon monoxide (13%), methane (9%), C2-C5 hydrocarbons (44%), and C6-C 27 Hydrocarbons (25%). 6+ The hydrocarbon olefin / paraffin ratio was about 5 to 1. This catalyst does not produce a "drop-in" fuel that meets ASTM specifications, and does not meet the catalyst quality and performance specifications listed above.

[0032] Wang et al. (2013) reported that two composts, which mainly produce methane and C2-C4 paraffins, Fe / ZrO2 catalysts were described for catalyzing the hydrogenation of carbon dioxide. The selectivity for the production of liquid-phase hydrocarbons was extremely low.

[0033] Wei et al. (2018) described an iron-based catalyst for the one-step conversion of carbon dioxide to isoparaffins. The carbon dioxide conversion efficiency was only 26%, and the carbon monoxide selectivity was about 17%. Coke (carbon) volume within the catalyst's micropores caused a rapid decline in isoparaffin yield over time.

[0034] Williamson et al. (2019) described the performance of a one-step catalyst composed of carbon nanotubes deposited with iron nanoparticles. The catalyst was calcined in air at 400 °C for 1 hour or at 570 °C for 40 minutes and activated with hydrogen at 400 °C for 3 hours. The catalyst was then heated at 370 °C and 221 psi using a 3.0 / 1.0 hydrogen / carbon dioxide mixture. (1,524kPa)The average carbon dioxide conversion was 54%, and the selectivities for carbon monoxide and hydrocarbons were 30% and 70%, respectively. The average composition of the hydrocarbon products was 43% methane, 55% C2-C4 hydrocarbons, and 2.0% C 5+ It was a hydrocarbon.

[0035] Pan et al. (2007) reported that 13 hr -1 described the use of a rhodium catalyst supported on carbon nanotubes in a tubular reactor for the production of ethanol from a mixture of carbon dioxide and hydrogen at an extremely low space velocity of 1000 kJ / s. In addition to ethanol, the catalyst produced a complex mixture of oxygenated hydrocarbons, including methanol, acetaldehyde, acetone, isopropanol, and acetic acid. The problem with this catalyst is that it is not amenable to scale-up to industrial scale due to the high pressure drop of the catalytic reactor, the low space velocity, and the production of a complex mixture of oxygenated hydrocarbons.

[0036] (Two-step process) (U.S. Pat. No. 8,198,338) described a process for the conversion of carbon dioxide to gasoline. Hydrogen and carbon dioxide (2.0 / 1.0 molar ratio) were converted to methanol in a catalytic reactor using a Cu / ZnO / Al2O3 catalyst operated at a pressure of about 50 bar and 500°C. Because of the low operating pressure, the selectivity for the methanol product was only about 10%. Methanol produced from the first catalytic process was fed into another catalytic reactor containing a ZSM-5 catalyst and operated at a pressure of about 4 bar and 390°C for the conversion of methanol to gasoline. The conversion efficiency of the two-stage process and the chemical and physical composition of the gasoline were not described. However, based on the selectivity for methanol production in the first reactor, the selectivity for the gasoline product was estimated to be less than 10%.

[0037] (3-step process) Sunfire implemented a pilot system to generate syngas using the electrolytic conversion of carbon dioxide and water using a solid oxide electrolysis cell (SOEC) to produce syngas (Zhu, 2019). The syngas was then converted to long-chain hydrocarbons using a traditional Fischer-Tropsch process. Wax was converted to gasoline and diesel fuels using a two-stage catalytic refining process. Thus, three stages were required for Sunfire's pilot plant to produce "drop-in" fuels.

[0038] (4-step process) Several four-stage processes have been described in the current art. One approach uses a one-stage process to produce a chemical intermediate such as methanol from a hydrogen / carbon dioxide mixture, followed by a three-stage process to convert the methanol to gasoline. Another approach uses a hydrogen / carbon dioxide mixture to produce synthesis gas, followed by Fischer-Tropsch conversion of the synthesis gas to wax, followed by a two-stage conversion of the wax to liquid fuels.

[0039] Kothandaraman et al. (2016) used polyamine (PEMA) in tetrahydrofuran (THF) to capture carbon dioxide. While this amine has good carbon dioxide capture efficiency, amines are known to deactivate catalysts. The captured carbon dioxide was converted to methanol in solution using a ruthenium PNP pincer catalyst. The catalyst is a ruthenium complex with organic ligands surrounding the ruthenium. This process was tested in the laboratory at a pressure of 75 atmospheres and a temperature of 145°C using a hydrogen / carbon dioxide reactant ratio of 3.0 / 1.0. The carbon conversion of carbon dioxide to methanol was 65%.

[0040] A plant to demonstrate this process was commissioned in Svartsengi, Iceland, during 2012. Hydrogen was produced electrochemically from water using 5.0 megawatts of geothermal power. Carbon dioxide was obtained from the Svartsengi power plant in Iceland. Methanol production was approximately 50,000 liters / year.

[0041] Gasoline can be produced from this methanol using a three-stage Exxon-Mobil patented process (Jafari, 2018). This process uses three catalytic reactors: Catalytic Conversion #1: Methanol to Dimethyl Ether; Catalytic Conversion #2: Dimethyl Ether to C2-C5 Olefins; and Catalytic Conversion #3: C2-C5 Olefins to Gasoline. MTG gasoline is generally composed of 53% paraffins, 12% olefins, 9% naphthenes, 26% aromatics, and 0.3% benzene, and is sulfur-free. The octane number (RON+MON) / 2 is 87, and the RVP (psi) is 9.0. (62.1kPa) is.

[0042] In conclusion, the prior art has not shown that a "drop-in" liquid fuel can be produced in two major steps from a carbon dioxide / hydrogen mixture that meets the performance and quality specifications outlined in Table 1.

[0043] (Metal-Alumina Spinel) Bahmanpour et al. (2019) published the only dated prior art on the performance of metals impregnated into and calcined on metal-alumina spinel substrates. They synthesized CuO on CuAl2O4 spinel with a Cu / Al ratio of 4 / 1. A relatively low carbon dioxide conversion of 47% was observed at 600 °C without detectable deactivation after 40 h of testing. However, copper-containing catalysts tend to become inactive due to sintering at high temperatures. Additionally, candidate catalyst compositions need to be tested for more than 1,000 h to assess their potential for commercialization.

[0044] No other prior art documents have been published on the RWGS activity of other metals impregnated into metallic spinels and calcined.

[0045] (Tail gas conversion) The first, second, third, and fourth stage processes produce a tail gas that is generally composed of unconverted hydrogen and carbon monoxide along with C1-C5 hydrocarbons and carbon dioxide, which must either be used as energy for an industrial-scale plant or converted to further synthesis gas.

[0046] The predominant process for converting tail gas to synthesis gas is the steam methane reforming (SMR) process. However, steam reforming has several drawbacks. Steam reforming is a highly endothermic reaction, and excess steam is required to suppress or retard deactivation from carbon deposition. As a result, SMR requires high energy, making the production of this additional synthesis gas expensive. Additionally, the SMR process produces carbon dioxide from the combustion of fuel gas to ignite the burners in the SMR.

[0047] Catalytic partial oxidation (POX) of tail gas to synthesis gas offers several advantages over SMR. The oxidation of hydrocarbons to synthesize a gas mixture is exothermic, and the process is much more energy efficient than both steam reforming and dry reforming processes (Gaffney et al., U.S. Pat. No. 6,402,989). However, POX has the following potential drawbacks: 1. A relatively high concentration of oxygen is required, the source of which is usually derived from the cryogenic separation of relatively high concentrations of oxygen from air. 2. The POX process can be highly exothermic, which can damage the catalyst or create problem sites on the catalyst that can cause thermal runaway.

[0048] Autoreforming of tail gas to synthesis gas (ATR) is another process that can be used for the conversion of the tail gas. The partial oxidation occurs at the reactor inlet and provides heat for the steam reforming reaction. As a result, there is no need to supply heat to the reactor (Ashcroft, 1991; Choudhary, 1995; and Ruckenstein, 1998).

[0049] Cobalt-nickel on alumina catalysts have been found to exhibit superior performance for the ATR of methane in terms of activity, stability, and synergistic effects compared to other catalysts. However, when a mixture of methane, carbon dioxide, and oxygen is heated to about 1300°F, (approx. 704℃) and 15 psi (103kPa) When modified with , some carbon formation is observed (Foo (2012) and Zhang (2007)). Summary of the Invention

[0050] In one aspect, the present invention provides a process for the conversion of carbon dioxide to liquid fuels, the process comprising: a) introducing a gaseous mixture of carbon dioxide and hydrogen, or a mixture of carbon dioxide, hydrogen, and light hydrocarbons, into a first catalytic reactor in a catalytic conversion process to produce synthesis gas, the first catalyst being a metal alumina spinel composed of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate impregnated with one or more of the following elements (Ba, Ca, Co, Fe, Mg, Mn, Ni, and Zn) to a concentration of about 35 parts by weight (e.g., 1 part to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight), and heating the first catalyst to 2150°F. (1,177℃) (e.g., 1000°F to 2150°F) (538℃~1,177℃) , 1500°F to 2150°F (816℃~1,177℃) , or 1750°F to 2150°F (954℃~1,177℃)and b) introducing the synthesis gas into a second catalytic reactor in the catalytic conversion system to produce tail gas, water, and liquid fuel, wherein the second catalyst is a catalyst selected from the group consisting of silica, alumina, and combinations thereof, and is selected from the group consisting of about 2 parts to about 25 parts by weight (e.g., 3 parts to 25 parts by weight, 5 parts to 25 parts by weight, or 10 parts to 25 parts by weight) of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, and the like, per 100 parts by weight of a support. and b) an element selected from the group consisting of ruthenium, barium, copper, and zinc, and about 0.1 parts by mass to about 5 parts by mass (e.g., 0.2 parts by mass to 5 parts by mass, 1 part by mass to 5 parts by mass, or 2 parts by mass to 5 parts by mass) of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, and rhenium, thereby producing a liquid fuel, a tail gas, and water; and c) separating the liquid fuel, the tail gas, and the water from each other, thereby producing the liquid fuel.

[0051] In another aspect, the present invention provides a catalyst for the conversion of carbon dioxide to synthesis gas, wherein the hydrogen / carbon dioxide introduced into the first catalytic reactor has a volume ratio of about 2.0 to 4.0 (e.g., 2.0 to 4.0), and the catalytic reactor is operated at a temperature of about 1550 to 1900°F. (approx. 843~1,038℃) (e.g., 1550-1900°F (843~1,038℃) ) temperature range; approximately 100 to 400 psi (approx. 689~2,758kPa) (e.g., 100-400 psi (689~2,758kPa) ) pressure within the range of 1000 hours -1 exceeding (e.g., 1000 hours) -1 ~50,000 hours -1 , 2500hr -1 ~25,000 hours -1 , or 5000hr -1 ~15,000 hours -1 ) space velocity.

[0052] In another aspect, the present invention provides a process for the direct production of liquid fuels, the process comprising: a) producing hydrogen and oxygen by electrolysis of water, wherein power (electricity) for the electrolysis is generated from a renewable or low carbon source selected from the group consisting of wind, sunlight, geothermal heat, hydrogen, ocean currents, biomass, flare gas, nuclear power, off-peak electricity from fossil fuel plants, and power (electricity) generated by an oxy-fuel combustion plant.

[0053] In another aspect, the present invention provides a process for the production of liquid fuels, the process comprising the steps of: a) producing hydrogen and oxygen from the electrolysis of water; and combusting waste polymeric materials (e.g., plastics) and / or other waste materials (e.g., biomass, paper, etc.) with a portion of the oxygen produced from the electrolysis; b) producing combustion gases comprising primarily carbon dioxide and water along with heat; c) passing the hot combustion gases through a gas turbine generator to generate electricity for operation of the two-stage catalytic process described herein; and d) extracting water from the combustion gases. and trace contaminants (e.g., sulfur and chlorine compounds) to provide a high purity carbon dioxide stream; e) mixing the carbon dioxide with hydrogen to provide a hydrogen / carbon dioxide mixture in a volumetric ratio of about 1.5 / 1.0 to 4.0 / 1.0; f) introducing the hydrogen / carbon dioxide mixture into the first catalytic reactor to produce synthesis gas; g) introducing the synthesis gas into the second catalytic reactor to produce tail gas, water, and liquid fuel; and h) separating the liquid fuel, tail gas, and water from each other, thereby producing the liquid fuel. [Brief explanation of the drawings]

[0054] [Figure 1] Figure 1 shows a process flow diagram for the improved catalyst and process described herein for the direct production of liquid fuels from carbon dioxide and renewable hydrogen. Figure 1 also shows an integrated conversion system and process for the production of low-carbon liquid fuels. [Figure 2] FIG. 2 outlines the potential reactions that occur when a mixture of carbon dioxide and hydrogen is catalytically converted to carbon monoxide. DETAILED DESCRIPTION OF THE INVENTION

[0055] The present invention relates to an improved catalyst and process for the efficient and economical conversion of carbon dioxide and hydrogen mixtures directly to synthetic liquid fuels in two stages.

[0056] The improved catalyst comprises impregnating a metallic alumina spinel comprising magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate with one or more of the following elements (barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc) to a concentration of about 35 parts by weight, and heating the impregnated spinel to 2150°F. (1,177℃) These improved catalysts have been found to be composed of 100% palladium, ...

[0057] Figure 1 shows a process flow diagram for the improved catalyst and process described herein for the direct production of liquid fuels from carbon dioxide and renewable hydrogen. Figure 1 also shows an integrated catalytic converter and process for the production of low carbon liquid fuels.

[0058] Electrolysis 101 is used to generate hydrogen. Power for hydrogen production may be generated from renewable and / or low carbon sources such as, but not limited to, wind, sunlight, geothermal, hydrogen, ocean currents, biomass, flare gas, atomic mass, and others. Other potential sources include efficient power generated from oxy-combustion plants.

[0059] The captured carbon dioxide 102 may be obtained from, but is not limited to, carbon dioxide collected from conventional wind power plants, gasification plants, oxyfuel combustion power plants, cement plants, grain fermentation plants, natural gas wellheads, chemical refineries, oil refineries, secondary oil recovery processes, and other plants that emit carbon dioxide, as well as carbon dioxide collected from ambient air.

[0060] Hydrogen from process 101; carbon dioxide from process 102; and syngas and heat (Q) from process 110 are mixed and heated 103 in the appropriate ratio and introduced into catalytic conversion system 104. Two innovative catalysts, namely, catalyst #1 105 and catalyst #2 107, are included in catalytic conversion system 104.

[0061] Catalyst #1 105 is a catalyst prepared by impregnating a metallic alumina spinel consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate with one or more of the following elements (barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc) to a concentration of about 35 parts by weight (e.g., 1 part to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight) and heating at 2150°F. (1,177℃) (e.g., 1000°F to 2150°F) (538℃~1,177℃) , 1500°F to 2150°F (816℃~1,177℃) , or 1750°F to 2150°F (954℃~1,177℃) ) impregnated spinel, synthesized by calcination, with high surface area (>15m 2 / g) catalyst. The improvements described herein include a manufacturing process for making stable catalysts consisting of selected metal spinels impregnated with one or more elements (Ba, Ca, Co, Fe, Mg, Mn, Ni, and Zn). 。

[0062] Catalyst #2 107 is a catalyst for the direct production of liquid fuels from syngas as described by Schetzle et al. in U.S. Patent Nos. 8,394,862, 9,090,831, and 9,631,147. Catalyst #1 105 and Catalyst #2 107 are suitable for use at pressures between about 100 and 350 psi. (approx. 689 to 2,413 kPa) (e.g., 100psi to 350psi (689kPa~2,413kPa) ) range of pressure.

[0063] Catalyst #1 is Catalyst # 2 Because the catalytic conversion system 104 operates at a higher temperature than catalyst #2 107, a heat exchanger 106 is included in the catalytic conversion system 104 to reduce the temperature of the gas relative to the operating temperature of catalyst #2 107. The products from the catalytic conversion process 104 are separated by product separator 108 into tail gas 109, water 111, and renewable liquid fuel 113. 。

[0064] A portion of the tail gas 109 is returned to the catalytic conversion process 104 until the desired conversion of carbon monoxide in the syngas is achieved. The remaining tail gas 109 is combusted 110 (autothermal reforming (ATR)) with oxygen produced from the electrolysis system 101. The products from the ATR process are syngas and heat. The syngas is mixed with other gases at 103, and the heat from 110 is used to help heat the gas mixing / heating system 103. Additional heat is added to the gas mixing system 103 to bring the gas up to the operating temperature of Catalyst #1 105.

[0065] The water (commonly referred to as catalytic reaction water) 111 can be used for grey water applications 112 or purified for the electrolysis process 101 and / or other uses. The renewable liquid fuel 113 can be used directly for off-road diesel engines, blended with petroleum derived diesel fuel 115, or distilled 116 into petroleum fuel products (e.g., #1 diesel, #2 diesel, #3 diesel, and jet fuel) 117.

[0066] Figure 2 outlines the potential reactions that occur when a mixture of carbon dioxide and hydrogen is catalytically converted to carbon monoxide. The catalysts described in this improved technology have been developed primarily to produce carbon monoxide from a mixture of carbon dioxide and hydrogen (if present with carbon dioxide) via reaction 201, and from a mixture of carbon dioxide and C1-C8 hydrocarbons via reactions 203 and 204.

[0067] The improved catalyst and process primarily produces carbon monoxide from carbon dioxide and hydrogen (reaction 201) or from carbon dioxide and hydrocarbons (reactions 203 and 204). These reactions are endothermic, requiring the addition of heat for the conversion to occur. As shown in FIG. 1, the first catalyst in the catalytic reactor is used to efficiently convert a mixture of carbon dioxide and water to carbon monoxide. This improved carbon dioxide reforming catalyst 105 operates at pressures between 150 and 300 psi. (1,034~2,068kPa) The first catalyst operates at a higher temperature than the second catalyst, producing predominantly carbon monoxide with a selectivity of over 95%. Because the first catalyst operates at a higher temperature than the second catalyst, a heat exchanger (FIG. 1-106) is included between the catalysts to reduce the temperature of the second catalyst to its ideal operating level.

[0068] The primary advantage of this process is that catalysts #1 and #2 can be efficiently operated continuously at similar pressures (recognizing that there is a pressure drop between catalyst system #1 and catalyst system #2), eliminating the need for compression between the two catalytic reactor systems.

[0069] Table 2 shows the results for the carbon dioxide reforming catalyst at 1650°F. (899℃) and 300 psi (2,068kPa) The selectivity for carbon monoxide and methane production from a hydrogen / carbon dioxide mixture (3.4 / 1.0) at 1000 s is summarized. The carbon dioxide conversion efficiency is about 71%, while the carbon monoxide selectivity is about 100% and the methane selectivity is zero.

[0070] Table 2. Improved CO reforming catalysts at 1650°F with H / CO (3.4 / 1.0) (899℃) and 300 psi (2,068kPa) Selectivity of CO and CH4 production after approximately 800 hours of operation at [Table 2]

[0071] Table 3 shows the temperature at 1650°F. (899℃) The effect of pressure on the conversion of a hydrogen and carbon dioxide mixture (3.4 / 1.0) to carbon monoxide at pressures between 150 and 300 psi is outlined. (1,034 to 2,068 kPa) As the pressure is increased to 150 psi, the carbon monoxide selectivity is nearly 100% and the methane selectivity is zero. (1,034kPa) Approximately 78% to 300 psi (2,068kPa) The figure has fallen to 73% in the past.

[0072] Table 3. 1650°F for improved CO2 reforming catalysts (899℃) Effect of pressure on the conversion efficiency of H2 / CO2 mixture (3.4 / 1.0) to CO at room temperature [Table 3]

[0073] The second catalyst 107 (FIG. 1) at the rear end of the converter uses a catalyst that produces fuel directly from syngas.

[0074] This composition of the improved catalyst 107 includes, per 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof, about 2 parts by weight to about 25 parts by weight of cobalt (e.g., 3 parts by weight to 25 parts by weight of cobalt, 5 parts by weight to 25 parts by weight of cobalt, or 10 parts by weight to 25 parts by weight of cobalt), and about 0.1 to 5 parts by weight (e.g., 0.2 to 5 parts by weight, 1 to 5 parts by weight, or 2.5 to 5 parts by weight) of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium.

[0075] Table 4 provides the relationship between the temperature of catalyst #2 during the conversion of carbon dioxide in the syngas produced from catalyst #1. Thus, catalyst #2 converts a portion of the carbon dioxide not converted by catalyst #1, depending on the operating temperature.

[0076] Table 4. Effect of temperature on CO2 conversion in syngas over catalyst #2 [Table 4]

[0077] The carbon dioxide used as injection into the process may be obtained from many different sources, including carbon dioxide collected from traditional blast furnace power plants, gasification plants, oxyfuel combustion power plants, cement plants, grain fermentation plants, natural gas wellheads, chemical refineries, oil refineries, secondary oil recovery processes, and other plants that emit carbon dioxide emissions. Additionally, carbon dioxide can be captured from ambient air using direct air capture systems and absorbed into a relatively pure carbon dioxide stream for use in the improved two-stage process described herein.

[0078] C2-C6 hydrocarbons containing carbon dioxide can also be used as process injections, as these hydrocarbons will also be converted to liquid fuels. Such streams include natural gas condensates, gases from reforming processes, and other gas streams containing carbon dioxide and C2-C6 hydrocarbons.

[0079] The integrated process requires carbon dioxide injection. In one embodiment, the carbon dioxide is sourced from the separation of carbon dioxide in a fuel gas stream using alkylamines. The alkylamines used in the process can include monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, aminoethoxyethanol, or combinations thereof. In another embodiment, the carbon dioxide is already present in the natural gas feed.

[0080] The manufacturing process for the first catalyst is significant in that it produces a robust catalyst composed of various impregnated spinels. This unique chemical structure results in enhanced resistance to coking compared to conventional metal-supported reforming catalysts. This also results in enhanced resistance to syngas poisons such as sulfur and ammonia. In addition, this catalyst has high catalytic activity at a lower surface area compared to monometallic, isolated catalytic phases, such as nickel on alumina. This catalyst does not require alkali promotion, which is necessary to suppress carbon deposition typically seen with feed gases such as those described herein. The catalyst also operates with a variety of feeds, including dry feed, steam feed, combined dry feed / steam feed, and tri-reforming feed. Mixtures of higher (heavy) hydrocarbon feeds can also be obtained using this catalyst.

[0081] (Preparation of catalyst #1) The improved catalyst is produced in two steps: 1) high surface area (>15 m 2 / g) of metallic spinel (e.g., 15m 2 / g~150m 2 / g, 20m 2 / g~150m 2 / g or 25m 2 / g~150m 2 / g) by impregnation of high surface area alumina with one of the following elements (magnesium, calcium, strontium, potassium, or sodium) and heating the impregnated alumina at 2150°F. (1,177℃) (e.g., 1000°F to 2150°F) (538℃~1,177℃) , 1500°F to 2150°F (816℃~1,177℃) , or 1650°F to 2150°F (899℃~1,177℃)) to form magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate. 2) These spinels are then impregnated with up to 35% by weight (e.g., 1 part to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight) of one or more of the following elements: barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc, and then heated to 2150°F. (1,177℃) (e.g., 1000°F to 2150°F) (538℃~1,177℃) , 1500°F to 2150°F (816℃~1,177℃) , or 1750°F to 2150°F (954℃~1,177℃) ) fired. Three specific examples are provided below.

[0082] (Example 1) Aluminum oxide Magnesium The synthesis of high surface area gamma alumina (Al2O3) pellets is provided as a first example. 2 The substrate chosen for the synthesis of spinels approximately 1-10 mm in diameter with a surface area exceeding 1 / g is magnesium acetate (Mg(C2H3O2)2) dissolved in distilled water to produce a 1.0 mg / ml solution. Approximately 100 ml of this solution is mixed with 100 g of the pellets and heated to 220°F. (104℃) The impregnated pellets are placed in a drying oven at a final temperature of 2050°F for 30 minutes. (1,121℃) 15°F / min until it reaches 15°F / min in about 2 hours (8.3℃ / min) The mixture is calcined by heating in air at a rate of 2050°F. (1,121℃) maintained for 30 minutes at approximately 15°F / min (approx. 8.3°C / min) The resulting product is magnesium-alumina spinel (MgAl2O4). Other spinels may be synthesized in a similar manner using acetates or nitrates of calcium, strontium, potassium, or sodium.

[0083] (Example 2) The synthesis of 10 wt. % magnesium to magnesium aluminate (MgAl2O4) in one step is provided as the first example. High surface area gamma alumina (Al2O3) pellets were prepared in a volume of approximately 35 m 2 The substrate chosen for the synthesis of spinels approximately 1-10 mm in diameter with a surface area exceeding 1 / g is magnesium acetate (Mg(C2H3O2)2) dissolved in distilled water to produce a 1.0 mg / ml solution. Approximately 180 ml of this solution is mixed with 100 g of the pellets and heated to 220°F. (104℃) The impregnated pellets are placed in a drying oven at a final temperature of 2050°F for 30 minutes. (1,121℃) 15°F / min until it reaches 15°F / min in about 2 hours (8.3℃ / min) The mixture is calcined by heating in air at a rate of 2050°F. (1,121℃) maintained for 30 minutes at approximately 15°F / min (approx. 8.3°C / min) The resulting product is magnesium-alumina spinel (MgAl2O4) impregnated with 10% by weight of magnesium.

[0084] (Example 3) The synthesis of magnesium aluminate (MgAlO) with 10% magnesium and 2.5% calcium by weight is provided as the following example. The magnesium aluminate synthesized in Example 1 was impregnated with a solution of magnesium acetate (Mg(CH0)) and calcium acetate (Ca(CH0)), resulting in the magnesium aluminate being impregnated with 10% magnesium and 2.5% calcium by weight. The impregnated pellets were then heated to a final temperature of 2050°F. (1,121℃) 15°F / min until it reaches 15°F / min in about 2 hours (8.3℃ / min) The mixture is fired by heating in air at a rate of 2050°F. (1,121℃) maintained for 30 minutes at approximately 15°F / min (approx. 8.3°C / min)The mixture is cooled to room temperature at a rate of 0.015 .mu.m. The resulting product is a 10 wt.% magnesium / 2.5 wt.% impregnated magnesium-alumina spinel (MgAl2O4). Spinels impregnated with other metals may be synthesized in a similar manner using calcium, strontium, potassium, or sodium acetates or nitrates.

[0085] (catalytic chemistry) Spinel produced from high-temperature calcination of gamma-alumina with Group II elements (magnesium, calcium, strontium, and barium) has a higher concentration of basic surface hydroxyl groups than gamma-alumina. Furthermore, impregnation with the metals (barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc) increases the concentration of these hydroxyl groups. We have demonstrated that formate is formed when a hydrogen / carbon dioxide mixture reacts with these hydroxyl groups according to Equation 1. H2 + CO2 = HCOO-metalloaluminate + H2O (Equation 1)

[0086] These formates decompose rapidly at high temperatures in the presence of hydrogen to form primarily carbon monoxide (Equation 2). 2HCOO-metalloaluminate + H2 = 2CO+2H2O (Equation 2)

[0087] (carbon dioxide source) Carbon capture is the process of recovering carbon dioxide from point sources. The two-stage catalytic process described herein requires that the carbon dioxide feedstock be recovered efficiently and economically with little contamination.

[0088] Several methods have been developed to capture carbon dioxide from one or more of the following sources: legacy blast power plants, gasification plants, oxyfuel combustion power plants, cement plants, grain fermentation plants, natural gas wellheads, chemical refineries, oil refineries, secondary petroleum processing, and other plants that emit large amounts of carbon dioxide (Schuetzle et al., 2010).

[0089] Power plants typically use control devices to remove sulfur oxides and sulfur particulates. Adding a carbon capture system requires significant additional capital and a concomitant increase in power generation. As a result, removal at a conventional power plant can increase the cost of electricity by 50% to 70% (IGCC, 2005). The cost of capturing carbon dioxide emissions from coal-fired and natural gas-fired power plants averages $130 / ton and $95 / ton, respectively (Metz et al., 2005).

[0090] Fermentation processes are used to produce distillates (e.g., rum), wine, beer, and fuel ethanol. As shown in Table 5, carbon dioxide is the predominant component in the fermentation process effluent. Ethanol concentrations are low, ranging from approximately 2000 to 4000 ppm. Because fermentation is an anaerobic process, oxygen is generally absent. Small amounts of sulfur compounds such as H2S and SO2 may be present in low concentrations (Safriet, 1995).

[0091] Table 5 - Typical concentrations of components in fermentation process effluents [Table 5]

[0092] Due to the low concentration of contaminants, fermentation process effluent is an ideal source of carbon dioxide for the improved direct fuel production process described in this invention. Low concentrations of sulfur compounds are easily removed using conventional adsorbents. Carbon dioxide capture costs range from $5 / ton to about $35 / ton. A second catalyst in the catalytic reactor will convert most of the ethanol (>50 mol%) to liquid fuel.

[0093] The cement industry currently represents approximately 7% of carbon dioxide (CO2) emissions globally and is the third-largest industrial energy consumer. Cement production involves the decomposition of limestone (calcium carbonate), which represents approximately two-thirds of the total carbon dioxide emissions generated during the process, with the remaining carbon dioxide emissions coming from the combustion of fuel. The industry has the second-largest share of all direct industrial carbon dioxide (CO2) emissions, accounting for 27% (2.2 gigatonnes) of annual carbon dioxide (GtCO2 / yr) in 2014 (IEA, 2018).

[0094] Cement plant emissions contain approximately 25% carbon dioxide by volume. Amine-based (MEA) adsorption capture technologies currently cost approximately $90 / ton. If oxy-fuel is used for heating, the cost drops to approximately $50 / ton of CO2 (Gardarsdottir et al., 2019). However, this cost can become prohibitive if significant cement plant modifications are required. Captured carbon dioxide from cement plants using amine capture or oxy-fuel combustion is an ideal feedstock for the production of renewable fuels from catalytic conversion units and processes.

[0095] Once the carbon dioxide is captured, it must be compressed to high pressures for storage in large volume vessels or cooled to produce liquid carbon dioxide that is stored in insulated vessels. These costs are therefore eliminated if the captured carbon dioxide is converted directly into liquid fuels at the plant site.

[0096] Several technologies have been developed to capture carbon dioxide from ambient air (U.S. Patent No. 9,095,813). Attempts at these ambient air capture processes have shown that the cost of carbon dioxide capture is very high (current costs range from $400 / metric ton to $600 / metric ton), but costs will decrease as these technologies become commercialized.

[0097] There are several sources of carbon dioxide that are associated with significant amounts of C1-C6 hydrocarbons. Some examples of such sources include carbon dioxide / light hydrocarbon mixtures from natural gas wellheads, emissions from secondary oil recovery using carbon dioxide, and biogas.

[0098] Injection of carbon dioxide into oil reservoirs is a common method of secondary oil recovery. After carbon dioxide injection, the recovered carbon dioxide contains light hydrocarbons that need to be separated before the carbon dioxide is re-injected. U.S. Pat. No. 9,159,105 describes a process for separating the light hydrocarbons from the carbon dioxide using a recovery unit. The carbon dioxide is re-injected into the wellhead for additional oil recovery, and the light hydrocarbons are used as fuel for local use.

[0099] [Various embodiments] (process) 1. A process for the conversion of carbon dioxide to liquid fuels, the process comprising: a) introducing a gaseous mixture of carbon dioxide and hydrogen, or a mixture of carbon dioxide, hydrogen, and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, the first catalyst in the catalytic conversion system being impregnated with magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate with up to 35% by weight (e.g., 1 part to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight) of one or more of the following elements: barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc; and then heating the impregnated spinel at 2150°F. (1,177℃)and b) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce tail gas, water, and liquid fuels, wherein the second catalyst is selected from the group consisting of silica, alumina, and combinations thereof, and is present in an amount of about 2 parts to about 35 parts by weight (e.g., 3 parts to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight) of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, and the like, per 100 parts by weight of a support. , copper, and zinc, and about 0.1 parts by mass to about 5 parts by mass (e.g., 0.2 parts by mass to 5 parts by mass, 1 part by mass to 5 parts by mass, or 2 parts by mass to 5 parts by mass) of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, and rhenium, thereby producing a liquid fuel, tail gas, and water; and c) separating the liquid fuel, the tail gas, and the water from each other, thereby producing the liquid fuel.

[0100] 2. The process according to process "1" above, wherein the carbon dioxide introduced into the first catalytic reactor is obtained from a source selected from the group of sources including conventional blast furnace power plants, gasification plants, oxyfuel combustion power plants, cement plants, grain fermentation plants, natural gas wellheads, chemical refineries, oil refineries, secondary oil recovery processes, and other plants that produce carbon dioxide emissions. Additionally, the carbon dioxide may be obtained from a direct air capture system.

[0101] 3. The process according to process "1", wherein hydrogen is produced using electrolysis, and the power for the electrolysis is generated from a renewable or low-carbon source, the renewable or low-carbon source being selected from the following sources: wind, sunlight, geothermal heat, hydrogen, ocean currents, biomass, flare gas, nuclear power, off-peak electricity from fossil fuel plants, and power generated by oxy-combustion plants.

[0102] 4. A process according to process "1" above, wherein the tail gas is recycled to the catalytic conversion system.

[0103] 5. The process according to process "1" above, wherein the water is used for grey water applications.

[0104] 6. The process according to the process "1", wherein the second catalytic reactor is operated at a pressure of about 150 psi to about 400 psi (approx. 1,034kPa to approx. 2,758kPa) (e.g., 150psi to 400psi (1,034kPa~2,758kPa) ), or preferably, about 250 psi to about 350 psi (approx. 1,724kPa to approx. 2,413kPa) (e.g., 250psi to 350psi (1,724kPa~2,413kPa) ) pressure.

[0105] 7. A process according to process "1" above, wherein a portion of the tail gas is combusted with oxygen from an electrolysis system used to generate synthesis gas and hydrogen to produce heat, and the synthesis gas is mixed with other gases introduced into the second catalytic reactor.

[0106] 8. A process according to process "1" above, wherein the liquid fuel is used without further processing in an off-road diesel engine.

[0107] 9. A process according to process "1" above, wherein the liquid fuel is mixed with a petroleum-based diesel fuel to provide a fuel mixture.

[0108] 10. The process according to process "1" above, wherein the liquid fuel is distilled to provide #1 diesel, #2 diesel, #3 diesel, and / or jet fuel.

[0109] (catalyst) 1. A catalyst for the conversion of carbon dioxide to synthesis gas, the first catalyst being formed by impregnation of magnesium aluminate spinel, calcium aluminate spinel, strontium aluminate spinel, potassium aluminate spinel, or sodium aluminate spinel with up to 35% by weight of one or more of the following elements: barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc, and then heating to 2150°F. (1,177℃) It is synthesized by a process which involves calcining impregnated spinel to

[0110] 2. A first catalyst, comprising a magnesium aluminate spinel impregnated with 5% to 35% by weight of barium, calcium, or cobalt.

[0111] 3. A first catalyst, comprising a magnesium aluminate spinel impregnated with 5% to 35% by weight of iron, magnesium, or manganese.

[0112] 4. A first catalyst, comprising a magnesium aluminate spinel impregnated with 5% to 35% by weight of nickel or zinc.

[0113] 5. A first catalyst, comprising a calcium aluminate spinel impregnated with 5% to 35% by weight of barium, calcium, or cobalt.

[0114] 6. A first catalyst, comprising a calcium aluminate spinel impregnated with 5% to 35% by weight of iron, magnesium, or manganese.

[0115] 7. A first catalyst, the first catalyst comprising a calcium aluminate spinel impregnated with 5% to 35% by weight of nickel or zinc.

[0116] 8. A first catalyst, comprising a strontium aluminate spinel impregnated with 5% to 35% by weight of barium, calcium, or cobalt.

[0117] 9. A first catalyst, comprising a strontium aluminate spinel impregnated with 5% to 35% by weight of iron, magnesium, or manganese.

[0118] 10. A first catalyst, the first catalyst comprising a strontium aluminate spinel impregnated with 5% to 35% by weight of nickel or zinc.

[0119] 11. A first catalyst, comprising a potassium aluminate spinel impregnated with 5% to 35% by weight of barium, calcium, or cobalt.

[0120] 12. A first catalyst, comprising a potassium aluminate spinel impregnated with 5% to 35% by weight of iron, magnesium, or manganese.

[0121] 13. A first catalyst, comprising a potassium aluminate spinel impregnated with 5% to 35% by weight of nickel or zinc.

[0122] 14. A first catalyst, comprising a sodium aluminate spinel impregnated with 5% to 35% by weight of barium, calcium, or cobalt.

[0123] 15. A first catalyst, comprising a sodium aluminate spinel impregnated with 5% to 35% by weight of iron, magnesium, or manganese.

[0124] 16. A first catalyst, the first catalyst comprising a sodium aluminate spinel impregnated with 5% to 35% by weight of nickel or zinc.

[0125] 17. A second catalyst comprising, per 100 parts by mass of support, 2 parts by mass to 25 parts by mass of cobalt and 0.1 parts by mass to 5 parts by mass of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0126] 18. A second catalyst comprising, per 100 parts by mass of support, 2 parts by mass to 25 parts by mass of iron and 0.1 parts by mass to 5 parts by mass of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0127] 19. A second catalyst comprising, per 100 parts by mass of support, 2 parts by mass to 25 parts by mass of magnesium and 0.1 parts by mass to 5 parts by mass of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0128] 20. A second catalyst comprising, per 100 parts by mass of support, 2 to 25 parts by mass of manganese and 0.1 to 5 parts by mass of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0129] 21. A second catalyst comprising, per 100 parts by mass of support, 2 parts by mass to 25 parts by mass of calcium and 0.1 parts by mass to 5 parts by mass of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0130] 22. A second catalyst comprising, per 100 parts by weight of support, 2 to 25 parts by weight of barium and 0.1 to 5 parts by weight of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0131] 23. A second catalyst comprising, per 100 parts by weight of support, 2 to 25 parts by weight of copper and 0.1 to 5 parts by weight of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0132] 24. A second catalyst comprising, per 100 parts by weight of support, 2 to 25 parts by weight of zinc and 0.1 to 5 parts by weight of cerium, ruthenium, lanthanum, platinum, rhenium, or a combination thereof.

[0133] (catalytic reactor) 1. A catalytic conversion system for the conversion of carbon dioxide to a liquid fuel, said catalytic conversion system comprising a first catalytic reactor and a second catalytic reactor, said first catalytic reactor comprising a first catalyst and a second catalyst in series, the compositions of which are as previously described.

[0134] 2. A catalytic conversion system according to the catalytic reactor "1", wherein the catalytic conversion system further includes a heat exchanger between the first catalytic reactor and the second catalytic reactor, and gas flows from the first catalytic reactor to the heat exchanger before flowing to the second catalytic reactor.

[0135] 3. A catalytic conversion system according to the catalytic reactor "1", wherein the catalytic conversion system further comprises a gas mixing chamber connected to the first catalytic reactor, allowing gas to flow between the gas mixing chamber and the first catalytic reactor.

[0136] 4. A catalytic conversion system according to the catalytic reactor "1", further comprising an electrolysis system for the production of hydrogen, the electrolysis system being connected to the gas mixing chamber so that the produced hydrogen can flow into the gas mixing chamber.

[0137] 5. A catalytic conversion system according to the catalytic reactor "1", wherein the catalytic conversion system further comprises a system for recovering carbon dioxide, the system for recovering carbon dioxide being connected to the gas mixing chamber, and the carbon dioxide obtained in the carbon dioxide recovery system can flow into the gas mixing chamber.

[0138] 6. A catalytic conversion system according to the catalytic reactor "4", wherein the catalytic conversion system further comprises a system for recovering carbon dioxide, the system for recovering carbon dioxide being connected to the gas mixing chamber, and the carbon dioxide obtained in the carbon dioxide recovery system can flow into the gas mixing chamber.

[0139] Further Processes and Catalysts 1. A process for efficiently converting a carbon dioxide / hydrogen mixture, or a mixture of carbon dioxide / hydrogen and light hydrocarbons, directly to synthetic liquid fuels by using a catalytic process including two catalysts, wherein the first catalyst in the catalytic conversion system comprises impregnating a metallic alumina spinel comprised of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, or sodium aluminate with one or more of the following elements (barium, calcium, cobalt, iron, magnesium, manganese, nickel, and zinc) to a concentration of about 35 parts by weight (e.g., 1 part to 35 parts by weight, 5 parts to 35 parts by weight, or 10 parts to 35 parts by weight) and heating the impregnated spinel to 2150°F. (1,177℃) (e.g., 1000°F to 2150°F) (538℃~1,177℃) , 1500°F to 2150°F (816℃~1,177℃) , or 1750°F to 2150°F (954℃~1,177℃) ), which process is efficient for producing synthesis gas from a mixture of carbon dioxide and hydrogen.

[0140] 2. A process according to the further process and catalyst "1" above, wherein hydrogen is produced from water using electrolysis.

[0141] 3. A process according to the further process and catalyst "1" above, wherein hydrogen may be produced from steam reforming of solid carbonaceous materials such as biomass, flare gas, biogas, methane, light hydrocarbons, and other components containing various stoichiometric mixtures of carbon, hydrogen, and oxygen.

[0142] 4. The process according to the further process and catalyst "1", wherein the carbon dioxide introduced into the first catalytic reactor is collected from one or more of the following sources: a conventional blast power plant, a gasification plant, an oxyfuel combustion power plant, a cement plant, a grain fermentation plant, a natural gas wellhead, a chemical refiner, an oil refinery, a secondary oil recovery plant, or any other plant that removes significant carbon dioxide emissions.

[0143] 5. A process according to the further process and catalyst "1", wherein the ratio of the hydrogen / carbon dioxide mixture entering the catalytic conversion process may be varied in the range of 1.5 / 1.0 to 4.0 / 1.0, preferably in the range of 2.0 / 1.0 to 3.5 / 1.0.

[0144] 6. The process according to the further process and catalyst "1", wherein the hydrogen / carbon dioxide mixture is heated to 150-350 psi (1,034~2,413kPa) wherein the catalytic converter is placed at a pressure in the range of

[0145] 7. A process according to the further process and catalyst "1", wherein the hydrogen / carbon dioxide mixture is heated to a temperature above the operating temperature of the first catalyst such that the first catalyst requires little or no additional heating.

[0146] 8. The process according to the further process and catalyst "1", which may be used in tubular fixed bed reactors, fluidized bed reactors, moving bed reactors, rotating bed reactors, slurry bed reactors, and other reactors common in the art.

[0147] 9. A process according to the above further process and catalyst "1", wherein the catalyst is heated to about 1200°F. (649℃) The process is reduced at temperatures up to

[0148] 10. A reduction catalyst according to the further process and catalyst "1", wherein the catalyst is 100 to 350 psi (689~2,413kPa) More preferably, in the range of 150 to 350 psi (1,034~2,413kPa) A reduction catalyst that efficiently converts a mixture of hydrogen and carbon dioxide to synthesis gas when operated at pressures in the range of

[0149] 11. A catalyst according to the further process and catalyst "1", wherein the catalyst is oxidized for 2500 hours -1 (e.g., 2500 hours) -1 ~40,000 hours -1 ) space velocity, which efficiently converts a mixture of hydrogen and carbon dioxide into synthesis gas.

[0150] 12. A catalyst according to the further process and catalyst "1" above, which efficiently converts a mixture of hydrogen and carbon dioxide into synthesis gas, and the ratio of hydrogen to carbon dioxide may be varied from 1.0 to 4.0, preferably from 1.5 to 3.5.

[0151] 13. A catalyst according to the further process and catalyst "1" above, wherein the catalyst is heated to 1650°F. (899℃) and 150 to 300 psi (1,034~2,068kPa) a catalyst that produces synthesis gas at a pressure of greater than about 65% (e.g., 65% to 100%) efficiency of carbon dioxide to carbon monoxide.

[0152] 15. A catalyst according to the further process and catalyst "1", which produces synthesis gas with a H2 / CO ratio in the range of 1.0 to 3.0, preferably in the range of 1.5 to 2.5.

[0153] 16. A catalyst according to the further process and catalyst "1" above, wherein the catalyst is heated to 2100°F. (1,149℃) Up to (e.g., 2100°F (1,149℃) A catalyst that is temperature stable.

[0154] 17. A catalyst according to the further process and catalyst "1" above, which is tolerant to contaminants present in the recovered carbon dioxide stream, natural gas, biogas, or other gas feed stream.

[0155] 18. A catalyst according to the further process and catalyst "1", wherein the catalyst does not form carbon or forms little carbon by coking.

[0156] 19. A catalyst according to the further process and catalyst "1", which when present in a carbon dioxide / hydrogen mixture efficiently converts methane to synthesis gas.

[0157] 20. A catalyst according to the further process and catalyst "1", which, when present in a carbon dioxide / hydrogen mixture, efficiently converts C2-C7 hydrocarbons to synthesis gas.

[0158] 21. A process according to the further process and catalyst "1" above, which efficiently produces synthesis gas when oxygen is added to a selected mixture of carbon dioxide, hydrogen, methane, and C2-C5 hydrocarbons.

[0159] 22. A process according to the further process and catalyst "1", wherein the synthesis gas is fed into another catalytic reactor to produce fuels and / or chemicals.

[0160] 23. A process according to the further process and catalyst "1", wherein the first catalyst is heated to the operating temperature of the second catalyst at 400 to 475°F. (204~246℃) In this process, a heat exchanger is used to reduce the temperature.

[0161] 24. A process according to the above further process and catalyst "1", wherein the cooled synthesis gas is fed to a second catalyst comprising, per 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof, about 2 parts by weight to about 25 parts by weight of cobalt (e.g., 2 parts by weight to 25 parts by weight), and about 0.1 parts by weight to about 10 parts by weight (e.g., 0.1 parts by weight to 10 parts by weight) of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, palladium, and rhenium, thereby producing a diesel fuel.

[0162] 25. The process according to the further process and catalyst "1", wherein the second catalyst is a hydrocarbon in the gas phase of C1-C5; C5-C 23 a liquid phase hydrocarbon of carbon monoxide, hydrogen, C1-C5 hydrocarbons, carbon dioxide, and water; a tail gas consisting of carbon monoxide, hydrogen, C1-C5 hydrocarbons, carbon dioxide, and water; and 24+ A process that produces hydrocarbons.

[0163] 26. A process according to the further process and catalyst "25", which comprises the steps of: 24+ introducing the product stream from said second catalytic reactor and catalyst system into a separator that separates hydrocarbons.

[0164] 27. The process according to the further process and catalyst "25", 23 C from hydrocarbons 24+ A process in which hydrocarbon fractionation is controlled by varying the temperature of the separator.

[0165] 28. A process according to the further process and catalyst "25", wherein the remaining liquid product stream is condensed into two fractions, an upper fraction comprising the liquid hydrocarbon fuel and a lower fraction comprising water.

[0166] 29. A process according to the further process and catalyst "25", wherein the liquid hydrocarbon fuel is separated from the water.

[0167] 30. The process according to the further process and catalyst "29", wherein the liquid hydrocarbon fuel is used directly for off-road diesel engines and vehicles.

[0168] 31. The process according to the further process and catalyst "29", wherein the liquid hydrocarbon fuel is blended with petroleum-based diesel fuel for use in on-road diesel engines and vehicles.

[0169] 32. A process according to the further process and catalyst "29", comprising: diesel fuel #1; diesel fuel #2; jet fuel; reformate; and heavy (C 24+ ) A process in which a synthetic liquid fuel is distilled to produce a minor fraction (less than about 5% by volume) of hydrocarbons.

[0170] 33. The process according to the further process and catalyst "29", wherein the reformulated gasoline blend is mixed with petroleum-based gasoline fuel for use in spark-ignition engines and vehicles.

[0171] 34. The process according to the further process and catalyst "29", wherein the diesel #1 (kerosene) is used for kerosene heaters and stoves.

[0172] 35. The process according to the further process and catalyst "29", wherein the diesel #1 (kerosene) is used for jet engines and turbines.

[0173] 36. A process according to the further process and catalyst "29", wherein the pure synthetic fuel or blended synthetic fuel reduces baseline engine emissions by at least 2% compared to petroleum-based fuel.

[0174] 37. A process according to the further process and catalyst "29", wherein the pure synthetic fuel or blended synthetic fuel improves one or more fuel properties by at least 2% compared to petroleum-based fuel.

[0175] 38. A process according to the further process and catalyst "29", wherein the pure synthetic fuel or blended synthetic fuel reduces greenhouse gas emissions by 2% compared to petroleum-based fuel.

[0176] 39. The process according to the further process and catalyst "29", wherein certain normal aliphatic hydrocarbons in the liquid aliphatic hydrocarbon fuel product are separated using distillation and / or adsorption.

[0177] 40. A process according to the further process and catalyst "29", wherein certain normal 1-alkanes in the liquid hydrocarbon fuel product are separated using distillation and / or adsorption.

[0178] 41. A process according to the further process and catalyst "29", wherein certain normal 1-hydroxyalkanes in the liquid hydrocarbon fuel product are separated using distillation and / or adsorption.

[0179] 42. A process according to the further process and catalysts "39" to "41", wherein separated specific normal aliphatic hydrocarbons, normal 1-alkanes, and normal 1-alkanes are produced having a purity of at least 95%, more preferably 98%, and even more preferably 99%.

[0180] 43. A process according to the further process and catalyst "40", wherein the C5-C 16 A process in which normal 1-alkanes are converted to normal 1-hydroxyalkanes by catalytic hydrogenation.

[0181] 44. A process according to the further process and catalyst "41", wherein normal 1-hydroxyalkanes in the liquid hydrocarbon fuel product are converted to normal 1-alkanes by catalytic dehydration.

[0182] 45. A process according to the further process and catalyst "40", wherein the C5-C 16 A process in which normal 1-alkanes are converted to synthetic lubricants by catalytic oligomerization.

[0183] 46. ​​A process according to the further process and catalyst "29", wherein a portion of the tail gas is recycled to catalyst #2 for the production of additional products.

[0184] 47. A process according to the further process and catalyst "29", wherein a portion of the tail gas is converted to additional synthesis gas by partial oxidation with oxygen (e.g., ATR conversion) or by autothermal reforming (ATR) resulting from electrolysis.

[0185] 48. A process according to the further process and catalyst "40", wherein heated synthesis gas is added to the hydrogen / carbon dioxide stream before it enters the first catalyst.

[0186] 49. A process according to the further process and catalyst "40", wherein the synthesis gas is fed into another type of catalytic process to produce fuels and / or chemicals.

[0187] 50. A process according to the further process and catalyst "40", wherein the synthesis gas is used to generate electricity using power sets, gas turbines, and other established gas power generation facilities.

[0188] 51. A process according to the further process and catalyst "40", wherein synthesis gas is used as a burner fuel to generate heat.

[0189] 52. The process according to the further process and catalyst "40", wherein a second catalyst is used for the production of ammonia.

[0190] 53. Further Processes and Catalysts. The process of "1", wherein the second catalyst is a Fischer-Tropsch (FT) type catalyst composition that produces wax, and then converts the wax to fuels and / or chemicals using conventional hydroreforming and hydrotreating processes.

[0191] 54. Further Processes and Catalysts. The process of "1" wherein the second catalyst produces methanol, ethanol, and / or other alcohols.

[0192] 55. Further Processes and Catalysts The process of "1" wherein a second catalyst is used for the production of methanol, which is then converted to gasoline using additional conventional catalysts and processes described in the state of the art.

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[0197] The present disclosure includes the following. [1] 1. A process for power and conversion of carbon dioxide to liquid fuel, comprising: a) producing hydrogen and oxygen from the electrolysis of water; b) introducing the hydrogen in combination with carbon dioxide into a first catalytic reactor comprising a first carbon dioxide hydrogenation catalyst to produce synthesis gas; c) introducing the synthesis gas into a second catalytic reactor using a second catalyst to produce primarily liquid fuels and tail gas; d) introducing the tail gas from the second catalytic reactor into a tail gas conversion system that utilizes oxygen from the electrolyzer to produce additional synthesis gas. process. [2] Hydrogen is generated using electrolysis, power for the electrolysis is generated from renewable or low-carbon sources; The renewable or low carbon source is selected from the group of sources consisting of wind, sunlight, geothermal, hydrogen, ocean currents, biomass, flare gas, nuclear power, and power generated by oxyfuel plants. The process described in [1] above. [3] The carbon dioxide introduced into the first catalytic reactor is collected from one or more of the following sources: a conventional blast furnace power plant, a gasification plant, an oxyfuel combustion power plant, a cement plant, a grain fermentation plant, a natural gas wellhead, a chemical refinery, an oil refinery, a secondary oil recovery process, and other plants that produce significant carbon dioxide emissions. The process described in [1] above. [4] The carbon dioxide is collected from ambient air using direct air capture technology The process described in [1] above. [5] the first catalyst comprises a metallic alumina spinel impregnated with a second element at a concentration of 1 part by weight or more and 35 parts by weight or less; the metal alumina spinel is selected from the group consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, and sodium aluminate; The second element is selected from the group consisting of Ba, Ca, Co, Fe, Mg, Ni, and Zn. The process described in [1] above. [6] The first catalytic reactor is operated at a pressure of at least 150 psi (1,034 kPa) and not more than 350 psi (2,413 kPa). The process described in [1] above. [7] The first catalytic reactor is operated at a temperature of at least 1,500°F (816°C) and not more than 2,000°F (1,093°C). The process described in [1] above. [8] The tail gas conversion system is a partial oxidation process The process described in [1] above. [9] The tail gas conversion system is an autothermal reforming (ATR) system. The process described in [1] above.

[10] The syngas is introduced into a heat exchanger to reduce the temperature of the syngas before it is introduced into the second catalytic reactor. The process described in [1] above.

[11] The second catalytic reactor is operated at a pressure of at least 150 psi (1,034 kPa) and not more than 350 psi (2,413 kPa). The process described in [1] above.

[12] the first catalyst is synthesized by impregnating a metal alumina spinel with a second element at a concentration of at least 1 part by weight and at most 35 parts by weight to provide an impregnated metal alumina spinel, and calcining the metal alumina spinel impregnated with the second element; The metal alumina spinel is selected from the group consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, and sodium aluminate, and the second element is selected from the group consisting of Ba, Ca, Co, Fe, Mg, Ni, and Zn. The process described in [1] above.

[13] 1. A process for the production of liquid fuels, comprising: a) producing oxygen and hydrogen from the electrolysis of water; b) utilizing the oxygen from the electrolysis to combust waste carbonaceous material to produce heat and waste combustion gases comprising carbon dioxide and water; c) removing any gaseous chlorine and sulfur containing gases that may be present in said waste combustion gases; d) removing water from the combustion gas to provide pure carbon dioxide vapor; e) recovering said carbon dioxide from the oxy-combustion process and adding it to other carbon dioxide recovered from ambient air or a stationary source to provide recovered carbon dioxide; f) mixing the hydrogen and the recovered carbon dioxide in a range of 1.5 / 1.0% by volume or more and 4.0 / 1.0% by volume or less to provide a hydrogen / carbon dioxide mixture; g) charging the hydrogen / carbon dioxide mixture in a ratio of 1.5 to 3.5 into a first catalytic reactor, the first catalytic reactor comprising a first catalyst, the first catalyst comprising a metal alumina spinel impregnated with a second element at a concentration of 1 to 35 parts by weight, the metal alumina spinel being selected from the group consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, and sodium aluminate, and the second element being selected from the group consisting of Ba, Ca, Co, Fe, Mg, Ni, and Zn; h) operating the first catalytic reactor at a temperature in the range of from 1,400°F (760°C) to 2,000°F (1,093°C) and a pressure in the range of from 100 psi (689 kPa) to 400 psi (2,758 kPa) to provide synthesis gas; i) introducing the synthesis gas into a second catalytic reactor, the second catalytic reactor comprising a second catalyst, the second catalyst comprising, per 100 parts by weight of a support, 2 to 25 parts by weight of a first element or a combination of first elements and 0.1 to 5 parts by weight of a second element or a combination of second elements, the first element or the combination of first elements being selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper, zinc, and combinations thereof, the second element or the combination of second elements being selected from the group consisting of cerium, ruthenium, lanthanum, platinum, and rhenium, and the support being selected from the group consisting of silica, alumina, and combinations thereof, thereby producing liquid fuel, tail gas, and water; j) separating the liquid fuel, the tail gas, and the water from one another, thereby producing the liquid fuel. process.

Claims

1. 1. A process for power and conversion of carbon dioxide to liquid fuel, comprising: a) producing hydrogen and oxygen from the electrolysis of water; b) introducing said hydrogen in combination with carbon dioxide into a first catalytic reactor comprising a first carbon dioxide hydrogenation catalyst to produce synthesis gas; c) introducing the synthesis gas into a second catalytic reactor using a second catalyst to produce primarily liquid fuel and tail gas; d) introducing the tail gas from the second catalytic reactor into a tail gas conversion system that utilizes oxygen from the electrolyzer to produce additional synthesis gas; the first catalytic reactor operates at a temperature of at least 1,500°F (816°C) and not more than 2,000°F (1,093°C); the first catalyst comprises a metallic alumina spinel impregnated with a second element at a concentration of 1 part by weight or more and 35 parts by weight or less; the metal alumina spinel is selected from the group consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, and sodium aluminate; The second element is selected from the group consisting of Ba, Ca, Co, Fe, Mg, Ni, and Zn. process.

2. Hydrogen is generated using electrolysis, power for the electrolysis is generated from renewable or low-carbon sources; The renewable or low carbon source is selected from the group of sources consisting of wind, sunlight, geothermal, hydrogen, ocean currents, biomass, flare gas, and nuclear power. The process of claim 1.

3. The carbon dioxide introduced into the first catalytic reactor is collected from one or more of the following sources: a conventional blast furnace power plant, a gasification plant, an oxyfuel combustion power plant, a cement plant, a grain fermentation plant, a natural gas wellhead, a chemical refinery, an oil refinery, a secondary oil recovery process, and other plants that produce significant carbon dioxide emissions. The process of claim 1.

4. The carbon dioxide is collected from ambient air using direct air capture technology The process of claim 1.

5. The first catalytic reactor is operated at a pressure of at least 150 psi (1,034 kPa) and not more than 350 psi (2,413 kPa). The process of claim 1.

6. The tail gas conversion system is a partial oxidation process The process of claim 1.

7. The tail gas conversion system is an autothermal reforming (ATR) system. The process of claim 1.

8. The syngas is introduced into a heat exchanger to reduce the temperature of the syngas before it is introduced into the second catalytic reactor. The process of claim 1.

9. The second catalytic reactor is operated at a pressure of at least 150 psi (1,034 kPa) and not more than 350 psi (2,413 kPa). The process of claim 1.

10. the first catalyst is synthesized by impregnating a metal alumina spinel with a second element at a concentration of from 1 part by weight to 35 parts by weight to provide an impregnated metal alumina spinel, and calcining the metal alumina spinel impregnated with the second element; The metal alumina spinel is selected from the group consisting of magnesium aluminate, calcium aluminate, strontium aluminate, potassium aluminate, and sodium aluminate, and the second element is selected from the group consisting of Ba, Ca, Co, Fe, Mg, Ni, and Zn. The process of claim 1.

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