Improved Catalysts and Processes for the Direct Production of Liquid Fuels from Carbon Dioxide and Hydrogen

Abstract

Embodiments of the present invention describe two improved catalysts and related methods for the direct conversion of carbon dioxide and hydrogen to liquid fuel. The catalytic converter consists of two catalysts in series operating at the same pressure to directly produce synthetic liquid fuel or synthetic natural gas. The carbon conversion efficiency from CO2 to liquid fuel is greater than 45%. The fuel is distilled to premium diesel fuel (approximately 70% by volume) and naphtha (approximately 30% by volume), which can be used directly as a "drop-in" fuel without further processing. Any light hydrocarbons present with carbon dioxide are also directly converted to fuel. The method is directly applicable to the conversion of carbon dioxide / hydrocarbon mixtures from ethanol plants, cement plants, power plants, biogas, secondary oil recovery, and CO2 collected from other carbon dioxide / hydrocarbon streams. The catalytic system is sustainable and efficient, maintaining a relatively constant level of fuel productivity over long periods of time without the need for catalyst reactivation or replacement.

Description

Technical Field

[0001] The present invention relates to an improved catalyst and method capable of efficiently and economically directly converting a mixture of CO2 and H2 into liquid fuel in two main steps. In the catalytic process, two enhanced catalysts that function efficiently continuously at similar pressures are employed to simplify the entire process of manufacturing fuel from non-petroleum raw materials. Catalyst #1 converts a mixture of H2 and CO2 into synthesis gas with a ratio of H2 to CO of about 1.5 to 2.5, and Catalyst #2 directly produces synthetic liquid fuel (and other products) from the synthesis gas. H2 and O2 are generated from water using electrolysis. The exhaust gas (C1-C5HC, H2, CO, and CO2) from the catalytic process is partially oxidized by O2, thereby generating additional synthesis gas and heat. This commercial-scale process is applicable to the conversion of CO2 collected from fermentation processes, cement plants, power plants, atmospheric CO2 capture systems (direct air capture), coal-fired power plants, natural gas processing plants, natural gas power plants, ammonia facilities, chemical facilities, and other important CO2 sources (IPCC, 2005; Schuetzle, et al, 2010; Wieclaw-Solny et al, 2013). The light hydrocarbons present in CO2 are also converted into synthesis gas. The liquid fuels produced include kerosene, diesel fuel, jet fuel, and gasoline blendstock. The reduction in greenhouse gas emissions by liquid fuels varies in the range of about 50 - 130% depending on the source of CO2 and the source of the electricity used for the production of H2. In addition to the reduction in greenhouse gas emissions, synthetic diesel fuel reduces the emissions of regulated pollutants and improves fuel efficiency. This simplified two-step catalytic process is sustainable and efficient, maintaining a relatively constant level of fuel productivity over a long period without the need for catalyst reactivation or replacement.

Background Art

[0002] The present invention is mainly focused on improved catalysts and related processes for efficiently and economically directly converting a mixture of CO2 and H2 into liquid fuels that reduce greenhouse gas emissions. These liquid fuels are often referred to as low-carbon liquid fuels (LCLF), zero-carbon fuels, ultra-low-carbon fuels or green fuels.

[0003] There are several reasons why fossil fuels continue to be common (Fulkerson et al. 1990). 1. Because the distribution infrastructure for gaseous and liquid fuels is extensive, fossil fuels are in fact available in some form in almost all regions of the world. 2. It can be effectively used to provide energy for countless applications on all scales. 3. Because it contains transportable and a significant amount of stored chemical energy, there is nothing comparable as a fuel for transportation.

[0004] Therefore, liquid fuels are likely to remain the dominant energy source for transportation.

[0005] However, since the production and combustion of fossil fuels produce significant amounts of the greenhouse gases CO2 and CH4, replacing fossil fuels with low-carbon liquid fuels (LCLF) and / or low-carbon natural gas (LCNG) has become a global goal (Schuetzle, 2018).

[0006] Although CO2 can be converted into low-carbon natural gas (LCNG) (Marti et al, 2016; Hill, 2018), there are several advantages to converting CO2 into LCLF rather than LCNG, as follows: 1. The energy densities of diesel fuel and gasoline fuel are approximately 38.6 and 34.2 MJ / liter, respectively. These energy densities are much higher than those of CH4 (9.0 MJ / liter at 250 bar), H2 (5.3 MJ / liter at 690 bar), dimethyl ether (21.2 MJ / liter at 5 bar), methanol (15.6 MJ / liter), lithium-ion battery (1.76 MJ / liter), and lead-acid battery (0.56 MJ / liter) (Wikipedia, 2019). 2. To produce CH4 from CO2, about four times as much H2 is required as for producing liquid fuel from CO2. 3. Diesel fuel and gasoline fuel can be stored at or near atmospheric pressure, as compared to 200 - 400 bar for CH4 and 340 - 690 bar for H2. 4. The global distribution infrastructure for liquid fuels is extensive and can be easily transported to almost all locations on Earth. 5. It is difficult to produce synthetic CH4 that meets natural gas pipeline standards (Zhou et al, 2010; Melaina et al, 2013; Zaki et al, 2016; SoCalGas, 2019).

[0007] As a result, there is growing interest in the development of efficient and economic technologies for converting CO2 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).

[0008] This improved catalyst and process offer interesting possibilities, such as using primary energy from renewable carbon-free resources (such as electricity obtained from sunlight, wind, wave / tidal power, hydropower, or nuclear power) to convert CO2 together with hydrogen into high-density vehicle fuels compatible with the current transportation infrastructure. Additionally, this next-generation technology is thought to contribute to the expansion of more efficient power plants that produce little or no emissions, such as oxy-fuel plants. An oxy-fuel plant refers to a power plant that generates electricity from natural gas and oxygen, and its emissions are a nearly pure CO2 stream (rather than the dilute CO2 streams produced by conventional power plants).

[0009] Its true attraction lies in the fact that this approach offers the prospect of significantly reducing carbon emissions from the transportation system without the need for a paradigm shift in the infrastructure required for electrifying the vehicle fleet or transitioning to a hydrogen economy (Pearson et al. 2009).

[0010] Most of the prior art in the development of liquid fuels from CO2 has focused on the production of gasoline and diesel fuels as "drop-in" fuels. Dimethyl ether (DME) is a potential low-emission fuel for diesel engines, but it is not a "drop-in" fuel because it requires modification of the diesel engine and its fuel infrastructure has not been developed (Semelsberger, 2006).

[0011] Methanol has long been proposed as a potential liquid fuel for engines, but it has not been accepted as a fuel because it is highly flammable, toxic, and its combustion releases toxic and carcinogenic formaldehyde. Instead, methanol is mainly used as an intermediate chemical product for manufacturing liquid fuels or chemicals.

[0012] The production of "drop-in" liquid fuels from a mixture of H2 and CO2 typically requires the following processes. 1. Conversion of the H2 / CO2 mixture to synthesis gas 2. Conversion of synthesis gas to fuel meeting ASTM and other fuel specifications. Typically, this process requires two or more major conversion processes.

[0013] For the process of converting CO2 to liquid fuel to be commercially viable, it is important that the manufactured catalysts for converting the H2 and CO2 mixture to synthesis gas and then converting this synthesis gas to liquid fuel meet one or more of the quality and performance specifications described in Table 1 below.

[0014] Table 1 - Quality and performance specifications for catalytic conversion of H2 / CO2 mixture to synthesis gas · The catalyst contains low-cost components (contains no [or almost no] rare metals). · The catalyst can be economically manufactured in quantities of several tons. · The catalyst is robust (e.g., Rockwell hardness greater than Mohs 03 - 04). · The catalyst is chemically and physically stable up to about 2,100°F (1,149℃) until. · The catalyst can be easily loaded into a catalytic reactor (e.g., tubular or packed bed reactor). · The pressure drop from the top to the bottom of the catalytic reactor is acceptable. · Activation of the catalyst (e.g., reduction by H2) can be carried out on-site. · The conversion efficiency of CO2 to CO is greater than about 50% per pass at a space velocity greater than about 10,000 hr -1 but preferably greater than about 65% per pass. · The CO production selectivity is greater than about 70% but preferably greater than about 85%. · Does not coke (e.g., does not form carbon deposits). · The catalyst has a long life and does not require systematic reactivation (reduction).

[0015] Two approaches have been described in the prior art for converting CO2 into syngas. The first and most widely described approach employs a catalytic process for converting a mixture of CO2 and H2 into syngas. This method is typically referred to as "CO2 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 converting a mixture of CO2 and H2O into syngas (Wang et al, 2016).

[0016] Catalytic conversion of H2 / CO2 mixtures to syngas - Many patent applications, patents, and publications describe the development of catalysts for converting mixtures of H2 and CO2 into syngas. This prior art is evaluated with respect to the quality and performance specifications outlined in Table 1.

[0017] Iwanani et al (1993) developed a catalyst containing transition metals with rare metals (Ni, Fe, Ru, Rh, Pt, W, Pd, Mo, etc.) on zinc oxide to reduce a mixture of CO2 and H2 to CO. They achieved a relatively low maximum conversion rate of 37%, and did not significantly lose catalytic activity after 50 hours, although tests for longer periods were not conducted.

[0018] Chen et al (2015) reported the synthesis of an intermetallic nanocatalyst (InNi3CO 0.5 ) and demonstrated that this catalyst is active and selective for the RWGS reaction. This catalyst was produced by carburizing an In-Ni intermetallic base to create dual active sites on the catalyst surface. They achieved a moderate CO2 conversion rate of 52 - 53% at 600 °C and a gas hourly space velocity of 300,000 ml / g(cat) / hr for 150 hours. Long-term tests of this catalyst were not conducted.

[0019] Bahmanpour et al (2019) discovered a Cu-Al spinel formed in situ as an active catalyst for hydrogenating CO2 with H2 to obtain syngas. They used coprecipitation and subsequent hydrogen treatment to form Cu-Al spinel in different weight ratios. A ratio of Cu:Al = 4:1 was found to be efficient for CO2 conversion. They maintained a relatively low CO2 conversion rate of 47% at a relatively high space velocity at 600 °C and observed no detectable deactivation even after 40 hours of testing. However, copper-containing catalysts tend to deactivate due to sintering at high temperatures. In addition, to evaluate potential commercial viability, it is necessary to test catalyst formulation candidates for over 1,000 hours.

[0020] CO 2 / H 2 Electrochemical conversion of a CO mixture to synthesis gas -The electrochemical conversion of CO2 is an active research area (Zhu, 2019). Much of this research and development effort has focused on improving fuel cells (Sunfire, 2016), as well as PEM and alkaline electrolysis systems (Messias et al, 2019).

[0021] PEM and alkaline electrolysis -Opus 12 developed a PEM electrolyzer that converts a mixture of CO2 and H2O into a mixture of 16 C1-C3 oxygenated hydrocarbons (alcohols, ketones, aldehydes, and acids) (Kuhl et al, US Patent Application No. 2017 / 0321333). A costly purification process is required to separate this complex mixture into specific compounds. Even if the separation is successful, the only suitable product that can be used as fuel (e.g., mixed with gasoline) is ethanol.

[0022] Fuel cell- Sunfire has developed a process based on the high-temperature co-electrolysis of CO₂ and H₂O that uses 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 subsequently converted to long-chain hydrocarbons using the conventional Fischer-Tropsch process. This wax is converted to gasoline and diesel fuel using a two-step catalytic purification process. Thus, three steps are required to produce Sunfire's "drop-in" fuel, and this process requires complex wax upgrading or purification.

[0023] With current technology, four main processes are possible to convert CO₂ into "drop-in" liquid fuels:

[0024] One-step process 1. Convert CO₂ directly into liquid fuel using a catalytic or electrochemical process.

[0025] Two-step process 1. Convert CO₂ into syngas using a catalytic or electrochemical process. 2. Convert the syngas directly into liquid fuel using a second catalyst.

[0026] Two-step process 1. Convert CO₂ into a primary chemical intermediate using a catalyst or electrochemical process. 2. Convert the chemical intermediate directly into liquid fuel using a second catalyst.

[0027] Three-step process 1. Convert CO₂ into syngas using a catalyst or electrochemical process. 2. Convert the syngas into a primary chemical intermediate (e.g., wax, methanol, etc.). 3. Convert the purified intermediate directly into liquid fuel.

[0028] Four-step process 1. Convert CO2 into syngas using a catalyst or an electrochemical process. 2. Convert the syngas into primary chemical intermediates (e.g., wax, methanol, etc.). 3. Convert the purified intermediate into liquid fuel using two major chemical processes.

[0029] Four-step process 1. Convert CO2 into syngas using a catalyst or an electrochemical process. 2. Convert the syngas into a mixture of organic intermediates (e.g., wax, methanol, etc.). 3. Employ a separation process to produce the desired purified intermediate. 4. Convert the purified intermediate into liquid fuel.

[0030] For these four processes to be commercially viable, it is essential that the catalysts and fuel products manufactured for the production of liquid fuels meet some of the quality and performance specifications outlined in Table 2.

[0031] Table 2 - Quality and Performance Specifications for the Catalytic Conversion of Syngas to Liquid Fuel 1. The catalyst contains low-cost components (contains no [or almost no] rare metals). 2. The catalyst can be economically manufactured in quantities of several tons. 3. The catalyst is robust (e.g., has a Rockwell hardness greater than Mohr 03 - 04). 4. The catalyst is chemically and physically stable up to approximately 1,800°F (982℃) 5. The catalyst can be easily loaded into a catalytic reactor (e.g., a tubular or packed-bed reactor). 6. The pressure drop from the top to the bottom of the catalytic reactor is acceptable. 7. The activation of the catalyst (e.g., reduction by H2) can be carried out on-site. ​8. The conversion efficiency from CO2 to liquid fuel is greater than about 35% per pass, preferably greater than about 55% per pass. 9. The catalyst has a long lifespan and does not require systematic reactivation (reduction). 10. The cost of the liquid fuel is comparable to that of petroleum-derived fuels. 11. The liquid fuel conforms to the fuel standards issued by ASTM and other fuel standardization agencies.

[0032] Summarize the prior art regarding one-step, two-step, three-step, and four-step processes and evaluate with respect to the quality and performance specifications outlined in Tables #1 and #2.

[0033] One-step process - Most of the effort to convert CO2 to liquid hydrocarbon fuels in a single reactor has been to develop a catalyst that first produces CO from CO2 by hydrogenation. The CO then reacts with H2 over the same catalyst to form liquid fuels by a mechanism based on the conventional Fischer-Tropsch reaction. One of the problems associated with this Fischer-Tropsch process using CO2 is the low concentration of CO present during the reaction. This limits chain growth, so the product distribution typically has a high proportion of light hydrocarbons that are not suitable as liquid fuels. To date, most research has focused on the use of iron-based catalysts that are active in the reverse water-gas shift reaction and Fischer-Tropsch chemistry (National Academy of Sciences, 2019).

[0034] Landau et al (Australian Patent Application No. 2015 / 203898) describe 20% Fe2O3 on an iron spinel catalyst. The catalyst particle sizes varied from 100 μm to 3.0 mm. This catalyst was tested using syngas with a H2 / CO2 ratio of 2.0 - 3.0 / 1.0, a very low space velocity of about 2.0 h -1 , a temperature of 325 - 350 °C, and a pressure of 20 - 40 atmospheres. The maximum conversion rate of CO2 was 36%. The product selectivities were CO (13%), CH4 (9%), C2-C5 (44%), and C6-C 27It was HC (25%). The olefin / paraffin ratio in C6+ hydrocarbons was approximately 5 / 1. This catalyst does not produce "drop-in" fuels that meet ASTM specifications and does not meet the quality and performance specifications of the above catalysts.

[0035] Wang et al. (2013) described an Fe / ZrO2 catalyst for catalyzing the hydrogenation of CO2 to mainly produce CH4 and C2-C4 paraffins. The selectivity for the production of liquid-phase hydrocarbons was very low.

[0036] Wei et al. (2018) described an iron-based catalyst for the one-step conversion of CO2 to isoparaffins. The conversion efficiency of CO2 was only 26%, and the selectivity for CO was approximately 17%. When coke (carbon) deposits inside the micropores of the catalyst, the isoparaffin yield decreases rapidly with time.

[0037] Williamson et al. (2019) described the performance of a one-step catalyst containing iron nanoparticles deposited on carbon nanotubes. This catalyst was calcined in air at 400 °C for 1 hour or at 570 °C for 40 minutes and activated with H2 at 400 °C for 3 hours. This catalyst was tested in a laboratory reactor at 370 °C and 221 psi using a 3.0 / 1.0 H2 / CO2 mixture. The average CO2 conversion rate was 54%, and the selectivities for CO and hydrocarbons were 30% and 70% respectively. The average composition of the hydrocarbon products was CH4 43%, C2-C4 55% and C5+ hydrocarbons 2.0%.

[0038] Pan et al. (2007) was about a very low 13 hr -1Describes the use of a Rh catalyst supported on carbon nanotubes in a tubular reactor for producing ethanol from a mixture of CO2 and H2 at a space velocity. In addition to ethanol, this 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 suitable for scaling up to commercial scale because of the large pressure drop in the catalytic reactor, low space velocity, and production of a complex mixture of oxygenated hydrocarbons.

[0039] Two-step process - Shulenberger et al (U.S. Patent No. 8,198,338) describe a process for converting CO2 to gasoline. H2 and CO2 (molar ratio 2.0 / 1.0) were converted to methanol in a catalytic reactor operating at about 50 bar pressure and 500 °C using a Cu / ZnO / Al2O3 catalyst. Because the operating pressure was low, the selectivity for methanol production was only about 10%. The methanol produced from the first contact process was fed to another catalytic reactor containing a ZSM-5 catalyst and operated at about 4 bar pressure and 390 °C to convert the methanol to gasoline. The conversion efficiency of the two-step process, as well as 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 gasoline production was estimated to be less than 10%.

[0040] Three-step process - Sunfire carried out the electrolytic conversion of CO2 and H2O using a solid oxide electrolysis cell (SOEC), thereby producing syngas (Zhu, 2019). The syngas was then converted to long-chain hydrocarbons using the conventional Fischer-Tropsch method. These waxes were converted to gasoline and diesel fuel using a two-step catalytic purification process. Therefore, three steps were required for the production of Sunfire's "drop-in" fuels.

[0041] Four-step process- Several four-step processes are described in the current technology. One approach is to use a one-step process to produce chemical intermediates such as methanol from an H2 / CO2 mixture, followed by a three-step process to convert the methanol to gasoline. Another approach is to produce syngas from an H2 / CO2 mixture, followed by Fischer-Tropsch conversion of the syngas to wax, and then a two-step conversion of the wax to liquid fuel.

[0042] In Kothandaraman et al (2016), polyamine (PEMA) in tetrahydrofuran (THF) was used to capture CO2 thereby. Although this amine has excellent CO2 capture efficiency, amines are known to deactivate catalysts. The captured CO2 was converted to methanol in solution using a ruthenium PNP pincer-type catalyst. This catalyst is a complex of ruthenium with an organic ligand surrounding the ruthenium. This process was tested in the laboratory using an H2 / CO2 reactant ratio of 3.0 / 1.0, a pressure of 75 atmospheres, and a temperature of 145 °C. The carbon conversion rate from CO2 to CH3OH was 65%.

[0043] A plant to demonstrate this process was commissioned in 2012 at Svartsengi, Iceland. H2 is produced electrochemically from H2O using 5.0 megawatts of geothermal power. CO2 is captured from the Svartsengi power plant in Iceland. The production volume of methanol is approximately 50,000 liters / year.

[0044] Gasoline can be produced from this methanol using a three - stage Exxon - Mobil patented process (Jafari, 2018). In this process, three catalytic reactors are used: Catalytic conversion #1: from methanol to dimethyl ether. Catalytic conversion #2: from dimethyl ether to C2 - C5 olefins. Catalytic conversion #3: from C2 - C5 olefins to gasoline. MTG gasoline typically contains 53% paraffin, 12% olefin, 9% naphthene, 26% aromatic, 0.3% benzene, and is sulfur - free. The octane number (RON + MON) / 2 is 87 and the RVP (psi) is 9.0 (62.1 kPa) is.

[0045] In conclusion, no prior art has been identified that can produce “drop - in” liquid fuels from a CO2 / H2 mixture in two main steps and meet the performance and quality specifications summarized in Tables 1 and 2.

[0046] Compared with other catalysts developed for this application, the improved catalyst described in this document utilizes only one transition metal, Ni, while all other CO2 hydrogenation catalysts employ two or more transition metals (Okado, US Patent No. 6,423,665; Choudhary, US Patent No. 7,432,222; Millar, International Publication No. 2000 / 016899). Some other prior - art formulations require the use of expensive metals (e.g., Pt, Pd, Rh, Ru, and Ir) (Okado, US Patent No. 6,409,940, and Green, US Patent No. 5,431,855).

[0047] Exhaust gas conversion - One - stage, two - stage, three - stage, and four - stage processes typically produce exhaust gases composed of C1 - C5 hydrocarbons and CO2, as well as unconverted H2 and CO. This exhaust gas needs to be used as energy in a commercial - scale plant or converted into additional syngas.

[0048] The main process for converting exhaust gas into synthesis gas is by the steam methane reforming (SMR) process. However, steam reforming has several drawbacks. This steam reforming is a very endothermic reaction and requires excess steam to prevent or delay deactivation due to carbon deposition. As a result, high energy is required for SMR, and consequently, the production cost of this additional synthesis gas becomes high. In addition, the SMR process produces CO2 from the combustion of fuel gas and thereby burns the burner within the SMR.

[0049] Partial oxidation (POX) of exhaust gas to synthesis gas has several advantages over SMR. Since the oxidation of hydrocarbons to synthesis gas mixtures is exothermic, this process is much more energy efficient than both the steam reforming process and the dry reforming process (Gaffney et al, U.S. Patent No. 6,402,989).

[0050] However, POX has several potential drawbacks as shown below: 1. Relatively pure oxygen is required and its source is usually by cryogenic separation from air. 2. The POX process is very exothermic and therefore there is a possibility of catalyst hot spots, which can damage the catalyst or cause thermal runaway.

[0051] Autothermal reforming (ATR) of exhaust gas to synthesis gas is another process that can be used for the conversion of exhaust gas. Partial oxidation occurs at the inlet of the reactor, thereby providing 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)).

[0052] Cobalt-nickel catalysts on alumina have been found to exhibit excellent performance for the ATR of methane in terms of activity, stability, and synergy when compared to other catalysts. However, a mixture of CH4, CO2, and O2 is about 1,300°F(704℃) and 15 psi (103 kPa) When reformed at, some carbon formation is observed (Foo (2012) and Zhang (2007)). SUMMARY OF THE INVENTION

[0053] In one aspect, the present invention is a method for converting carbon dioxide into a liquid fuel, 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, thereby producing synthesis gas, wherein the first catalyst is a solid solution catalyst formed from nickel and magnesium, ideally containing Ni2Mg; b) introducing the synthesis gas into a second catalytic reactor in the catalytic conversion system, thereby producing exhaust gas, water and a liquid fuel, wherein the second catalyst comprises about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum or rhenium, based on 100 parts by weight of a support selected from the group consisting of silica, alumina and combinations thereof, thereby producing a liquid fuel, exhaust gas and water; c) separating the liquid fuel, exhaust gas and water from each other, thereby producing a liquid fuel; and providing a method.

[0054] In another aspect, the present invention is a catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, ruthenium, lanthanum, platinum or rhenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of a silica support.

[0055] In another aspect, the present invention is a method for producing a liquid fuel, comprising: a) separating oxygen from the atmosphere using a cryogenic air separator; b) mixing the oxygen with natural gas at high pressure and high temperature in the presence of heated supercritical carbon dioxide, thereby combusting the natural gas to produce a combustion gas containing carbon dioxide, water and heat; c) passing the combustion gas through a gas turbine generator to generate electricity for at least two purposes, the at least two purposes being distribution to an electrical grid and use in the liquid fuel production process, and discharging the combustion gas from the gas turbine generator; d) further passing the combustion gas through a heat exchanger, the heat exchanger reducing the temperature of the combustion gas; e) removing water from the combustion gas, thereby providing carbon dioxide; f) introducing a portion of the carbon dioxide, either with hydrogen or a mixture of a portion of the carbon dioxide, hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, the first catalyst being a solid solution catalyst of nickel and magnesium, preferably containing Ni2Mg, and compressing the remaining carbon dioxide while heating it to provide supercritical carbon dioxide; g) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce exhaust gas, water and liquid fuel, the second catalyst comprising about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum or rhenium, per 100 parts by weight of a support selected from the group consisting of silica, alumina and combinations thereof, thereby producing liquid fuel, exhaust gas and water; h) separating the liquid fuel, exhaust gas and water from each other to produce the liquid fuel. Provided is a method including

[0056] In another aspect, there is provided a liquid fuel production plant which can produce at least 400 barrels of drop-in synthetic liquid fuel per day while producing very little CO2 and having an electricity consumption of less than 80 MW. The plant a) a cryogenic air separator for separating oxygen from the atmosphere, the cryogenic air separator being connected to a combustion system which uses the oxygen to burn natural gas to produce carbon dioxide and water; b) a gas turbine generator connected to the combustion system, which allows combustion products containing gaseous carbon dioxide and water to pass through the gas turbine generator to enable the production of electricity; c) a heat exchanger connected to the gas turbine generator, which allows the gaseous carbon dioxide and water exiting the gas turbine to be introduced into the heat exchanger, and the heat exchanger cools the gaseous carbon dioxide and water; d) a cooler and mist separator connected to the heat exchanger, which allows the cooled gas from the heat exchanger to flow into the cooler and mist separator, thereby removing water from the gas stream to produce carbon dioxide; e) a first catalytic reactor connected to the cooler and mist separator, which allows the carbon dioxide to be introduced into the first catalytic reactor, the first catalyst being a solid solution catalyst of nickel and magnesium, preferably containing Ni2Mg, and the first catalytic reactor being capable of producing synthesis gas; f) A second catalytic reactor connected to the first catalytic reactor, whereby synthesis gas flows from the first catalytic reactor to the second catalytic reactor, the second catalytic reactor containing a second catalyst, the second catalyst comprising from about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper, and zinc, and from about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, per 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof, the second catalytic reactor being capable of producing liquid fuel from the synthesis gas, the second catalytic reactor A liquid fuel production plant is provided which includes the same.

Brief Description of the Drawings

[0057]

Figure 1

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Figure 3

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Figure 5

Embodiments for Carrying Out the Invention

[0058] The present invention relates to an improved catalyst and process for efficiently and economically converting a mixture of CO2 and H2 into liquid fuels in two steps.

[0059] Figure 1 illustrates the process flow diagram of the improved catalyst and method described herein for the direct production of liquid fuels from CO2 and renewable H2. Further, Figure 1 illustrates an integrated catalyst converter and method for producing renewable liquid fuels.

[0060] Electrolysis 101 is used to generate H2. The power for producing H2 can be generated from renewable and / or low-carbon sources such as, but not limited to, wind, solar, geothermal, hydro, ocean current, biomass, flare gas, nuclear power, etc. Other possible sources include low-cost (off-peak) power from conventional fossil fuel plants or efficient power produced from oxy-fuel plants.

[0061] The captured CO2 102 can be obtained from, but not limited to, fermentation processes, cement plants, conventional power plants, oxy-fuel power plants, atmospheric CO2 capture systems, natural gas wellheads, secondary oil recovery processes, and other CO2 sources.

[0062] The H2 from process 101, the CO2 from process 102, the syngas and heat (Q) from process 110 are mixed 103 in appropriate proportions, heated, and fed into the catalytic conversion system 104. Two innovative catalysts, catalyst #1 105 and catalyst #2 107, are incorporated into the catalytic conversion system 104.

[0063] Catalyst #1 105 is a high surface area nickel and magnesium solid solution catalyst. Ideally, the catalyst contains Ni2Mg and is a solid solution catalyst for efficiently converting the CO2 and H2 mixture described herein into syngas. This catalyst represents a significant improvement over the low surface area solid solution catalysts described in Schuetzle et al. U.S. Patent No. 9,611,145 and Canadian Patents Nos. 2,936,903 and 2,993,671. The catalyst species described in this prior art contained primarily Ni in the lowest possible valence state before being reduced (activated) by H2 + compounds (e.g., Ni2O and Ni2MgO2). Ni2O is called nickel suboxide and has a tetragonal crystal structure (Wagner et al. U.S. Patent No. 4,990,491).

[0064] The reduction of Ni2MgO2 by H2 produces the active CO2 reforming catalyst Ni2Mg, and the reduction of Ni2O at high temperature by H2 in the presence of MgO produces primarily elemental Ni. Since the burning of H2 is not 100% efficient, some Ni and Ni2MgO2 still remain. The improvements described herein include a manufacturing process that produces a robust catalyst that is primarily a catalyst containing Ni2Mg and has a surface area approximately 10 times larger than the catalysts described in the prior art.

[0065] Catalyst #2 107 is a catalyst developed for the direct production of liquid fuels from syngas, as described in Schuetzle et al. U.S. Patent Nos. 8,394,862, 9,090,831 and 9,631,147. Catalyst #1 105 and catalyst #2 107 were developed to operate at approximately the same pressures in the range of about 50 - 350 psi (about 345 - 2,413 kPa) .

[0066] Since Catalyst #1 operates at a higher temperature than Catalyst #1, a heat exchanger 106 is incorporated into the catalytic conversion system 104 to lower the temperature of the gas to the operating temperature of Catalyst #2 107. The products from the catalytic conversion process 104 are separated by a product separator 108 into exhaust gas 109, water 111 and renewable liquid fuel 113.

[0067] Part of the exhaust gas 109 is returned to the catalytic conversion process 104 and reused until the CO in the syngas reaches the desired conversion efficiency. The remaining exhaust gas 109 is combusted 110 (autothermal reforming (ATR)) with the oxygen produced from the electrolysis system 101. The products from the ATR process 110 are syngas and heat. This syngas is mixed with other gases at 103, and the heat from this 110 is used to assist in heating the gas mixing / heating system 103. Additional heat is added to the gas mixing system 103 to bring these gases to the operating temperature of the catalyst #1 105.

[0068] Water (generally referred to as catalytic reaction water) 111 can be used for intermediate water applications 112 or purified for the electrolysis process 101 and / or other applications. The renewable liquid fuel 113 can be used directly (neat) in the off-road diesel engine 114, mixed with petroleum-derived diesel fuel 115, or distilled 116 to produce higher-grade fuel products (e.g., #1 diesel, #2 diesel, #3 diesel, and jet fuel) 117.

[0069] Figure 2 summarizes the possible reactions that can occur when a mixture of CO2 and H2 is catalytically converted to CO. The catalyst described in this improved technology is developed to mainly produce CO from a mixture of CO2 and H2 by reaction 201 and, when a mixture of CO2 and C1-C8 hydrocarbons is present (when CO2 is present), through reactions 203 and 204.

[0070] This improved catalyst and process mainly produce CO from CO2 and H2 (reaction 201) or mainly produce CO from CO2 and hydrocarbons (reactions 203 and 204). Since these reactions are endothermic, heat needs to be added for the conversion to occur. As shown in Figure 1, the first catalyst in the catalytic reactor is used to efficiently convert a mixture of CO2 and H2 to CO. This improved CO2 reforming catalyst 105 operates under low-pressure conditions (<350 psi(< 2,413 kPa) ) produces mainly CO with a selectivity greater than about 90%.

[0071] Figure 3 shows the effect of operating temperature on the production of CO from CO2 by this improved CO2 reforming catalyst at 50 psi (345 kPa) . The conversion of CO2 increases exponentially at temperatures of about 750 °F - 1,300°F (399℃~704℃) . The conversion of CO2 then levels off at about 1,300 °F - 1,700°F (704℃~927℃) and follows a power fit (y = 0.45x - 309). The CO2 conversion efficiency is about 75%, and the CO production selectivity at 1,700°F (927℃) is about 100%.

[0072] Table 3 summarizes the selectivity of CO and CH4 production from CO2 at about 1,600°F (871℃) and 50 psi (345 kPa) . The CO2 conversion efficiency is about 72%, and the selectivity of CO is about 100% at this time. Under these conditions, other products such as CH4 formation (reactions 202 and 205) and carbon (reactions 209, 210, 211, 212 and 213) are not formed. Since the concentration of H2O in the CO2 / H2 stream is very low, reactions 206, 207 and 208 are very few.

[0073]

Table 3

[0074] Table 4 summarizes the effect of pressure on the conversion of CO2 to CO at 1,600°F (871℃) . As the pressure increases from 50 psi (345 kPa) to 300 psi (2,068 kPa) , the selectivity of CO decreases from about 100% to 89%, while the selectivity of CH4 increases from 0% to 11%. This change in pressure has no effect on the CO2 conversion efficiency.

[0075]

Table 4

[0076] The second catalyst 107 at the rear end of the converter (Figure 1) utilizes the Greyrock direct fuel production catalyst described in Schuetzle et al. U.S. Patents Nos. 8,394,862 and 9,909,071 in the past, and this catalyst is improved to operate efficiently down to a low pressure of about 50 psi in this process. (about 345 kPa)

[0077] The composition of this improved catalyst 107 contains about 2 to about 25 parts by weight of cobalt and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, based on 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof. This catalyst is commercially produced using a fixed calcination furnace such that the aspect ratio (ratio of length to width) of the catalyst particles, surface area, pore size distribution beneath and on the surface, pore volume, and crystallinity of the catalyst are maintained within about 5% of the specifications.

[0078] Figure 4 illustrates the relationship between the operating pressure of catalyst #2 107 and the CO conversion efficiency at 450°F. (232℃) It was found that the % change in the CO conversion rate follows the relationship given in Equation 2. Here, P1 and P2 are the pressures being compared. % change in CO conversion rate = (P1 / P2) 0.5 Equation (2) Since the first catalyst operates at a higher temperature than the second catalyst, a heat exchanger (Figure 1 - 106) is incorporated between these catalysts, thereby reducing the temperature of the second catalyst to its ideal operating level.

[0079] The most important advantage of this process is that catalysts #1 and #2 can be operated efficiently in parallel at the same pressure, thereby eliminating the need for compression between the two catalytic reactors.

[0080] Table #5 provides the relationship between the temperature of Catalyst #2 for the conversion of CO2 in the syngas produced from Catalyst #1. Thus, Catalyst #2 converts a portion of the CO2 that was not converted by Catalyst #1.

Table 5

[0081] 1,600°F (871℃) and 150 psi (1,034 kPa) Since the conversion of CO2 at 1,600°F and 150 psi is 72% efficient (Table 3), the resulting syngas contains approximately 28% CO2. Thus, when Catalyst #2 is operated at 450°F (232℃) approximately 25% of the syngas flowing into Catalyst #2 is converted to CO2, resulting in an exhaust gas containing 34.1% H2, 17.1% CO, 23.1% CH4, and 25.6% CO2.

[0082] Table 6 summarizes the products produced under two different pressure operating conditions. When an H2 / CO2 mixture (2.2 / 1.0) is fed into an improved CO2 reforming catalyst operated at 300 psi (2,068 kPa) and 1,600°F (871℃) syngas with an H2 / CO ratio of approximately 2.0 - 2.3 / 1.0 is produced.

[0083] When this syngas is fed into a direct fuel production catalyst operated at 415°F (213℃) and 300 psi (2,068 kPa) liquid fuel (C5 - C 23 hydrocarbons) is produced with a single - pass selectivity of 47.5%. The by - products include gaseous C1 - C4 hydrocarbons, solid - phase C 24 + hydrocarbons, and unreacted CO2, and their selectivities are 21.2%, 2.5%, and 25.8% respectively.

Table 6

[0084] The CO2 used as an input to this process can be obtained from many different sources, including the atmosphere, fermentation processes, cement plants, conventional power plants, oxy-fuel processes, biogas, gases recovered from secondary oil production processes, and the like.

[0085] CO2-containing C2-C6 hydrocarbons can also be used as process inputs because they are converted to liquid fuels or methane. Such streams include natural gas condensates, gases from refinery processes, and other gas streams containing CO2 and light hydrocarbons.

[0086] The integrated process described above requires an input of carbon dioxide. In one embodiment, the carbon dioxide is supplied from the separation of carbon dioxide in a flue gas stream using an alkylamine. The alkylamines used in this process can include monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, aminoethoxyethanol, or combinations thereof. In another embodiment, the carbon dioxide is already present within the natural gas feedstock.

[0087] The process for manufacturing the first catalyst is important in that it produces a catalyst that forms a binary metal crystalline phase, which is a unique solid solution phase where no separation of the metal phase occurs. This unique chemical structure improves the resistance to coking compared to conventional metal-supported reforming catalysts. This also improves the resistance to synthesis gas poisons such as sulfur and ammonia. Furthermore, this catalyst has a higher catalytic activity at a lower surface area compared to a single metal-separated catalyst phase such as Ni on alumina. This catalyst does not require an alkali promotion necessary to suppress carbon deposition typically seen in the feed gases described herein. This catalyst can also be used in various dry feeds, steam feeds, combinations of dry feed / steam feeds, and ternary reformed feeds. With this catalyst, mixtures of higher hydrocarbon feedstocks are also achievable.

[0088] The production of an improved CO2 hydrogenation catalyst to achieve an effective and economic commercial solid solution catalyst may include some or all of the following steps: a. Synthesis of a high surface area (>50 m 2 / g) metal spinel that may be composed of Co-alumina spinel, Fe-alumina spinel, Mg-alumina spinel, Mn-alumina spinel, Ca-alumina spinel, Ba-alumina spinel, Cu-alumina spinel, or Zn-alumina spinel. b. Modification of the spinel by impregnating it with up to 20 wt% of additional Fe, Mg, Mn, Ca, Ba, Cu, or Zn that is not chemically bonded to one or more of the spinels listed above. c. Impregnation of the metal-coated spinel with a solution containing a mixture of a water-soluble nickel salt and a rare earth metal salt (e.g., nitrate or acetate). d. Calcination of the metal-coated spinel at a temperature up to 2,100°F (1,149℃) e. Optional additional impregnation and calcination. This produces an impregnated spinel containing 2-20 wt% Ni and 0.1-5.0 wt% rare earth metal.

[0089]

[0090]

[0091] Several methods have been developed for collecting CO2 from fermentation processes, conventional power plants, oxy-fuel power plants, cement plants, and CO2 / hydrocarbon streams from biogas sources, refineries, and secondary oil recovery processes (Schuetzle et al., 2010). ​​In power plants, typically, control devices for removing sulfur oxides and particulate matter are employed. To add a carbon capture system, a large amount of additional capital cost and an increase in parasitic power are required. As a result, when removal is carried out in a conventional power plant, the power cost may be 50% - 70% higher (IGCC, 2005). The costs of capturing CO2 emissions from coal-fired power plants and natural gas-fired power plants are on average $130 / ton and $95 / ton respectively (Metz et. al, 2005).

[0092] Oxy-fuel power plants have the potential to produce high-quality CO2 at low cost. NET Power is a leader in the development and deployment of these power plants (Allam et al, 2017). NET Power is developing and deploying a new power generation system that produces electricity from natural gas at a cost comparable to current technologies with a net energy efficiency of about 59% and zero emissions to the atmosphere.

[0093] The NET Power system is based on a new thermodynamic cycle called the Allam cycle (Allam et al, 2013). This system uses a high-pressure and resilient oxy-fuel supercritical CO2 cycle that incorporates emissions capture as part of the core power generation process. As a result, highly efficient power generation that essentially produces CO2 by-products is achieved without incurring additional costs to the system's performance. The CO2 produced from this oxy-fuel process is an ideal feedstock for the production of ultra-low carbon liquid fuels by this catalytic converter and method.

[0094] Fermentation processes are used to produce distillates, wine, beer, and ethanol fuels. As shown in Table 7, CO2 is a major component of the emissions from fermentation processes. The ethanol concentration is low, in the range of about 2,000 - 4,000 ppm. Since fermentation is an anaerobic process, typically O2 is not present. Small amounts of sulfur compounds such as H2S and SO2 may be present at low concentrations (Safriet, 1995).

Table 7

[0095] Due to the low concentration of pollutants, this effluent is an ideal CO2 source for the improved direct fuel production process described in the present invention. The low concentration of sulfur compounds can be easily removed using conventional adsorbents. The cost of the captured CO2 ranges from $5 / ton to about $35 / ton. The second catalyst in the catalytic reactor will convert most (>50 mol%) of the ethanol into liquid fuel.

[0096] The cement industry currently accounts for about 7% of the world's carbon dioxide (CO2) emissions and is the third largest industrial energy consumer. The production of cement involves the decomposition of limestone (calcium carbonate), which accounts for about two-thirds of the total CO2 emissions generated in the process, and the remaining CO2 emissions are due to fuel combustion. This industry accounts for the second largest proportion in the total direct industrial carbon dioxide (CO2) emissions, and the proportion is 27% (2.2 gigatons) of the annual carbon dioxide [GtCO2 / year] in 2014 (IEA, 2018).

[0097] The emissions from cement plants contain about 25% by volume of CO2. The current cost of amine (MEA)-based adsorption capture technology is about $90 / ton. When oxyfuel is used for heating, the cost is reduced to about $50 per ton of CO2 (Gardarsdottir et al., 2019). However, this cost can be much higher if significant changes to the cement plant are required. The CO2 captured from cement plants using amine capture or oxyfuel combustion is an ideal raw material for producing renewable fuels from this catalytic converter and method.

[0098] When CO2 is captured, it needs to be compressed to high pressure for storage in a large container or cooled to produce liquid CO2 for storage in an insulated container. Therefore, if the captured CO2 is directly converted into liquid fuel at the factory site, these costs can be reduced.

[0099] Several technologies have been developed to collect CO2 from the atmosphere (U.S. Patent No. 9,095,813). The challenge with these atmospheric collection processes is that the cost of CO2 collection is very high, currently over $400 - $600 per ton, but the cost may decrease as these technologies are commercialized.

[0100] There are several CO2 sources associated with significant levels of C1 - C6 hydrocarbons. Examples of such sources include mixtures of CO2 / light hydrocarbons from natural gas wellheads, emissions from secondary oil recovery using CO2, and biogas.

[0101] Injecting CO2 into oil reservoirs is a common method for secondary oil recovery. After CO2 injection, the recovered CO2 contains light hydrocarbons, which need to be separated before the CO2 is reinjected. U.S. Patent No. 9,159,105 describes a process for separating light hydrocarbons from CO2 using an air capture unit. This CO2 is reinjected into the well for additional oil recovery, and this light hydrocarbon is used as fuel for local applications.

[0102] Various embodiments Method 1. A method for converting carbon dioxide into a liquid fuel, comprising: a) Introducing a gas 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, wherein the first catalyst is a solid solution catalyst of nickel and magnesium, preferably containing Ni2Mg; b) introducing the syngas into a second catalytic reactor in the catalytic conversion system, thereby producing exhaust gas, water, and liquid fuel, wherein the second catalyst comprises from about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper, and zinc, and from about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, per 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof, thereby producing liquid fuel, exhaust gas, and water; c) separating the liquid fuel, exhaust gas, and water from each other, thereby producing liquid fuel; A method comprising the steps of.

[0103] 2. The method according to method 1 above, wherein the syngas is introduced into a heat exchanger to lower the temperature of the syngas before the syngas is introduced into the second catalytic reactor.

[0104] 3. The method according to method 1 above, wherein the carbon dioxide introduced into the first catalytic reactor is obtained from a source selected from the group consisting of an oxy-fuel power plant, an atmospheric CO2 capture system, a natural gas wellhead, and a secondary oil recovery process.

[0105] 4. The method according to method 1 above, wherein the hydrogen is produced using electrolysis, and the power for the electrolysis is generated from a renewable source or a low-carbon source selected from the group consisting of wind power, solar power, geothermal power, hydropower, ocean current, biomass, flare gas, nuclear power, off-peak power from a fossil fuel plant, and power produced by an oxy-fuel plant.

[0106] 5. The method according to method 1 above, wherein the exhaust gas is returned to the catalytic conversion system for reuse.

[0107] 6. The method according to method 1 above, wherein the water is used for non-potable water applications.

[0108] 7. The method according to method 1 above, wherein the second catalytic reactor is operated at a pressure of about 50 psi to about 400 psi (about 345 kPa - about 2,758 kPa) 、about 50 psi to about 300 psi (about 345 kPa - about 2,068 kPa) 、about 50 psi to about 250 psi (about 345 kPa - about 1,724 kPa) 、about 50 psi to about 200 psi (about 345 kPa - about 1,379 kPa) 、about 50 psi to about 150 psi (about 345 kPa - about 1,034 kPa) 、or about 50 psi to about 100 psi (about 345 kPa - about 689 kPa) of the method according to method 1 above.

[0109] 8. The method according to method 1 above, wherein the exhaust gas is partially combusted with oxygen from an electrolysis system used to generate hydrogen, thereby generating the synthesis gas and heat, and the synthesis gas is mixed with other gases introduced into the second catalytic reactor.

[0110] 9. The method according to method 1 above, wherein the liquid fuel is used as fuel for an off-road diesel engine without further treatment.

[0111] 10. The method according to method 1 above, wherein the liquid fuel is mixed with petroleum diesel fuel, thereby providing a blended fuel.

[0112] 11. The method according to method 1 above, wherein the liquid fuel is distilled, thereby providing #1 diesel, #2 diesel, #3 diesel or jet fuel.

[0113] 12. The first catalyst is a) synthesizing at least one metal spinel having a surface area greater than about 50 m 2 / g, wherein the metal spinel is selected from the group consisting of Co-alumina spinel, Fe-alumina spinel, Mg-alumina spinel, Mn-alumina spinel, Ca-alumina spinel, Ba-alumina spinel, Cu-alumina spinel and Zn-alumina spinel; b) Coating the spinel with from about 1 wt% to about 20 wt% of an additional chemical element that is not chemically bonded to the spinel, thereby providing a metal-coated spinel, wherein the additional chemical element is selected from the group consisting of Co, Fe, Mg, Mn, Ca, Ba, Cu, or Zn; c) Impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) Calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing from about 2 wt% to about 20 wt% nickel and from about 0.1 wt% to about 5.0 wt% rare earth metal; and A method according to Method 1, synthesized by a method comprising the above steps.

[0114] 13. The first catalyst is a) Synthesizing a Co-alumina spinel having a surface area greater than about 50 m 2 / g; b) Coating the spinel with from about 1 wt% to about 20 wt% Co, thereby providing a metal-coated spinel; c) Impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) Calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing from about 2 wt% to about 20 wt% nickel and from about 0.1 wt% to about 5.0 wt% rare earth metal; and A method according to Method 1, synthesized by a method comprising the above steps.

[0115] 14. The first catalyst is a) Synthesizing an Fe-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with from about 1 wt% to about 20 wt% of Fe, thereby providing a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing from about 2 wt% to about 20 wt% of nickel and from about 0.1 wt% to about 5.0 wt% of a rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0116] 15. The first catalyst is a) synthesizing Mg-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with from about 1 wt% to about 20 wt% of Mg, thereby providing a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing from about 2 wt% to about 20 wt% of nickel and from about 0.1 wt% to about 5.0 wt% of a rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0117] 16. The first catalyst is a) synthesizing Mn-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with about 1 wt% to about 20 wt% of Mn, thereby providing a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing about 2 wt% to about 20 wt% of nickel and about 0.1 wt% to about 5.0 wt% of a rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0118] 17. The first catalyst is a) synthesizing a Ca-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with about 1 wt% to about 20 wt% of Ca, thereby providing a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) thereby synthesizing the first catalyst, which is an impregnated spinel containing about 2 wt% to about 20 wt% of nickel and about 0.1 wt% to about 5.0 wt% of a rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0119] 18. The first catalyst is a) synthesizing a Ba-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with about 1 wt% to about 20 wt% of Ba, thereby providing a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) to thereby synthesize the first catalyst, which is an impregnated spinel containing about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0120] 19. The first catalyst is a) synthesizing a Cu-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with about 1 wt% to about 20 wt% Cu to thereby provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) to thereby synthesize the first catalyst, which is an impregnated spinel containing about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal; and The method according to Method 1, synthesized by a method comprising the above steps.

[0121] 20. The first catalyst is a) synthesizing a Zn-alumina spinel having a surface area greater than about 50 m 2 / g; b) coating the spinel with about 1 wt% to about 20 wt% Zn to thereby provide a metal-coated spinel; ​​c) impregnating the metal-coated spinel with a solution containing a water-soluble nickel salt and either a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2,100°F (1,149℃) to thereby synthesize the first catalyst, which is an impregnated spinel containing about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal; and The method according to Method 1, synthesized by a method comprising:

[0122] 21. The method according to Method 1, wherein the first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2 wt% to about 20 wt% nickel.

[0123] 22. The method according to Method 1, wherein the first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2 wt% to about 20 wt% nickel.

[0124] 23. The method according to Method 1, wherein the first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2 wt% to about 20 wt% nickel.

[0125] 24. The method according to Method 1, wherein the first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2 wt% to about 20 wt% nickel.

[0126] 25. The method according to Method 1, wherein the first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2An impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, wherein the first catalyst further contains about 2% to about 20% by weight of nickel, the method according to Method 1 above.

[0127] 26. The first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2% to about 20% by weight of nickel, the method according to Method 1 above.

[0128] 27. The first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2% to about 20% by weight of nickel, the method according to Method 1 above.

[0129] 28. The first catalyst is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 / g, and the first catalyst further contains about 2% to about 20% by weight of nickel, the method according to Method 1 above.

[0130] Catalyst 1. A catalyst for converting carbon dioxide into synthesis gas, which contains about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2% to about 20% by weight of nickel, based on 100 parts by weight of the alumina support, and is an impregnated and metal-coated spinel.

[0131] 2. A catalyst for converting carbon dioxide into synthesis gas, which contains about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2% to about 20% by weight of nickel, based on 100 parts by weight of the alumina support, and is an impregnated and metal-coated spinel.

[0132] 3. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of the alumina support.

[0133] 4. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of the alumina support.

[0134] 5. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of the alumina support.

[0135] 6. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of the silica support.

[0136] 7. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of the silica support.

[0137] 8. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel, which is an impregnated and metal-coated spinel.

[0138] 9. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel, which is an impregnated and metal-coated spinel.

[0139] 10. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of cobalt having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel, which is an impregnated and metal-coated spinel.

[0140] 11. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel, which is an impregnated and metal-coated spinel.

[0141] 12. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel, which is an impregnated and metal-coated spinel.

[0142] 13. A catalyst for converting carbon dioxide into synthesis gas, comprising about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m for every 100 parts by weight of an alumina support2 A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0143] 14. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0144] 15. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0145] 16. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0146] 17. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0147] 18. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0148] 19. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0149] 20. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of iron having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of iron having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0150] 21. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0151] 22. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0152] 23. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0153] 24. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0154] 25. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0155] 26. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0156] 27. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0157] 28. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel containing from about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, from about 0.1 to about 5 parts by weight of lanthanum, and from about 2 wt% to about 20 wt% of nickel.

[0158] 29. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains from about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing from about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, from about 0.1 to about 5 parts by weight of platinum, and from about 2 wt% to about 20 wt% of nickel.

[0159] 30. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains from about 2 to about 25 parts by weight of magnesium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing from about 2 to about 25 parts by weight of magnesium having a surface area greater than / g, from about 0.1 to about 5 parts by weight of rhenium, and from about 2 wt% to about 20 wt% of nickel.

[0160] 31. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains from about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing from about 2 to about 25 parts by weight of manganese having a surface area greater than / g, from about 0.1 to about 5 parts by weight of cerium, and from about 2 wt% to about 20 wt% of nickel.

[0161] 32. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains from about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing from about 2 to about 25 parts by weight of manganese having a surface area greater than / g, from about 0.1 to about 5 parts by weight of ruthenium, and from about 2 wt% to about 20 wt% of nickel.

[0162] 33. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains from about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2A catalyst, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0163] 34. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of an alumina support.

[0164] 35. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of an alumina support.

[0165] 36. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of a silica support.

[0166] 37. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of a silica support.

[0167] 38. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of manganese having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0168] 39. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of manganese having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0169] 40. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains about 2 to about 25 parts by weight of manganese having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of manganese having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0170] 41. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0171] 42. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0172] 43. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0173] 44. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0174] 45. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0175] 46. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0176] 47. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0177] 48. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0178] 49. A catalyst for converting carbon dioxide into synthesis gas, comprising, based on 100 parts by weight of a silica support, about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0179] 50. A catalyst for converting carbon dioxide into synthesis gas, comprising, based on 100 parts by weight of a silica support, about 2 to about 25 parts by weight of calcium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of calcium having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0180] 51. A catalyst for converting carbon dioxide into synthesis gas, comprising, based on 100 parts by weight of an alumina support, about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0181] 52. A catalyst for converting carbon dioxide into synthesis gas, comprising, based on 100 parts by weight of an alumina support, about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0182] 53. A catalyst for converting carbon dioxide into synthesis gas, comprising, based on 100 parts by weight of an alumina support, about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0183] 54. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0184] 55. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, contains about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0185] 56. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0186] 57. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0187] 58. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, contains about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0188] 59. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0189] 60. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of a silica support, there are about 2 to about 25 parts by weight of barium having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of barium having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0190] 61. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0191] 62. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0192] 63. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of an alumina support, there are about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0193] 64. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of an alumina support.

[0194] 65. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of an alumina support.

[0195] 66. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of a silica support.

[0196] 67. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel, based on 100 parts by weight of a silica support.

[0197] 68. A catalyst for converting carbon dioxide into synthesis gas, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel, containing about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0198] 69. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, containing about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0199] 70. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of copper having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, containing about 2 to about 25 parts by weight of copper having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0200] 71. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, containing about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0201] 72. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 A catalyst which is an impregnated and metal-coated spinel, containing about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0202] 73. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel containing about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2A catalyst which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0203] 74. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0204] 75. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of an alumina support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0205] 76. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of cerium, and about 2 wt% to about 20 wt% of nickel.

[0206] 77. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 / g, about 0.1 to about 5 parts by weight of ruthenium, and about 2 wt% to about 20 wt% of nickel.

[0207] 78. A catalyst for converting carbon dioxide into synthesis gas, which, based on 100 parts by weight of a silica support, is an impregnated and metal-coated spinel comprising about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2A catalyst, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of lanthanum, and about 2 wt% to about 20 wt% of nickel.

[0208] 79. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of the silica support, there is about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 A catalyst, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of platinum, and about 2 wt% to about 20 wt% of nickel.

[0209] 80. A catalyst for converting carbon dioxide into synthesis gas, wherein, based on 100 parts by weight of the silica support, there is about 2 to about 25 parts by weight of zinc having a surface area greater than about 50 m 2 A catalyst, which is an impregnated and metal-coated spinel, comprising about 2 to about 25 parts by weight of zinc having a surface area greater than / g, about 0.1 to about 5 parts by weight of rhenium, and about 2 wt% to about 20 wt% of nickel.

[0210] Reactor 1. A catalytic conversion system for converting carbon dioxide into liquid fuel, wherein the catalyst system includes a first catalytic reactor and a second catalytic reactor, the first catalytic reactor contains a first catalyst, the first catalyst is a solid solution catalyst of nickel and magnesium, ideally containing Ni2Mg, the second catalytic reactor contains a second catalyst, and the second catalyst contains about 2 to about 25 parts by weight of cobalt and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, based on 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof.

[0211] 2. The catalytic conversion system according to reactor 1 above, wherein the catalytic conversion system further includes a heat exchanger between the first catalytic reactor and the second catalytic reactor, and the gas flows from the first catalytic reactor to the heat exchanger and then to the second catalytic reactor.

[0212] 3. The catalyst conversion system further includes a gas mixing chamber connected to the first catalyst reactor, whereby gas can flow between the gas mixing chamber and the first catalyst reactor. The catalyst conversion system according to Reactor 1.

[0213] 4. The catalyst conversion system further includes an electrolysis system for generating hydrogen, the electrolysis system being connected to the gas mixing chamber, whereby hydrogen produced within the electrolysis system can flow into the gas mixing chamber. The catalyst conversion system according to Reactor 1.

[0214] 5. The catalyst conversion system further includes a system for capturing carbon dioxide, the system for capturing carbon dioxide being connected to the gas mixing chamber, whereby carbon dioxide obtained in the system for capturing carbon dioxide can flow into the gas mixing chamber. The catalyst conversion system according to Reactor 3.

[0215] 6. The catalyst conversion system further includes a system for capturing carbon dioxide, the system for capturing carbon dioxide being connected to the gas mixing chamber, whereby carbon dioxide obtained in the system for capturing carbon dioxide can flow into the gas mixing chamber. The catalyst conversion system according to Reactor 4.

[0216] Integrated conversion system 1. A method for producing liquid fuel, comprising: a) separating oxygen from the atmosphere using a cryogenic air separator; b) mixing the oxygen with natural gas at high pressure and high temperature in the presence of heated supercritical carbon dioxide, thereby burning the natural gas to produce a combustion gas containing carbon dioxide, water, and heat; c) Pass the combustion gas through a gas turbine generator to thereby generate electricity for at least two purposes, wherein the at least two purposes are power distribution to the power grid and use in the manufacturing process of the liquid fuel, and discharge the combustion gas from the gas turbine generator; d) Further pass the combustion gas through a heat exchanger, wherein the heat exchanger reduces the temperature of the combustion gas; e) Remove water from the combustion gas to thereby provide carbon dioxide; f) Introduce a part of the carbon dioxide, either together with hydrogen or a mixture of a part of the carbon dioxide, hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to thereby produce synthesis gas, wherein the first catalyst is a solid solution catalyst of nickel and magnesium, ideally containing Ni2Mg, and compress the remaining carbon dioxide while heating it to thereby provide supercritical carbon dioxide; g) Introduce the synthesis gas into a second catalytic reactor in a catalytic conversion system to thereby produce exhaust gas, water and liquid fuel, wherein the second catalyst contains about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum or rhenium per 100 parts by weight of a support selected from the group consisting of silica, alumina and combinations thereof, to thereby produce liquid fuel, exhaust gas and water; h) Separate the liquid fuel, exhaust gas and water from each other to thereby produce liquid fuel; A method comprising the above steps.

[0217] Production plant 1. A liquid fuel production plant, which can produce at least 400 barrels of drop-in synthetic liquid fuel per day while having a very low carbon dioxide emission and a power consumption of less than 80 MW, and the plant a) A cryogenic air separator for separating oxygen from the atmosphere, the cryogenic air separator being connected to a combustion system, the combustion system using the oxygen to burn natural gas to produce carbon dioxide and water, the cryogenic air separator, b) A gas turbine generator connected to the combustion system, thereby allowing combustion products containing gaseous carbon dioxide and water to pass through the gas turbine generator to generate electricity, the gas turbine generator, c) A heat exchanger connected to the gas turbine generator, thereby allowing the gaseous carbon dioxide and water exiting the gas turbine to be introduced into the heat exchanger, the heat exchanger cooling the gaseous carbon dioxide and water, the heat exchanger, d) A cooler and mist separator connected to the heat exchanger, thereby allowing the cooled gas from the heat exchanger to flow into the cooler and mist separator, thereby removing water from the gas stream to produce carbon dioxide, the cooler and mist separator, e) A first catalytic reactor connected to the cooler and mist separator, thereby allowing the carbon dioxide to be introduced into the first catalytic reactor, the first catalyst being a solid solution catalyst of nickel and magnesium, preferably containing Ni2Mg, the first catalytic reactor being capable of producing synthesis gas, the first catalytic reactor, f) A second catalytic reactor connected to the first catalytic reactor, thereby allowing the synthesis gas to flow from the first catalytic reactor to the second catalytic reactor, the second catalytic reactor containing a second catalyst, the second catalyst being about 2 to about 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum or rhenium, per 100 parts by weight of a support selected from the group consisting of silica, alumina and combinations thereof, the second catalytic reactor being capable of producing liquid fuel from the synthesis gas, the second catalytic reactor comprising a liquid fuel production plant.

[0218] Further Methods and Catalysts 1. A method for efficiently converting a CO2 / H2 mixture, or a mixture of CO2 / H2 and a light hydrocarbon, directly into synthetic liquid fuel by employing a catalytic process comprising two catalysts, wherein the first catalyst is an improved high surface area solid solution catalyst for producing synthesis gas, and the second catalyst is an improved structured catalyst for directly converting synthesis gas into synthetic fuel.

[0219] 2. The method according to the further method and catalyst 1, wherein H2 is produced from water using electrolysis.

[0220] 3. The method according to the further method and catalyst 1, wherein H2 can be produced from steam reforming of solid carbonaceous materials, including biomass, flare gas, biogas, methane, light hydrocarbons, and other components such as various stoichiometric mixtures of carbon, hydrogen, and oxygen.

[0221] 4. The method according to the further method and catalyst 1, wherein the CO2 can be captured from conventional power plants, oxy-fuel power plants, fermentation processes, cement plants, atmospheric CO2 capture systems, biogas, wastewater treatment plants, secondary oil recovery, oil refineries, chemical production plants, geothermal power plants, nylon plants, or ammonia plants.

[0222] 5. The method according to the further method and catalyst 1, wherein the ratio of the H2 / CO2 mixture input into the catalytic conversion process can vary from 1.5 / 1.0 to 5.0 / 1.0, preferably from 2.0 / 1.0 to 3.0 / 1.0.

[0223] 6. The method according to the further method and catalyst 1, wherein the H2 / CO2 mixture is introduced into the catalytic converter at a pressure between 25 and 400 psi (172 - 2,758 kPa)

[0224] 7. The method according to the further method and catalyst 1, wherein the H2 / CO2 mixture is introduced into the catalytic converter at a pressure of 150 to 325 psi (1,034 - 2,241 kPa)

[0225] ​​ 8. A further method according to the above method and catalyst 1, wherein the H2 / CO2 mixture is heated to a temperature higher than the operating temperature of the first catalyst so that the first catalyst requires little or no additional heating.

[0226] 9. A further method according to the above method and catalyst 1, wherein the first catalyst and the second catalyst in the catalytic reactor operate at substantially the same pressure.

[0227] 10. The first catalyst is an improved solid solution catalyst composed of Ni2Mg2 to 35% by weight supported on a high surface area alumina spinel which may include Co-alumina spinel, Fe-alumina spinel, Mg-alumina spinel, Mn-alumina spinel, Ca-alumina spinel, Ba-alumina spinel, Ni-alumina spinel, Cu-alumina spinel and Zn-alumina spinel, and M is a metal such as Mg, Mn, Ca, Ba, Cu, Zn or Sr. A method according to the above further method and catalyst 1.

[0228] 11. The improved solid solution catalyst according to the above further method and catalyst 9, wherein the first catalyst may contain 0.1 to about 5.0 parts by weight of a promoter composed of at least one transition or rare earth metal per 100 parts by weight of the support.

[0229] 12. The improved solid solution catalyst according to the above further method and catalyst 9, wherein the catalyst contains less than 0.05% of rare metals.

[0230] 13. The improved solid solution catalyst according to the above further method and catalyst 9, wherein a water-soluble salt of nickel and the promoter are impregnated on a spinel substrate, dried, and calcined at a temperature up to 2,100°F (1,149℃) up to a temperature of 2,100°F.

[0231] 14. The improved solid solution catalyst according to the above further method and catalyst 9, mainly containing Ni2MgO25 to 35% by weight and 0.2 to 5.0% by weight of the oxide of the promoter.

[0232] 15. The additional method and the catalyst 13 or the calcined catalyst related thereto that can be used in a tubular fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a rotating bed reactor, a slurry bed reactor, and other reactors commonly used in the art.

[0233] 16. Reduced with H2 or other reducing agents typically used in the art at a temperature up to about 1,200°F (649℃) to form primarily elemental forms of Ni2Mg and one or more transition metals or rare earth metals, the additional method and the catalyst 13 or the calcined catalyst related thereto.

[0234] 17. When the catalyst is operated at a pressure in the range of 20 - 200 psi (138 - 1,379 kPa) more preferably in the range of 50 - 150 psi (345 - 1,034 kPa) to efficiently convert a mixture of H2 and CO2 into synthesis gas, the reduced catalyst related to the additional method and the catalyst 15.

[0235] 18. When the catalyst is operated at a space velocity of 5,000 - 200,000 hr 1 to efficiently convert a mixture of H2 and CO2 into synthesis gas, the catalyst related to the additional method and the catalyst 15.

[0236] 19. A catalyst related to the additional method and the catalyst 15 that efficiently converts a mixture of CO2 and H2 into synthesis gas, where the ratio of H2 to CO2 can vary in the range of 1.0 - 4.0, preferably 1.5 - 3.5, more preferably 2.0 - 3.0.

[0237] 20. A catalyst related to the additional method and the catalyst 15, where the synthesis gas is produced at a pressure of 1,600°F (871℃) , 50 - 300 psi (345 - 2,068 kPa) with a conversion efficiency of CO2 to CO greater than about 55%.

[0238] 21. A catalyst related to the additional method and the catalyst 15 that produces synthesis gas with an H2 / CO ratio in the range of 1.0 - 3.0, preferably 1.5 - 2.5.

[0239] 22.2, 100°F (1,149℃) The catalyst according to the above further method and catalyst 15, having thermal stability up to

[0240] The catalyst according to the above further method and catalyst 15, which is resistant to contaminants present in the captured CO2 stream, natural gas, biogas or other gas feedstock streams.

[0241] The catalyst according to the above further method and catalyst 15, wherein the catalyst forms no or little carbon by coking.

[0242] The catalyst according to the above further method and catalyst 15, wherein CH4 is efficiently converted to syngas when present in a CO2 / H2 mixture.

[0243] The catalyst according to the above further method and catalyst 15, wherein C2-C7 hydrocarbons are efficiently converted to syngas when present in a CO2 / H2 mixture.

[0244] The method according to the above further method and catalyst 15, wherein syngas is efficiently produced when O2 is added to a selected mixture of CO2, H2, CH4, and C2-C5 hydrocarbons.

[0245] The method according to the above further method and catalyst 15, wherein the syngas is fed into another catalytic reactor to produce fuels and / or chemicals thereby.

[0246] 29. A heat exchanger is used to reduce the temperature from the first catalyst to the operating temperature of the second catalyst to 400 °F ~475°F (204℃~246℃) The method according to the above further method and catalyst 15.

[0247] 30. The cooled synthesis gas is supplied into a second catalyst, and the second catalyst contains about 2 to about 50 parts by weight of cobalt and about 0.1 to about 10 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, palladium, or rhenium per 100 parts by weight of a support selected from the group consisting of silica, alumina, and combinations thereof, thereby producing diesel fuel. The method further includes the above method and the catalyst 28.

[0248] 31. The second catalyst produces C1-C5 gas-phase hydrocarbons; C5-C 23 liquid-phase hydrocarbons; exhaust gas composed of CO, H2, C1-C5 hydrocarbons, CO2; H2O; and C 24 + hydrocarbons. The method further includes the above method and the catalyst 28.

[0249] 32. The method further includes introducing the product stream from the second reactor system into a separator that separates C 24 + hydrocarbons from other products. The method further includes the above method and the catalyst 30.

[0250] 33. By changing the temperature of the separator, the distribution of C 23 + hydrocarbons from the C5-C 24 hydrocarbons is controlled. The method further includes the above method and the catalyst 30.

[0251] 34. The remaining liquid product stream is condensed into two fractions, the upper fraction contains the liquid hydrocarbon fuel, and the lower fraction contains water. The method further includes the above method and the catalyst 31.

[0252] 35. The liquid hydrocarbon fuel is separated from the water. The method further includes the above method and the catalyst 33.

[0253] 36. The liquid hydrocarbon fuel is directly used in off-road diesel engines and vehicles. The method further includes the above method and the catalyst 34.

[0254] 37. A method according to the above further method and catalyst 34, wherein a liquid hydrocarbon fuel is mixed with petroleum diesel fuel and used in an on-road diesel engine and a vehicle.

[0255] 38. A method according to the above further method and catalyst 34, wherein the synthetic liquid fuel is distilled, thereby producing diesel fuel #1, diesel fuel #2, jet fuel, reformulated gasoline blendstock, and a small fraction (less than about 5% by volume) of heavy (C 24 +) hydrocarbons.

[0256] 39. A method according to the above further method and catalyst 37, wherein the reformulated gasoline blendstock is mixed with petroleum gasoline fuel and used in a spark ignition engine and a vehicle.

[0257] 40. A method according to the above further method and catalyst 37, wherein the diesel #1 (kerosene) is used in a kerosene heater and a stove.

[0258] 41. A method according to the above further method and catalyst 37, wherein the diesel #1 (kerosene) is used in a jet engine and a turbine.

[0259] 42. A method according to the above further method and catalyst 37, wherein the neat or blended synthetic fuel reduces engine emission standards by at least 2% compared to a petroleum-based fuel.

[0260] 43. A method according to the above further method and catalyst 37, wherein the neat or blended synthetic fuel improves one or more fuel properties by at least 2% compared to a petroleum-based fuel.

[0261] 44. A method according to the above further method and catalyst 37, wherein the neat or blended synthetic fuel reduces greenhouse gas emissions by at least 2% compared to a petroleum-based fuel.

[0262] 45. The method according to the further method and catalyst 34, wherein a part of the exhaust gas is returned to the catalyst #2 for producing additional products and reused.

[0263] 46. The method according to the further method and catalyst 34, wherein a part of the exhaust gas is converted into additional synthesis gas by partial oxidation with oxygen (e.g., ATR conversion) or by autothermal reforming (ATR) produced from electrolysis.

[0264] 47. The method according to the further method and catalyst 45, wherein the heated synthesis gas is added to the H2 / CO2 stream before being introduced into the first catalyst.

[0265] 48. The method according to the further method and catalysts 1 to 28, wherein the synthesis gas is fed into another type of catalytic process to produce fuel and / or chemicals thereby.

[0266] 49. The method according to the further method and catalyst 47, wherein the second catalyst is a Fischer-Tropsch type catalyst formulation for producing wax, and subsequently the wax is converted into fuel and / or chemicals using conventional wax hydrocracking and hydrotreating methods.

[0267] 50. The method according to the further method and catalyst 47, wherein the second catalyst produces methanol, ethanol, and / or other alcohols.

[0268] 51. The method according to the further method and catalyst 47, wherein the second catalyst is used to produce methanol, and subsequently the methanol is converted into gasoline using additional conventional catalysts and methods described in the current technology.

[0269] 52. The method according to the further method and catalyst 47, wherein the synthesis gas is used to generate electricity using a generator set, gas turbine, and other established gas-to-power facilities.

[0270] 53. The method according to the further method and catalyst 47, wherein the synthesis gas is used as a burner fuel for generating heat.

[0271] 54. The method according to the further method and catalyst 47, wherein the second catalyst is used for generating ammonia.

Examples

[0272] In this exemplary embodiment, the conversion of CO2 from an oxy-fuel combustion power plant to liquid fuel will be described. As described above, in the direct production of liquid fuels from CO2 using these improved catalysts and processes, CO2 obtained from, but not limited to, conventional power plants, oxy-fuel combustion power plants, ethanol fuel production plants, cement plants, atmospheric CO2 capture systems, geothermal power plants, and other CO2 emission sources can be used.

[0273] The main differences between these sources are the cost of obtaining relatively pure CO2 and the cost of the electricity used to generate H2 by electrolysis of water. Oxy-fuel combustion power plants have the ability to produce CO2 directly at little or no cost and supply electricity for H2 production at reasonable cost, so the direct conversion of liquid fuels produced from CO2 is an important example described here.

[0274] Oxy-fuel combustion is a process of burning hydrocarbon fuels in a nearly pure oxygen environment, as opposed to air. Coal has been tested in oxy-fuel combustion facilities, but the combustion of coal produces large amounts of particulate matter (fly ash) and sulfur oxides (SO, SO2, SO3, etc.). Therefore, the preferred hydrocarbon fuel is natural gas.

[0275] One of the most promising oxygen fuel combustion processes utilizes the Allam cycle (Allam et al, 2017). This system uses a semi-closed loop, high-pressure, low-pressure ratio reheat Brayton cycle with supercritical CO2 as the working fluid, dramatically reducing energy losses compared to steam and air-based cycles. In conventional cycles, separating and removing impurities resulting from low-concentration combustion such as CO2 incurs substantial additional capital costs and increases parasitic power output, raising the electricity cost by 50% - 70%. The Allam cycle's compelling economics are driven by a high target efficiency of 59% net for natural gas (LHV basis) while capturing nearly 100% of CO2 at the pressure of a pipeline with low predicted capital and O&M costs. Furthermore, this cycle can operate with substantially no water in exchange for a slight performance degradation. This system employs only a single turbine, has a small plant footprint, and requires fewer components and is smaller than conventional hydrocarbon fuel systems.

[0276] Figure 5 illustrates the Allam oxygen fuel combustion process and the main processes for the integration of the direct liquid fuel production process and the Allam oxygen fuel combustion process. The cryogenic air separator 501 is used to separate oxygen 503 from the atmosphere 502. Oxygen 503 is mixed with natural gas 504 at high pressure (about 320 bar) and high temperature (about 720 °C) in the presence of heated supercritical carbon dioxide.

[0277] Combustion produces additional carbon dioxide, water, and a large amount of heat 506. Some CO can be produced depending on the ratio of oxygen to natural gas, combustion pressure and temperature, and the power load under gas turbine conditions (Wang and Stiegel, 2017). However, when the combustion system operates under stoichiometric conditions (O2 / fuel = 1.00) or very close to them, CO production is very low.

[0278] Next, the high-temperature high-pressure mixture passes through the gas turbine generator 507, where the high-pressure gas flow rotates the shaft, thereby generating electricity. Most of the power is distributed to the grid 508, and the remainder is used directly in the liquid fuel production process 510. The pressure of the gas flow 511 exiting the gas turbine drops to about 30 bar at about 720 °C.

[0279] The gas flow 511 passes through the heat exchanger 512, which reduces the temperature of the gas flow 511 to 43 °C while maintaining a pressure of 30 bar. The cooler 513 and the mist separator 514 remove water 515 from the CO2 stream. This water contains a small amount of sulfate derived from the combustion of sulfur in the natural gas. The sulfates, other particulates, and dissolved contaminants in the water are removed by the direct liquid fuel manufacturing process 510.

[0280] A portion of the CO2 516 is used by the direct liquid fuel production plant, and the remainder of the CO2 517 is compressed 518 and heated 512 to about 320 bar and 720 °C. These conditions produce supercritical CO2 519. Any excess CO2 520 can be used for other purposes such as the production of dry ice.

[0281] As a result, this process produces no emissions. The heat transfer in this process is very efficient such that for each unit of energy contained within the natural gas, this cycle produces 0.8 units of electricity (compared to 0.6 units produced by a state-of-the-art natural gas power plant).

[0282] This example describes an innovative method for manufacturing direct liquid fuels from CO2 that employs an innovative catalyst converter and method integrated with a 300 MW Allam cycle oxy-fuel plant. This direct liquid fuel production plant is designed to produce approximately 450 barrels per day of drop-in synthetic liquid fuel from 91,000 metric tons per year of CO2, 78.06 MW of electricity, and condensate produced by the oxy-fuel plant.

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Claims

1. A method for converting carbon dioxide into a liquid fuel, comprising: a) generating hydrogen and oxygen from the electrolysis of water; b) introducing the hydrogen, together with carbon dioxide, into a first catalytic reactor using a first catalyst, wherein the product from the first catalytic reactor is synthesis gas, the first catalyst is a solid solution catalyst of a transition metal, and reacting carbon dioxide and hydrogen with the first catalyst at a temperature of 1,300°F (704°C) or higher and 1,700°F (927°C) or lower and a pressure of 50 psi (345 kPa) or higher and 300 psi (2,068 kPa) or lower to convert them into the synthesis gas; c) introducing the synthesis gas into a second catalytic reactor using a second catalyst to produce exhaust gas, water, and liquid fuel; d) introducing the exhaust gas from the second catalytic reactor into an exhaust gas conversion system that uses oxygen from an electrolysis device to produce additional synthesis gas. The first catalyst contains, per 100 parts by weight of the silica support, 2 to 25 parts by weight of magnesium having a surface area greater than 50 m ２ / g, 0.1 to 5 parts by weight of cerium, ruthenium, lanthanum, platinum or rhenium, and 2% to 20% by weight of nickel, and is an impregnated and metal-coated spinel. A method.

2. wherein the first solid solution catalyst contains Ni ２ Mg, the method according to claim 1.

3. The method according to claim 1, wherein the exhaust gas conversion system is partial oxidation.

4. The method according to claim 1, wherein the exhaust gas conversion system is autothermal reforming.

5. The method according to claim 1, wherein the first catalytic reactor and the second catalytic reactor operate with a pressure difference of 50 psi (345 kPa) or less between each other.

6. The method according to claim 1, wherein the synthesis gas is introduced into a heat exchanger to lower the temperature of the synthesis gas before the synthesis gas is introduced into the second catalytic reactor.

7. The carbon dioxide introduced into the first catalytic reactor is obtained from a source selected from the group consisting of an oxy-fuel power plant, an atmospheric CO ２ recovery system, a natural gas wellhead, an ethanol production facility, a chemical production facility, and a secondary oil recovery process, the method according to claim 1.

8. The method according to claim 1, wherein the hydrogen is generated using electrolysis, and the electric power for the electrolysis is generated from a renewable source or a low-carbon source selected from the group consisting of wind power, solar power, geothermal power, hydraulic power, ocean current power, biomass, flare gas, nuclear power, off-peak power from a fossil fuel plant, and electric power produced by an oxy-fuel combustion plant.

9. The method according to claim 1, wherein the second catalytic reactor is operated at a pressure of 50 psi to 300 psi (345 kPa to 2,068 kPa), 50 psi to 250 psi (345 kPa to 1,724 kPa), 50 psi to 200 psi (345 kPa to 1,379 kPa), 50 psi to 150 psi (345 kPa to 1,034 kPa), or 50 psi to 100 psi (345 kPa to 690 kPa).

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