Improved catalysts and processes for direct production of liquid fuels from carbon dioxide and hydrogen

Abstract

Embodiments of the present invention relate to two improved catalysts and associated processes for directly converting carbon dioxide and hydrogen into liquid fuels. The catalytic converter consists of two catalysts in series, which operate at the same pressure to directly produce synthetic liquid fuels or synthetic natural gas. The carbon conversion efficiency of CO2 to liquid fuel is greater than 45%. The fuel is distilled into high-quality diesel fuel (about 70 volume %) and naphtha (about 30 volume %), which are directly used as "drop-in" fuels without any further treatment. Any light hydrocarbons present with carbon dioxide are also directly converted into fuels. The process is directly applicable to the conversion of CO2 collected from ethanol plants, cement plants, power plants, biogas, carbon dioxide / hydrocarbon mixtures from secondary oil recovery, and other carbon dioxide / hydrocarbon streams. The catalyst system is durable, efficient, and maintains a relatively constant level of fuel productivity over a long period of time without the need for reactivation or replacement.

Description

Technical Field

[0001] The present invention relates to a method for converting CO into 2 With H 2 An improved catalyst and process for efficiently and economically converting a mixture of H2O2 directly into liquid fuels. The catalytic process employs two enhanced catalysts that operate efficiently in tandem at similar pressures, thereby simplifying the overall process of producing fuels from non-petroleum feedstocks. Catalyst #1 converts H 2 With CO 2 The mixture is converted into H 2 The ratio of H to CO is about 1.5-2.5, and catalyst #2 produces synthetic liquid fuels (and other products) directly from the syngas. 2 and O 2 is produced from water using electrolysis. The tail gas (C 1 -C 5 HC, H 2 , CO and CO 2 ) 2 Partial oxidation to produce additional syngas and heat. This commercial-scale process is suitable for use in CO2 from fermentation processes; cement plants; power plants; ambient air 2 Capture systems (direct air capture); coal-fired power plants, natural gas processing plants, natural gas power plants, ammonia facilities, chemical facilities, and other important CO 2 CO collected from sources 2 conversion (IPCC, 2005; Schuetzle et al., 2010; Wieclaw-Solny et al., 2013). 2 Light hydrocarbons present in the gas are also converted into synthesis gas. Liquid fuels produced include high-quality kerosene, diesel and jet fuels, as well as gasoline blend stock. 2 Source and use for H 2 The source of power produced, greenhouse gas emissions from liquid fuels are reduced by approximately 50-130%. In addition to reducing greenhouse gas emissions, synthetic diesel fuel also reduces emissions of standard pollutants and improves fuel economy. This simplified two-step catalytic process is durable, efficient, and maintains a relatively constant level of fuel productivity over long periods of time without the need for catalyst reactivation or replacement. Background Art

[0002] The present invention focuses on the efficient and economical conversion of CO 2 With H 2Improved catalysts and associated processes for converting mixtures of carbon dioxide directly into liquid fuels with reduced 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 remain so popular (Fulkerson et al., 1990).

[0004] 1. Since the infrastructure for the distribution of gaseous and liquid fuels is very extensive, they are available in one form or another in almost all regions of the world.

[0005] 2. They can be efficiently used to provide energy for a variety of applications at all scales.

[0006] 3. As transportation fuels, they are unmatched because they are portable and contain large amounts of stored chemical energy. Therefore, liquid fuels will continue to be an unstoppable source of transportation energy.

[0007] However, the production and combustion of fossil fuels produces a large amount of greenhouse gas CO 2 and CH 4 , the global goal is to replace fossil fuels with low carbon liquid fuel (LCLF) and / or low carbon natural gas (LCNG) (Schuetzle, 2018).

[0008] Although CO 2 can be converted into low-carbon natural gas (LCNG) (Marti et al., 2016; Hill, 2018), but CO 2 Converting to LCLF instead of LCNG has the following advantages:

[0009] 1. The energy densities of diesel fuel and gasoline fuel are approximately 38.6 MJ / liter and 34.2 MJ / liter, respectively. These energy densities are much higher than the energy densities of: CH 4 (9.0 MJ / L at 250 bar); H 2 (5.3 MJ / L at 690 bar); dimethyl ether (21.2 MJ / L at 5 bar); methanol (15.6 MJ / L); lithium-ion batteries (1.76 MJ / L) and lead-acid batteries (0.56 MJ / L) (Wikipedia, 2019).

[0010] 2. From CO 2 Production CH 4 Required H 2is the H needed to produce liquid fuels from CO2 2 About four times.

[0011] 3. With CH 4 200-400 bar and for H 2 Diesel and gasoline fuels can be stored at or near atmospheric pressure, compared to 340-690 bar.

[0012] 4. The global distribution infrastructure for liquid fuels is extensive, and they can be easily transported to almost any location on Earth.

[0013] 5. Produce synthetic CH that meets natural gas pipeline standards 4 is challenging (Zhou et al., 2010; Melaina et al., 2013; Zaki et al., 2016; SoCalGas, 2019).

[0014] Therefore, there is increasing interest in developing efficient and economical methods for CO 2 Technologies for conversion to 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).

[0015] The improved catalyst and process provide for the conversion of CO2 to CO2 using primary energy from renewable, carbon-free sources such as electricity derived from solar, wind, wave / tidal, hydro or nuclear power. 2 Together with hydrogen, this has the interesting possibility of being converted into a high-density vehicle fuel that is compatible with our current transportation infrastructure. In addition, this next-generation technology will help expand more efficient power plants that produce little or no emissions, such as oxy-combustion power plants. Oxy-combustion power plants are power plants that produce power from natural gas and oxygen, with the effluent of the power plant being nearly pure CO. 2 stream (rather than the diluted CO generated from conventional power plants 2 material flow).

[0016] The real appeal is that this approach offers the prospect of significantly reducing carbon emissions from the transportation system without requiring a paradigm shift in the infrastructure required to electrify the fleet or transition to a hydrogen economy (Pearson et al., 2009).

[0017] CO 2Most existing technologies developed into liquid fuels have focused on producing gasoline and diesel fuel as "ready-to-use" fuels. Dimethyl ether (DME) is a potential low-emission fuel for diesel engines, but it is not a "ready-to-use" fuel because diesel engines must be modified for its use and the infrastructure to deliver the fuel has not yet been developed (Semelsberger, 2006).

[0018] Although methanol has been suggested for many years as a potential liquid fuel for engines, it has not been accepted as a fuel because it is highly flammable, toxic, and its combustion produces toxic and carcinogenic formaldehyde emissions. Instead, it is primarily used as an intermediate chemical product in the production of liquid fuels or chemicals.

[0019] From H 2 With CO 2 The following process is usually required to produce a "ready-to-use" liquid fuel from a mixture of

[0020] 1. H 2 / CO 2 Conversion of mixture into synthesis gas

[0021] 2. Convert the syngas into fuels that meet ASTM and other fuel specifications. This process typically requires two or more major conversion processes.

[0022] In order to make CO 2 The commercial viability of the process of converting H 2 With CO 2 The catalysts manufactured for converting a mixture of syngas into synthesis gas and converting such synthesis gas into liquid fuels must meet one or more of the quality and performance specifications listed in Table 1 below.

[0023] Table 1 - For H 2 / CO 2 Quality and performance specifications for the catalytic conversion of mixtures into synthesis gas

[0024] The catalyst contains low-cost ingredients (no [or nominal] rare metals).

[0025] It can be manufactured economically in quantities of several tons.

[0026] • The catalyst is strong (eg, Rockwell hardness greater than Mohr 03-04).

[0027] • It is chemically and physically stable up to 2100°F.

[0028] • It can be easily loaded into catalytic reactors (eg tubular or packed bed reactors).

[0029] • The pressure drop from top to bottom of the catalytic reactor is acceptable.

[0030] Catalyst activation (e.g., with H 2 Reduction) can be performed in situ.

[0031] · At more than about 10,000 hr -1 At an airspeed of 2 The conversion rate to CO is greater than about 50% per pass, but preferably greater than about 65% per pass.

[0032] • CO production selectivity greater than about 70%, but preferably greater than about 85%.

[0033] It does not coke (i.e. form carbon deposits).

[0034] It has a longer lifespan and does not require system reactivation (restoration).

[0035] Two methods for converting CO to 2 The first and most widely described method uses the 2 With H 2 The catalytic process of converting the mixture of 2 Hydrogenation or reverse water gas shift (RWGS) (Senderens et al., 1902; Daza et al., 2016; Vogt et al., 2019). The second method involves the use of 2 With H 2 O mixture into syngas through electrolysis (Wang et al., 2016).

[0036] H 2 / CO 2 Catalytic conversion of mixtures into synthesis gas - Many patent applications, patents and publications describe methods for converting H 2 With CO 2 Development of a catalyst for converting a mixture of pyrolysis products into synthesis gas. This prior art was evaluated with respect to the quality and performance specifications outlined in Table 1.

[0037] Iwanani et al. (1993) developed a catalyst composed of transition metals and rare metals (e.g., Ni, Fe, Ru, Rh, Pt, W, Pd, Mo) on zinc oxide for the conversion of CO 2 With H 2A mixture of 200 mol / L was reduced to CO. They achieved relatively low conversions of up to 37% without significant loss of catalyst activity after 150 h, but were not tested for longer periods.

[0038] Chen et al. (2015) reported a nanometallic compound catalyst (InNi 3 CO 0.5 ) was synthesized by a team of researchers from the University of Michigan and the University of Michigan, and the catalyst was shown to be active and selective for the RWGS reaction. The catalyst was made by carburizing an In-Ni intermetallic matrix that produced dual active sites on the catalyst surface. At 600°C and a gas rate of 300,000 ml / g (catalyst) / hr, they achieved 52-53% CO conversion in 150 hours. 2 This catalyst was not tested over longer periods of time.

[0039] Bahmanpour et al. (2019) discovered an in situ formed Cu-Al spinel as a novel nanostructured carbon nanotube 2 CO 2 They used coprecipitation followed by hydrogen treatment to form Cu-Al spinels of different weight ratios. A 4:1 Cu to Al ratio was found to be effective for CO 2 The conversion was efficient. They maintained a relatively low CO of 47% at 600°C at relatively high space velocities. 2 The conversion rate was 2.33 %, and no detectable deactivation was observed after 40 hours of testing. However, copper-containing catalysts tend to deactivate upon sintering at high temperatures. In addition, candidate catalyst formulations need to be tested for 1,000 hours or more to evaluate potential commercial viability.

[0040] CO 2 / H 2 O mixture is electrochemically converted into syngas— CO 2 Electrochemical conversion of energy has been an area of ​​research that has evolved (Zhu, 2019). Much of the research and development (R&D) effort has focused on fuel cells (Sunfire, 2016) and PEM and alkaline electrolysis systems (Messias et al., 2019).

[0041] PEM and alkaline electrolysis —Opus 12 has developed a method to convert CO 2 With H 2 O mixture into sixteen C 1 -C 3PEM electrolyzers (Kuhl et al., U.S. Patent Application Publication 2017 / 0321333) oxidize a mixture of hydrocarbons (alcohols, ketones, aldehydes, and acids). Separating this complex mixture into specific compounds requires expensive refining processes. If this separation is successful, ethanol is the only suitable product that can be used as a fuel (e.g., blended with gasoline).

[0042] Fuel Cells —Sunfire has developed a solid oxide electrolysis cell (SOEC) based on the use of CO 2 and H 2 O is a process for high temperature co-electrolysis to produce synthesis gas. SOEC operates at high pressure (>1MPa) and high temperature (>800℃). The synthesis gas is then converted into long chain hydrocarbons using the conventional Fischer-Tropsch process. The wax is converted into gasoline fuel and diesel fuel using a two-step catalytic refining process. Therefore, Sunfire requires three steps to produce "ready-to-use" fuels, and this process requires complex wax upgrading or refining.

[0043] In the prior art, CO 2 Four main processes for conversion into "ready-to-use" liquid fuels are possible:

[0044] One-step process

[0045] 1. Use catalytic or electrochemical processes to convert CO 2 Direct conversion into liquid fuel.

[0046] Two-step process

[0047] 1. Use catalytic or electrochemical processes to convert CO 2 Converted into synthesis gas.

[0048] 2. Use a second catalyst to convert the syngas directly into liquid fuels.

[0049] Two-step process

[0050] 1. Use catalytic or electrochemical processes to convert CO 2 conversion into primary chemical intermediates;

[0051] 2. Use a second catalyst to convert the chemical intermediate directly into a liquid fuel.

[0052] Three-step process

[0053] 1. Use catalytic or electrochemical processes to convert CO 2 conversion into synthesis gas;

[0054] 2Converting synthesis gas into primary chemical intermediates (such as wax; methanol, etc.);

[0055] 3. Convert the purified intermediates directly into liquid fuels.

[0056] Four-step process

[0057] 1. Use catalytic or electrochemical processes to convert CO 2 conversion into synthesis gas;

[0058] 2. Converting synthesis gas into primary chemical intermediates (e.g. wax; methanol, etc.);

[0059] 3. The purified intermediate products are converted into liquid fuels using two main chemical processes.

[0060] Four-step process

[0061] 1. Use catalytic or electrochemical processes to convert CO 2 Converted into synthesis gas.

[0062] 2. Converting synthesis gas into a mixture of organic intermediates (such as wax; methanol, etc.);

[0063] 3. Using separation processes to produce the desired purified intermediates;

[0064] 4. Convert the purified intermediate products into liquid fuels.

[0065] In order for these four processes to be commercially viable, it is critical that the catalysts manufactured for the production of liquid fuels and fuel products meet some of the quality and performance specifications listed in Table 2.

[0066] Table 2 - Quality and performance specifications for catalytic conversion of synthesis gas to liquid fuels

[0067] 1. The catalyst contains low-cost ingredients (no [or nominal] rare metals).

[0068] 2. It can be manufactured economically in quantities of several tons.

[0069] 3. The catalyst is strong (eg, Rockwell hardness greater than Mohr 03-04).

[0070] 4. It is chemically and physically stable up to 1800°F.

[0071] 5. It can be easily loaded into catalytic reactors (e.g. tubular reactors).

[0072] 6. The pressure drop from top to bottom of the catalytic reactor is acceptable.

[0073] 7. Catalyst activation (e.g., with H 2 Reduction) can be performed in situ.

[0074] 8. The CO to liquid fuel conversion efficiency is greater than about 35% per pass, preferably about or greater than 55% per pass.

[0075] 9. It has a longer lifespan and does not require system reactivation (restore).

[0076] 10. Liquid fuels are cost competitive with petroleum-derived fuels.

[0077] 11. Liquid fuels meet the fuel standards published by ASTM and other fuel standards organizations.

[0078] The prior art for one-step, two-step, three-step and four-step processes was summarized and rated with respect to the quality and performance specifications summarized in Table No. 1 and Table No. 2.

[0079] One-step process —CO is converted into 2 Most efforts to convert carbon dioxide into liquid hydrocarbon fuels have been directed toward developing a catalyst that first converts carbon dioxide into liquid hydrocarbon fuels through hydrogenation. 2 CO is then reacted with H 2 react over the same catalyst to form liquid fuels via a mechanism based on the conventional FT reaction. 2 One of the challenges associated with the FT process is that only low concentrations of CO are present during the reaction. This limits chain growth, and as a result the product profile is often rich in 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 for the reverse water gas shift reaction and FT chemistry (National Academy of Sciences, 2019).

[0080] Landau et al. (Australian Patent Application 2015 / 203898) described a 20% Fe on iron-spinel catalyst. 2 O 3 The catalyst particle size varied from 100 μm to 3.0 mm. 2 / CO 2 Syngas with a ratio of 2.0-3.0 / 1.0 is about 2.0hr -1 The catalyst was tested at very low space velocities, temperatures of 325-350°C and pressures of 20-40 atmospheres. 2 The maximum conversion rate is 36%. The selectivity of the products is: CO (13%), CH 4 (9%), C2 -C 5 (44%) and C 6 -C 27 HC(25%) 6 The olefin / paraffin ratio of the + hydrocarbons is about 5 / 1. This catalyst does not produce a "ready to use" fuel that meets ASTM specifications, and it also does not meet the catalyst quality and performance specifications listed above.

[0081] Wang et al. (2013) described a Fe / ZrO 2 Catalyst for catalyzing CO 2 The hydrogenation mainly produces CH 4 and C 2 -C 4 Paraffins. Very low selectivity for producing liquid hydrocarbons.

[0082] Wei et al. (2018) described a method for converting CO 2 One-step conversion of CO into isoparaffins using an iron-based catalyst. 2 The conversion efficiency is only 26% and the CO selectivity is about 17%. Coke (carbon) deposition within the catalyst micropores causes the isoparaffin yield to drop rapidly over time.

[0083] Williamson et al. (2019) described the performance of a one-step catalyst consisting of iron nanoparticles deposited on carbon nanotubes. The catalyst was calcined in air at 400 °C for 1 h or at 570 °C for 40 min and heated at 400 °C with H 2 Activate for 3 hours. Use 3.0 / 1.0 H 2 / CO 2 mixture, and the catalyst was tested in a laboratory reactor at 370°C and 221 psi. The average CO 2 The conversion rate was 54%, and the CO and hydrocarbon selectivities were 30% and 70%, respectively. The average composition of the hydrocarbon products was 43% CH 4 55% C 2 -C 4 hydrocarbons and 2.0% C 5 + Hydrocarbons.

[0084] Pan et al. (2007) described a method for using a 13 hr -1 The very low air velocity from CO 2 With H 2Rh catalyst supported on carbon nanotubes is used in a tubular reactor for producing ethanol from a mixture of ethanol and methanol. In addition to ethanol, this catalyst also produces 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 due to the high catalytic reactor pressure drop, low space velocity and the production of a complex mixture of oxygenated hydrocarbons.

[0085] Two-step process Shulenberger et al. (U.S. Pat. No. 8,198,338) describe a method for converting CO 2 The process of converting the Cu / ZnO / Al into gasoline is carried out in a catalytic reactor operated at about 50 bar pressure and 500 °C. 2 O 3 The catalyst converts H 2 and CO 2 (molar ratio of 2.0 / 1.0) is converted into methanol. Due to the low operating pressure, the selectivity for methanol production is only about 10%. The methanol produced from the first catalytic process is fed to another catalytic reactor containing a ZSM-5 catalyst and operated at about 4 bar pressure and 390°C to convert methanol into gasoline. The conversion efficiency of the two-step process and the chemical and physical composition of the gasoline are not described. However, based on the selectivity of methanol production in the first reactor, it is estimated that the selectivity for gasoline production is less than 10%.

[0086] Three-step process —Sunfire uses a solid oxide electrolyzer (SOEC) to 2 and H 2 O is electrolytically converted to produce syngas (Zhu, 2019). The syngas is then converted into long-chain hydrocarbons using the conventional Fischer-Tropsch process. The wax is converted into gasoline fuel and diesel fuel using a two-step catalytic refining process. Thus, Sunfire requires three steps to produce "ready-to-use" fuels.

[0087] Four-step process Several four-step processes have been described in the prior art. One method uses a one-step process to 2 / CO 2 The mixture produces chemical intermediates such as methanol, which is then converted into gasoline using a three-step process. Another method is to convert H 2 / CO 2 The mixture produces syngas, which is then converted by Fisher Tropsch into wax, and then the wax is converted into liquid fuel in two steps.

[0088] Kothandaraman et al. (2016) used a solution of polyamine (PEMA) in tetrahydrofuran (THF) to capture CO2 Although this amine has good CO 2 The capture efficiency is high, but amines are known to deactivate the catalyst. 2 The catalyst is a complex of ruthenium with organic ligands surrounding it. In the laboratory, a 3.0 / 1.0 H 2 / CO 2 The process was tested at a reactant ratio of 75 atmospheres, a pressure of 75 atmospheres and a temperature of 145°C. 2 to CH 3 The carbon conversion rate of OH was 65%.

[0089] During 2012, a plant was commissioned in Svartsengi, Iceland to demonstrate the process. 2 is using 5.0 MW of geothermal energy from H 2 O is electrochemically generated. CO 2 It is captured from the Svartsengi power plant in Iceland. The methanol production is about 50,000 liters / year.

[0090] Gasoline can be produced from this methanol using a three-step process patented by Exxon-Mobil (Jafari, 2018). The process uses three catalytic reactors: Catalytic Conversion #1: Methanol to DME; Catalytic Conversion #2: DME to C 2 -C 5 Olefins; Catalytic Conversion #3: C 2 -C 5 Olefins to gasoline. MTG gasoline is typically composed of 53% paraffins, 12% olefins, 9% naphtha, 26% aromatics, 0.3% benzene and contains no sulfur. The octane number (RON+MON) / 2 is 87, and the RVP (psi) is 9.0.

[0091] In summary, no existing technology has been identified that can be used to generate CO in two main steps. 2 / H 2 The blend produced a "ready to use" liquid fuel that met the performance and quality specifications summarized in Tables 1 and 2.

[0092] Compared to other catalysts developed for this application, the improved catalyst described in this document utilizes only one transition metal, Ni, while all other CO 2Hydrogenation catalysts use two or more transition metals (Okado, U.S. Pat. No. 6,423,665; Choudhary, U.S. Pat. No. 7,432,222; Millar, WO 2000 / 016899). Several other prior art formulations require the use of expensive metals (e.g., Pt, Pd, Rh, Ru, and Ir) (Okado, U.S. Pat. No. 6,409,940 and Green, U.S. Pat. No. 5,431,855).

[0093] Exhaust conversion - The tail gas produced by the one-step process, two-step process, three-step process and four-step process is usually C 1 -C 5 Hydrocarbons and CO 2 and the unconverted H 2 and CO. This tail gas needs to be used as energy in commercial-scale plants or converted into additional synthesis gas.

[0094] The main process for converting tail gas into synthesis gas is by means of the Steam Methane Reforming (SMR) process. However, steam reforming has several disadvantages. It is a highly endothermic reaction and requires excess steam to prevent or delay deactivation due to carbon deposition. Therefore, the high energy requirements of SMR lead to high costs for producing this additional synthesis gas. In addition, the SMR process produces CO by burning fuel gas to ignite the burners in the SMR. 2 .

[0095] Catalytic partial oxidation (POX) of tail gas to syngas has several advantages over SMR. Because the oxidation of hydrocarbons to a syngas mixture is exothermic, this process is much more energy efficient than steam reforming and dry reforming processes (Gaffney et al., U.S. Pat. No. 6,402,989).

[0096] However, POX has several potential disadvantages:

[0097] 1. Relatively pure oxygen is required, the source of which is usually cryogenically separated from air.

[0098] 2. The POX process can be highly exothermic, which leads to catalyst hot spots that can damage the catalyst or cause thermal runaway.

[0099] Autothermal reforming (ATR) of tail gas to synthesis gas is another process that can be used for tail gas conversion. Partial oxidation occurs in the inlet of the reactor, which provides heat for the steam reforming reaction. Therefore, it is not necessary to supply heat to the reactor (Ashcroft (1991); Choudhary (1995); and Ruckenstein (1998)).

[0100] It has been found that cobalt-nickel catalysts on alumina show superior methane ATR performance in terms of activity, stability, and synergy when compared with other catalysts. 4 , CO 2 and O 2 When a mixture of was reformed at about 1300°F and 15 psi, some carbon formation was observed (Foo (2012) and Zhang (2007)). Summary of the invention

[0101] In one aspect, the present invention provides a process for converting carbon dioxide into liquid fuels, wherein the process comprises the following steps: a) introducing a gaseous mixture of carbon dioxide and hydrogen, or a mixture of carbon dioxide, hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, wherein the first catalyst is a solid solution catalyst formed of nickel and magnesium, preferably comprising Ni 2 Mg; b) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce exhaust gas, water and liquid fuel, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of an element selected from the group consisting of silica, alumina and combinations thereof, per 100 parts by weight of a carrier selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 parts by weight to about 5 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or 0.1 parts to 5.0 parts of rhenium, thereby producing liquid fuel, exhaust gas and water; c) separating the liquid fuel, exhaust gas and water from each other, thereby producing the liquid fuel.

[0102] In another aspect, the present invention provides a catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising about 2 to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 to about 5 parts by weight of cerium, ruthenium, lanthanum, platinum or rhenium, and about 2 to about 20 weight % of nickel.

[0103] In another aspect, the present invention provides a process for producing liquid fuels, wherein the process comprises the following steps: a) separating oxygen from ambient air using a cryogenic air separator; b) mixing oxygen with natural gas at high pressure and temperature in the presence of heated supercritical carbon dioxide, thereby combusting the natural gas to produce combustion gas comprising carbon dioxide and water and heat; c) passing the combustion gas through a gas turbine generator to produce electricity for at least two purposes, and wherein the at least two purposes are distribution to a power grid and use in the process of producing liquid fuels, and allowing the combustion gas to leave the gas turbine generator; d) further passing the combustion gas through a heat exchanger, wherein the heat exchanger reduces the temperature of the combustion gas; e) removing water from the combustion gas to provide carbon dioxide; f) introducing a portion of the carbon dioxide together with hydrogen, or a mixture of a portion of the carbon dioxide with hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and the catalyst ideally comprises Ni 2 Mg, and compressing any remaining carbon dioxide while heating to provide supercritical carbon dioxide; g) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce tail gas, water and liquid fuel, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of an element selected from the group consisting of silica, alumina and combinations thereof, per 100 parts by weight of a carrier selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 parts by weight to about 5 parts by weight of at least one metal selected from the following items: cerium, ruthenium, lanthanum, platinum, or rhenium, thereby producing liquid fuel, tail gas and water; h) separating the liquid fuel, tail gas and water from each other, thereby producing the liquid fuel.

[0104] In another aspect, the present invention provides a liquid fuel production facility, wherein the facility can produce at least 400 barrels per day of ready-to-use synthetic liquid fuel while producing very little CO 2and uses less than 80 MW of power, wherein the equipment includes: a) a cryogenic air separator that separates oxygen from ambient air, wherein the cryogenic air separator is connected to a combustion system that uses oxygen to burn natural gas to produce carbon dioxide and water; b) a gas turbine generator that is connected to the combustion system to allow combustion products including gaseous carbon dioxide and water to flow through the gas turbine generator to produce electricity; c) a heat exchanger that is connected to the gas turbine generator so that gaseous carbon dioxide and water leaving the gas turbine are introduced into the heat exchanger, and the heat exchanger cools the gaseous carbon dioxide and water; d) a cooler and moisture separator that is connected to the heat exchanger so that cooled gas from the heat exchanger flows into the cooler and moisture separator, thereby removing water from the gas stream and producing carbon dioxide; e) a first catalytic reactor that is connected to the cooler and moisture separator so that carbon dioxide is introduced into the first catalytic reactor, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and ideally the catalyst comprises Ni 2 Mg, and the first catalytic reactor is capable of producing synthesis gas; f) a second catalytic reactor, the second catalytic reactor is connected to the first catalytic reactor so that synthesis gas flows from the first catalytic reactor to the second catalytic reactor, wherein the second catalytic reactor contains a second catalyst, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of cobalt and about 0.1 parts by weight to about 5 parts by weight of at least one metal per 100 parts by weight of a carrier selected from the group consisting of silica, alumina and combinations thereof, the at least one metal being selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, and the second catalytic reactor is capable of producing liquid fuels from the synthesis gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0105] FIG. 1 shows a method for extracting CO from a 2 and renewable H 2 Process flow diagram of improved catalyst and process for direct production of liquid fuels. The diagram further illustrates the integrated conversion system and process for producing renewable liquid fuels.

[0106] Figure 2 summarizes the 2 With H 2 Desired reactions (201, 203, and 204) and undesired side reactions (202, 205-213) that may occur when the mixture is catalytically converted into CO.

[0107] FIG. 3 shows the effect of operating temperature on CO production by catalyst #1 105 at 50 psi.

[0108] FIG. 4 shows the relationship between the operating pressure and CO conversion efficiency of catalyst #2 107 at 450°F.

[0109] FIG. 5 shows the main processes for the Allam oxy-fuel combustion process and the integration of the direct liquid fuel production process with the Allam oxy-fuel combustion process. DETAILED DESCRIPTION

[0110] The present invention relates to a method for converting CO into 2 With H 2 Improved catalysts and processes for efficiently and economically converting mixtures directly into synthetic liquid fuels.

[0111] FIG. 1 shows a method for extracting CO from a 2 and renewable H 2 Process flow diagram of improved catalyst and process for direct production of liquid fuels. The diagram further illustrates an integrated catalytic converter and process for producing renewable liquid fuels.

[0112] Using electrolysis to generate H 2 101. For H 2 The power produced may come from, but is not limited to, renewable and / or low-carbon sources such as wind, solar, geothermal, hydro, ocean currents, biomass, flare gas, nuclear, etc. Other possible sources include low-cost (off-peak) power from traditional fossil fuel power plants or high-efficiency power from oxy-combustion power plants.

[0113] Captured CO 2 102 can be obtained from, but not limited to, the following sources: fermentation process; cement plant; conventional power plant; oxygen combustion power plant; ambient air CO 2 Capture systems; natural gas well pipes, secondary oil recovery processes; and other CO 2 source.

[0114] H from Craft 101 2 ; CO from process 102 2 and the synthesis gas and heat (Q) from the process 110 are mixed 103 in appropriate proportions, heated, and input into the catalytic conversion system 104. Two innovative catalysts, catalyst #1 105 and catalyst #2 107, are incorporated into the catalytic conversion system 104.

[0115] Catalyst #1 105 is a high surface area nickel and magnesium solid solution catalyst, ideally comprising Ni 2 Mg, and the method described herein for converting CO 2 With H 2A solid solution catalyst is provided to effectively convert a mixture of H into synthesis gas. This catalyst is a significant improvement over the low surface area solid solution catalysts described by Schuetzle et al. in U.S. Pat. No. 9,611,145 and Canadian Pat. Nos. 2,936,903 and 2,993,671. 2 Before reduction (activation), the catalytic material described in the prior art is mainly composed of Ni in the lowest possible valence state. + Compounds (such as Ni 2 O and Ni 2 MgO 2 ) 2 O is known as a nickel suboxide having a tetragonal structure (Wagner et al., U.S. Pat. No. 4,990,491). 2 Reduction of Ni 2 MgO 2 Produces active CO 2 Reforming Catalyst Ni 2 Mg, and at high temperature in the presence of MgO with H 2 Reduction of Ni 2 O mainly produces element Ni. 2 Calcination is not 100% effective, so there is still some Ni and Ni 2 MgO 2 .

[0116] The improvement described herein involves producing a product composed primarily of Ni 2 A process for producing a robust catalyst composed of magnesium having a surface area increased by about ten times over that of catalysts described in the prior art.

[0117] Catalyst #2 107 is a catalyst developed for direct production of liquid fuels from syngas as described by Schuetzle et al. in U.S. Pat. Nos. 8,394,862; 9,090,831; and 9,631,147. Catalyst #1 105 and Catalyst #2 107 have been developed to operate at approximately the same pressure in the range of about 50 psi to 350 psi.

[0118] Since catalyst #1 operates at a higher temperature than catalyst #2 107, a heat exchanger 106 is incorporated into the catalytic conversion system 104 to reduce 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 tail gas 109, water 111, and renewable liquid fuel 113.

[0119] Some of the tail gas 109 is recycled back to the catalytic conversion process 104 until the desired conversion efficiency of CO in the syngas is achieved. The remaining tail gas 109 is combusted 110 (autothermal reforming (ATR)) with oxygen produced from the electrolysis system 101. The products from the ATR process 110 are syngas and heat. The syngas is blended with other gases in 103, and the heat from 110 is used to help heat the gas blending / heating system 103. Additional heat is added to the gas blending system 103 to bring the gas temperature to the operating temperature of catalyst #1 105.

[0120] The water (often referred to as catalyst reaction water) 111 can be used for grey water applications 112, or purified for use in the electrolysis process 101 and / or other uses. The renewable liquid fuel 113 can be used directly (purely) in off-road diesel engines 114, blended with petroleum-derived diesel fuel 115, or distilled 116 into premium fuel products (e.g., No. 1 diesel, No. 2 diesel, No. 3 diesel, and jet fuel) 117.

[0121] Figure 2 summarizes the 2 With H 2 The catalyst described in this improved technology has been developed to convert mainly CO 2 With H 2 The mixture is reacted by reaction 201 and from CO 2 With C 1 -C 8 The hydrocarbon mixture is reacted via reactions 203 and 204 (if with CO 2 If present together), CO is produced.

[0122] Improved catalysts and processes mainly from CO 2 and H 2 (Reaction 201) produces CO, or from CO 2 and hydrocarbons (reactions 203 and 204) to produce CO. These reactions are endothermic, meaning that heat is added to make the conversion occur. As shown in FIG. 1 , the first catalyst in the catalytic reactor is used to efficiently convert CO 2 With H 2 The mixture is converted into CO. This improved CO 2 The reforming catalyst 105 produces CO primarily under low pressure operating conditions (<350 psi) with a selectivity greater than about 90%.

[0123] Figure 3 shows the effect of operating temperature on the CO 2 The reforming catalyst was heated from CO at 50 psi. 2 As the temperature increases from about 750°F to 1300°F, CO 2The conversion rate increases exponentially. Then, from about 1300°F to 1700°F, CO 2 The conversion rate flattens out, which is consistent with the power fit (y = 0.45x-309). At 1700°F, CO 2 The conversion efficiency was about 75% and the selectivity to CO production was about 100%.

[0124] Table 3 summarizes the CO 2 The reforming catalyst is suitable for heating from CO at about 1600°F and 50 psi. 2 Produces CO and CH 4 The selectivity of CO 2 The conversion efficiency is about 72% and the selectivity to CO is about 100%. No other products are formed under these conditions, such as CH 4 (Reactions 202 and 205); and carbon (Reactions 209, 210, 211, 212, and 213). Reactions 206, 207, and 208 are very minor because CO 2 / H 2 H in the material flow 2 O concentration is very low. Table 3 - Improved CO 2 The reforming catalyst produces CO and CH at about 1600°F and 50 psi. 4 Selectivity

[0125]

[0126] Table 4 summarizes the effect of pressure on CO at 1600°F. 2 As the pressure increases from 50 psi to 300 psi, the CO selectivity decreases from approximately 100% to 89%, while CH 4 The selectivity increases from 0% to 11%. This pressure change has an effect on the CO 2 There is no impact on conversion efficiency.

[0127] Table 4 - Effect of operating pressure on improved CO 2 The reforming catalyst converts CO to 2 Effect of conversion efficiency to CO

[0128]

[0129] The second catalyst 107 (FIG. 1) in the back end of the converter utilizes a Greyrock direct fuel production catalyst previously described by Schuetzle et al. in US Pat. Nos. 8,394,862 and 9,909,071 that has been modified in this process to operate efficiently down to about 50 psi.

[0130] This composition of the 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 per 100 parts by weight of a carrier selected from the group consisting of silica, alumina and combinations thereof. This catalyst is commercially produced using a stationary calciner such that the catalyst particle aspect ratio (length-to-width ratio), surface area, subsurface and surface pore size distribution, pore volume and catalyst crystallinity are maintained within about 5% of the specification.

[0131] FIG4 shows the relationship between the operating pressure and CO conversion efficiency of catalyst #2 107 at 450°F. It was found that the change in % CO conversion rate conforms to the relationship given by Equation 2, where P 1 and P 2 is the pressure to be compared:

[0132] CO conversion rate change % = (P 1 / P 2 ) 0.5 Equation 2

[0133] Since the first catalyst operates at a higher temperature than the second catalyst, a heat exchanger (FIG. 1-106) is incorporated between the catalysts to reduce the temperature of the second catalyst to its ideal operating level.

[0134] The most important advantage of this process is that catalysts #1 and #2 can be effectively operated in series at the same pressure, which eliminates the need for compression between the two catalytic reactors.

[0135] Table #5 provides the temperature of Catalyst #2 and the CO content of the syngas produced from Catalyst #1 2 Therefore, catalyst #2 converts some of the CO that was not converted by catalyst #1. 2 .

[0136] Table 5 - Effect of Temperature on CO in Syngas Passing Catalyst #2 2 The impact of conversion

[0137] T(℉) <![CDATA[CO 2 Conversion rate (%)]]> 400 1.71 410 3.23 420 5.39 430 9.25 440 14.6 450 24.5

[0138] Since CO at 1600°F and 150 psi 2 The conversion is 72% efficient (Table 3), so the resulting syngas contains about 28% CO 2 Thus, when Catalyst #2 was operated at 450°F, approximately 25% of the incoming syngas for Catalyst #2 was converted to CO 2 , resulting in the tail gas containing 34.1% H 2, 17.1% CO, 23.1% CH 4 and 25.6% CO 2 .

[0139] Table 6 summarizes the products produced under two different pressure operating conditions. 2 / CO 2 The mixture (2.2 / 1.0) was fed into a modified CO 2 When the reforming catalyst is in the 2 The synthesis gas has a / CO ratio of about 2.0-2.3 / 1.0.

[0140] When this syngas is fed into a direct fuel production catalyst operating at 415°F and 300 psi, the liquid fuel (C 5 -C 23 Hydrocarbons) are produced at a single pass selectivity of 47.5%. By-products include gas phase C 1 -C 4 Hydrocarbon, solid phase C 24 + hydrocarbons and unreacted CO 2 , with selectivities of 21.2%, 2.5% and 25.8% respectively.

[0141] Table 6 - Catalyst operating conditions for H 2 / CO 2 Effect of operating conditions on catalytic converters for producing synthetic liquid fuels from mixtures (2.2 / 1.0)

[0142]

[0143] CO used as process input 2 It can be obtained from many different sources including ambient air, fermentation processes, cement plants, conventional power plants, oxy-combustion processes, biogas, gas recovered from secondary oil recovery processes, and the like.

[0144] Contains C 2 -C 6 CO of hydrocarbons 2 They can also be used as process inputs, as these hydrocarbons are also converted into liquid fuels or methane. Such streams include natural gas condensate, gases from refinery processes, and other materials containing CO 2 and gas streams of light hydrocarbons.

[0145] The above integrated process requires carbon dioxide input. In one embodiment, carbon dioxide is supplied by separating carbon dioxide from a flue gas stream using an alkylamine. The alkylamine used in the process may include monoethanolamine, diethanolamine, methyldiethanolamine, dipropylamine, aminoethoxyethanol, or a combination thereof. In another embodiment, carbon dioxide is already present in the natural gas feedstock.

[0146] The manufacturing process of the first catalyst is important because the catalyst produced by the manufacturing process forms a unique solid solution phase, i.e. a bimetallic crystalline phase, which results in no separation of the metal phase. When compared with conventional metal-supported reforming catalysts, this unique chemical structure results in enhanced coking resistance. This also results in enhanced resistance to synthesis gas poisons such as sulfur and ammonia. In addition, compared with a single metal separation catalyst phase (e.g. Ni on alumina), this catalyst has enhanced catalytic activity at a lower surface area. This catalyst does not need to suppress the base promotion required for carbon deposition seen when using feed gas as described herein. The catalyst can also be operated with various dry, steam, combined dry / steam and triple reforming feeds. A mixture of high-grade hydrocarbon feedstocks can also be obtained with this catalyst.

[0147] Improved CO 2 The manufacture of hydrogenation catalysts may involve some or all of the following steps which will result in an effective and economical commercial solid solution catalyst:

[0148] a. High surface area (>50m 2 / g) synthesis of metal-spinel, wherein the metal-spinel 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.

[0149] b. Modification of the spinels listed above by impregnation with up to 20 wt % of additional Fe, Mg, Mn, Ca, Ba, Cu or Zn not chemically bonded to one or more of the spinels listed above.

[0150] c. Impregnation of the metal-coated spinel with a solution consisting of a mixture of a water-soluble nickel salt and a rare earth metal salt (eg, nitrate or acetate).

[0151] d. Calcination of metal coated spinel at temperatures up to 2100°F.

[0152] e. Additional impregnation and calcination are performed as needed to produce an impregnated spinel composed of 2-20 wt% Ni and 0.1-5.0 wt% rare earth metal.

[0153] CO2 Source – Carbon capture is the capture of CO from point sources 2 The pioneering catalytic converter and process described in this article require CO 2 Feedstock can be captured efficiently and economically with lower contaminant levels.

[0154] Several methods have been developed to capture CO from fermentation processes, conventional power plants, oxy-combustion power plants, cement plants, 2 , and CO2 collection from biogas sources, refineries, and secondary oil recovery processes 2 / hydrocarbon streams (Schuetzle et al., 2010).

[0155] Power plants typically use control devices to remove sulfur oxides and particulates. The addition of carbon capture systems requires significant additional capital costs and increased parasitic power. Therefore, removal in conventional power plants can increase the cost of electricity by 50% to 70% (IGCC, 2005). Capturing CO from coal-fired and natural gas-fired power plants 2 The average cost of emissions is $130 / ton and $95 / ton, respectively (Metz et al., 2005).

[0156] Oxy-combustion power plants have the potential to produce high-quality CO at low cost 2 NET Power is a leader in the development and deployment of these power plants (Allam et al., 2017). NET Power has developed and deployed a novel power generation system that generates electricity from natural gas at approximately 59% net energy efficiency, at a cost comparable to current technology, and generates zero atmospheric emissions.

[0157] The NET Power system is based on a new thermodynamic cycle called the Allam cycle (Allam et al., 2013). It uses high pressure, high recuperative, oxygen-fuel, supercritical CO 2 cycle, which makes emissions capture part of the core power generation process. The result is high-efficiency power generation that inherently produces CO without adding cost to system performance. 2 Byproduct. CO produced from this oxygen combustion process 2 It is an ideal feedstock for producing ultra-low carbon liquid fuels through this catalytic converter and process.

[0158] Fermentation processes are used to produce distillates, wine, beer, and ethanol fuel. As shown in Table 7, CO 2 It is the main component of the fermentation process discharge. Ethanol concentration is low, ranging from about 2000-4000ppm. Since fermentation is an anaerobic process, O 2 Usually absent. Small amounts of sulfur compounds, such as H2 S and SO 2 May be present in low concentrations (Safriet, 1995).

[0159] Table 7 - Typical concentrations of components in effluents from fermentation processes

[0160] Element concentration <![CDATA[CO 2 ]]> 99.6％ Ethanol 3000-4000ppm <![CDATA[H 2 S]]> 1.1ppm <![CDATA[SO 2 ]]> <0.2ppm <![CDATA[O 2 ]]> <0.1ppm

[0161] Due to the low concentration of pollutants, this is an ideal CO source for the improved direct fuel production process described in the present invention. 2 Source. Low concentrations of sulfur compounds are easily removed using conventional adsorbents. The captured CO 2 The cost of ethanol is in the range of $5 / ton to $35 / ton. The second catalyst in the catalytic reactor converts a large portion (>50 mole %) of the ethanol into liquid fuel.

[0162] The cement industry currently accounts for 2 ) emissions and is the third largest industrial energy consumer. Cement production involves the decomposition of limestone (calcium carbonate), which accounts for about 7% of the total CO generated in the process. 2 About two-thirds of emissions, the remaining CO 2 Emissions are due to the combustion of fuels. This industry accounts for 2.3% of the total direct industrial carbon dioxide (CO 2 ) emissions, accounting for the second largest share, at 27% (220 million tonnes) of CO2 / year in 2014 [GtCO 2 / year](IEA, 2018).

[0163] Cement plant emissions contain about 25% CO by volume 2 Amine (MEA)-based capture technology currently costs about $90 / ton. If oxygen-containing fuels are used for heating, the cost drops to about $50 / ton CO. 2 (Gardarsdottir et al., 2019). However, this cost could be much higher if major modifications to the cement plant are required. CO captured from cement plants using amine capture or oxyfuel combustion 2 It is an ideal feedstock for producing renewable fuels from this catalytic converter and process.

[0164] Once CO is captured 2 , it must be compressed to high pressure for storage in large containers, or cooled to produce liquid CO 2 , the liquid CO 2 stored in insulated containers. 2 These costs can be eliminated by converting directly to liquid fuels at the plant site.

[0165] Several methods have been developed to collect CO from ambient air. 2 The challenge with these ambient air collection processes is that CO 2 The cost of collection is very high, currently in the range of $400-600 / metric ton or more, although costs are likely to fall as these technologies become commercialized.

[0166] Some CO 2 Source and significant level of C 1 -C 6 Some examples of such sources include CO from natural gas wellheads 2 / light hydrocarbon mixture, from the use of CO 2 Emissions from secondary oil recovery using biogas.

[0167] CO 2 Injection into oil reservoirs is a common method of secondary oil recovery. 2 After injection, the recovered CO 2 Contains light hydrocarbons, which require CO 2 Separation is performed before re-injection. U.S. Patent No. 9,159,105 describes a process for separating light hydrocarbons from CO2 using an air capture unit. 2 The wells are reinjected for additional oil recovery, and the light hydrocarbons are used as fuel for local use.

[0168] Various Implementation Methods

[0169] Technology

[0170] 1. A process for converting carbon dioxide into liquid fuels, wherein the process comprises the following steps: a) introducing a gaseous mixture of carbon dioxide and hydrogen, or a mixture of carbon dioxide, hydrogen and light hydrocarbons into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and ideally the catalyst comprises Ni 2 Mg; b) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce exhaust gas, water and liquid fuel, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of an element selected from the group consisting of silica, alumina and combinations thereof, per 100 parts by weight of a carrier selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 parts by weight to about 5 parts by weight of at least one metal selected from the following items: cerium, ruthenium, lanthanum, platinum, or rhenium, thereby producing liquid fuel, exhaust gas and water; c) separating the liquid fuel, exhaust gas and water from each other, thereby producing the liquid fuel.

[0171] 2. The process according to process 1 above, wherein the synthesis gas is introduced into a heat exchanger to reduce the temperature of the synthesis gas before the synthesis gas is introduced into the second catalytic reactor.

[0172] 3. The process according to process 1 above, wherein the carbon dioxide introduced into the first catalytic reactor is obtained from a source, wherein the source is selected from the group consisting of: an oxy-combustion power plant, ambient air CO 2 capture systems, gas wellheads and secondary recovery processes.

[0173] 4. A process according to process 1 above, wherein hydrogen is generated using electrolysis, wherein the power used for the electrolysis is generated from a renewable or low-carbon source, and wherein the renewable or low-carbon source is selected from the group of sources consisting of wind power, solar power, geothermal power, hydropower, ocean currents, biomass, flare gas, nuclear power, off-peak power from fossil fuel plants, and power produced by oxygen combustion plants.

[0174] 5. A process according to process 1 above, wherein the exhaust gas is recirculated back to the catalytic conversion system.

[0175] 6. The process according to process 1 above, wherein the water is used for grey water applications.

[0176] 7. A process according to process 1 above, wherein the second catalytic reactor is operated at a pressure of about 50 psi to about 400 psi, about 50 psi to about 300 psi, about 50 psi to about 200 psi, about 50 psi to about 150 psi, or about 50 psi to about 100 psi.

[0177] 8. A process according to process 1 above, wherein the tail gas is partially combusted with oxygen from an electrolysis system, the electrolysis system is used to generate hydrogen to produce synthesis gas and heat, and wherein the synthesis gas is mixed with other gases introduced into the second catalytic reactor.

[0178] 9. A process according to process 1 above, wherein the liquid fuel is used as a fuel for off-road diesel engines without further processing.

[0179] 10. The process according to process 1 above, wherein the liquid fuel is mixed with petroleum diesel fuel to provide a fuel blend.

[0180] 11. The process according to process 1 above, wherein the liquid fuel is distilled to provide No. 1 diesel, No. 2 diesel, No. 3 diesel or jet fuel.

[0181] 12. The process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing at least one catalyst having a surface area greater than about 50 m 2 / g of a metal spinel, 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 about 1 wt % to about 20 wt % of an additional chemical element that is not chemically bonded to the spinel to provide a metal-coated spinel, wherein the additional chemical element Selected from the group consisting of: Co, Fe, Mg, Mn, Ca, Ba, Cu or Zn; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0182] 13. A process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Co-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Co to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0183] 14. A process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Fe-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Fe to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize the first catalyst, which is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0184] 15. The process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Mg-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Mg to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize the first catalyst, which is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0185] 16. The process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Mn-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Mn to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0186] 17. A process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Ca-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Ca to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0187] 18. A process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Ba-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Ba to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0188] 19. A process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Cu-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Cu to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize the first catalyst, which is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0189] 20. The process according to process 1 above, wherein the first catalyst is synthesized by a process comprising the following steps: a) synthesizing a catalyst having a surface area greater than about 50 m 2 / g of Zn-alumina spinel; b) coating the spinel with about 1 wt% to about 20 wt% Zn to provide a metal-coated spinel; c) impregnating the metal-coated spinel with a solution comprising a water-soluble nickel salt and a nitrate or acetate of a rare earth metal; d) calcining the impregnated metal-coated spinel at a temperature up to 2100°F to synthesize a first catalyst, wherein the first catalyst is an impregnated spinel composed of about 2 wt% to about 20 wt% nickel and about 0.1 wt% to about 5.0 wt% rare earth metal.

[0190] 21. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of cobalt, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0191] 22. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of iron, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0192] 23. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of magnesium, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0193] 24. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of manganese, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0194] 25. The process of process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of calcium, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0195] 26. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of barium, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0196] 27. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of copper, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0197] 28. The process according to process 1 above, wherein the first catalyst is an impregnated metal-coated spinel comprising about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m 2 / g of zinc, wherein the first catalyst further comprises about 2 wt % to about 20 wt % of nickel.

[0198] catalyst

[0199] 1. A catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of an alumina support having a surface area greater than about 50 m2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0200] 2. A catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of an alumina support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0201] 3. A catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0202] 4. A catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0203] 5. A catalyst for converting carbon dioxide into synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of an alumina support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0204] 6. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0205] 7. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0206] 8. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0207] 9. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0208] 10. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of cobalt, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0209] 11. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0210] 12. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0211] 13. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0212] 14. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0213] 15. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0214] 16. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m2 per 100 parts by weight of a silica support. 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0215] 17. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0216] 18. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of a surface area greater than about 50 m2 per 100 parts by weight of a silica support. 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0217] 19. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0218] 20. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of iron, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0219] 21. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0220] 22. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0221] 23. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0222] 24. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0223] 25. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0224] 26. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0225] 27. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0226] 28. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0227] 29. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0228] 30. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of magnesium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0229] 31. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0230] 32. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0231] 33. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0232] 34. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0233] 35. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0234] 36. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0235] 37. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0236] 38. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0237] 39. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0238] 40. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of manganese, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0239] 41. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0240] 42. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0241] 43. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0242] 44. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0243] 45. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0244] 46. ​​A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0245] 47. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0246] 48. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0247] 49. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0248] 50. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of calcium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0249] 51. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0250] 52. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0251] 53. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0252] 54. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0253] 55. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0254] 56. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0255] 57. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0256] 58. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0257] 59. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0258] 60. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of barium, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0259] 61. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0260] 62. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0261] 63. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0262] 64. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0263] 65. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0264] 66. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0265] 67. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0266] 68. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0267] 69. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0268] 70. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of copper, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0269] 71. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0270] 72. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0271] 73. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0272] 74. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0273] 75. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight of alumina support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0274] 76. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of cerium, and about 2% by weight to about 20% by weight of nickel.

[0275] 77. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of ruthenium, and about 2% by weight to about 20% by weight of nickel.

[0276] 78. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of lanthanum, and about 2% by weight to about 20% by weight of nickel.

[0277] 79. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of platinum, and about 2% by weight to about 20% by weight of nickel.

[0278] 80. A catalyst for converting carbon dioxide to synthesis gas, wherein the catalyst is an impregnated metal-coated spinel comprising from about 2 parts by weight to about 25 parts by weight per 100 parts by weight of a silica support having a surface area greater than about 50 m 2 / g of zinc, about 0.1 parts by weight to about 5 parts by weight of rhenium, and about 2% by weight to about 20% by weight of nickel.

[0279] Reactor

[0280] 1. A catalytic conversion system for converting carbon dioxide into liquid fuel, wherein the catalytic system comprises a first catalytic reactor and a second catalytic reactor, wherein the first catalytic reactor contains a first catalyst, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and ideally the catalyst comprises Ni 2 Mg, wherein the second catalytic reactor contains a second catalyst, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of cobalt and about 0.1 parts by weight 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 carrier selected from the group consisting of silica, alumina, and combinations thereof.

[0281] 2. A catalytic conversion system according to the above-mentioned reactor 1, wherein the catalytic conversion system further comprises a heat exchanger between the first catalytic reactor and the second catalytic reactor, wherein the gas flows from the first catalytic reactor to the heat exchanger and then flows to the second catalytic reactor.

[0282] 3. The catalytic conversion system according to the above-mentioned reactor 1, wherein the catalytic conversion system further comprises a gas mixing chamber, which is connected to the first catalytic reactor so that the gas can flow between the gas mixing chamber and the first catalytic reactor.

[0283] 4. A catalytic conversion system according to the above-mentioned reactor 1, wherein the catalytic conversion system further comprises an electrolysis system for generating hydrogen, wherein the electrolysis system is connected to the gas mixing chamber so that the hydrogen generated in the electrolysis system can flow to the gas mixing chamber.

[0284] 5. A catalytic conversion system according to the above-mentioned reactor 3, wherein the catalytic conversion system further comprises a system for capturing carbon dioxide, wherein the system for capturing carbon dioxide is connected to the gas mixing chamber so that the carbon dioxide obtained in the carbon dioxide capture system can flow to the gas mixing system.

[0285] 6. A catalytic conversion system according to the above-mentioned reactor 4, wherein the catalytic conversion system further comprises a system for capturing carbon dioxide, wherein the system for capturing carbon dioxide is connected to the gas mixing chamber so that the carbon dioxide obtained in the carbon dioxide capture system can flow to the gas mixing system.

[0286] Integrated conversion system

[0287] 1. A process for producing liquid fuels, wherein the process comprises the following steps: a) separating oxygen from ambient air using a cryogenic air separator; b) mixing oxygen with natural gas at high pressure and temperature in the presence of heated supercritical carbon dioxide, thereby combusting the natural gas to produce combustion gases comprising carbon dioxide and water and heat; c) passing the combustion gases through a gas turbine generator to produce electricity for at least two purposes, and wherein the at least two purposes are distribution to a power grid and use in the process of producing liquid fuels, and allowing the combustion gases to leave the gas turbine generator; d) further passing the combustion gases through a heat exchanger, wherein the heat exchanger reduces the temperature of the combustion gases; e) removing water from the combustion gases to provide carbon dioxide; f) introducing a portion of the carbon dioxide together with hydrogen, or a mixture of the carbon dioxide portion with hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and the catalyst desirably comprises Ni 2 Mg, and compressing any remaining carbon dioxide while heating to provide supercritical carbon dioxide; g) introducing the synthesis gas into a second catalytic reactor in a catalytic conversion system to produce tail gas, water and liquid fuel, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of an element selected from the group consisting of silica, alumina and combinations thereof, per 100 parts by weight of a carrier selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and about 0.1 parts by weight to about 5 parts by weight of at least one metal selected from the following items: cerium, ruthenium, lanthanum, platinum, or rhenium, thereby producing liquid fuel, tail gas and water; h) separating the liquid fuel, tail gas and water from each other, thereby producing the liquid fuel.

[0288] Production Equipment

[0289] 1. A liquid fuel production facility, wherein the facility can produce at least 400 barrels / day of ready-to-use synthetic liquid fuel while producing very little carbon dioxide emissions and using less than 80 MW of power, wherein the facility comprises: a) a cryogenic air separator that separates oxygen from ambient air, wherein the cryogenic air separator is connected to a combustion system that uses the oxygen to burn natural gas to produce carbon dioxide and water; b) a gas turbine generator that is connected to the combustion system to allow combustion products including gaseous carbon dioxide and water to flow through the gas turbine generator to produce electricity; c) a heat exchanger; a heat exchanger connected to the gas turbine generator such that gaseous carbon dioxide and water leaving the gas turbine are introduced into the heat exchanger, which cools the gaseous carbon dioxide and water; d) a cooler and moisture separator connected to the heat exchanger such that the cooled gas from the heat exchanger flows into the cooler and moisture separator, thereby removing water from the gas stream and producing carbon dioxide; e) a first catalytic reactor connected to the cooler and moisture separator such that carbon dioxide is introduced into the first catalytic reactor, wherein the first catalyst is a nickel and magnesium solid solution catalyst, and the catalyst desirably comprises Ni 2 Mg, and the first catalytic reactor is capable of producing synthesis gas; f) a second catalytic reactor, the second catalytic reactor is connected to the first catalytic reactor so that synthesis gas flows from the first catalytic reactor to the second catalytic reactor, wherein the second catalytic reactor contains a second catalyst, wherein the second catalyst comprises about 2 parts by weight to about 25 parts by weight of cobalt and about 0.1 parts by weight to about 5 parts by weight of at least one metal per 100 parts by weight of a carrier selected from the group consisting of silica, alumina and combinations thereof, the at least one metal being selected from the group consisting of cerium, ruthenium, lanthanum, platinum, or rhenium, and the second catalytic reactor is capable of producing liquid fuels from the synthesis gas.

[0290] Further processes and catalysts

[0291] 1. A catalytic process comprising two catalysts to convert CO 2 / H 2 Mixture or CO 2 / H 2 A method for efficiently converting a mixture of syngas and light hydrocarbons directly into synthetic liquid fuels, 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 the synthesis gas into synthetic fuels.

[0292] 2. A process according to the above further process and catalyst 1, wherein H is produced from water using electrolysis 2 .

[0293] 3. A process according to the above further process and catalyst 1, wherein H 2 It may be produced from steam reforming of solid carbonaceous materials such as biomass, flare gas, biogas, methane, light hydrocarbons, and other components of various stoichiometric mixtures containing carbon, hydrogen, and oxygen.

[0294] 4. A process according to the above further process and catalyst 1, wherein CO 2 It can be used from conventional power plants, oxygen combustion power plants, fermentation processes, cement plants, ambient air CO 2 capture systems, biogas, wastewater treatment plants, secondary oil recovery, refineries, chemical production plants, geothermal power plants, nylon plants or ammonia plants capture.

[0295] 5. A process according to the above further process and catalyst 1, wherein the H input to the catalytic conversion process is 2 / CO 2 The ratio of the mixture may vary from 1.5 / 1.0 to 5.0 / 1.0, preferably from 2.0 / 1.0 to 3.0 / 1.0.

[0296] 6. A process according to the above further process and catalyst 1, wherein the H 2 / CO 2 The mixture is input into the catalytic converter at a pressure between 25 psi and 400 psi.

[0297] 7. A process according to the above further process and catalyst 1, wherein the H 2 / CO 2 The mixture is input into the catalytic converter at a pressure between 150 psi and 325 psi.

[0298] 8. A process according to the above further process and catalyst 1, wherein the H 2 / CO 2 The mixture is heated to a temperature greater than the operating temperature of the first catalyst such that little or no additional heating of the first catalyst is required.

[0299] 9. The process according to the above further process and catalyst 1, wherein the first catalyst and the second catalyst in the catalytic reactor are operated at almost the same pressure.

[0300] 10. A process according to the above further process and catalyst 1, wherein the first catalyst is mainly composed of 2-35 wt% Ni supported on a high surface area alumina spinel. 2 An improved solid solution catalyst composed of Mg, wherein the alumina spinel can be composed of Co-alumina spinel, Fe-alumina spinel, Mg-alumina spinel, Mn-alumina spinel, Ca-alumina spinel, Ba-alumina spinel, Ni-alumina spinel, Cu-alumina spinel or Zn-alumina spinel, and wherein M is a metal, such as Mg, Mn, Ca, Ba, Cu, Zn or Sr.

[0301] 11. An improved solid solution catalyst according to the above further process and catalyst 9, wherein the first catalyst may contain 0.1 weight part to about 5.0 weight parts of a promoter per 100 weight parts of the carrier, the promoter being composed of at least one or more transition or rare earth metals.

[0302] 12. The improved solid solution catalyst according to the further process and catalyst 9 above, wherein the catalyst contains less than 0.05% of rare metals.

[0303] 13. The improved solid solution catalyst according to further process and catalyst 9 above, wherein a water soluble salt of nickel and said promoter are impregnated onto said spinel substrate, dried and calcined at a temperature up to 2100°F.

[0304] 14. The calcined catalyst according to the above further process and catalyst 12, wherein the calcined catalyst is mainly composed of 5-35 wt.% Ni 2 MgO 2 and 0.2-5.0 wt % of a promoter oxide.

[0305] 15. The calcined catalyst according to the above further process and catalyst 13 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.

[0306] 16. The calcined catalyst according to the further process and catalyst 13 above, wherein the calcined catalyst is heated to a temperature of up to about 1200°F with H 2 Or other reducing agents commonly used in the art to reduce to mainly form Ni 2 Mg and the one or more transition or rare earth metals in elemental form.

[0307] 17. The reduced catalyst according to further process and catalyst 15 above, which is effective to convert H to CO when operated at a pressure in the range of 20-200 psi, more preferably in the range of 50-150 psi. 2 With CO 2 The mixture is converted into synthesis gas.

[0308] 18. The catalyst according to the above further process and catalyst 15, wherein the catalyst is heated to 5000 hr. -1 Up to 200000hr -1 When operating at an airspeed of 2 With CO 2 The mixture is converted into synthesis gas.

[0309] 19. A catalyst according to the above further process and catalyst 15, wherein the catalyst effectively converts H 2 With CO 2 The mixture is converted into synthesis gas, in which H 2 With CO 2 The ratio may vary between 1.0 and 4.0, preferably between 1.5 and 3.5, more preferably between 2.0 and 3.0.

[0310] 20. The catalyst according to the above further process and catalyst 15, wherein the syngas is at a pressure of 50-300 psi at 1600°F with greater than about 55% CO 2 to CO conversion efficiency.

[0311] 21. A catalyst according to the above further process and catalyst 15, wherein the catalyst produces H 2 Synthesis gas having a / CO ratio in the range of 1.0-3.0, preferably in the range of 1.5-2.5.

[0312] 22. The catalyst according to the further process and catalyst 15 above, which is thermally stable up to 2100°F.

[0313] 23. A catalyst according to the above further process and catalyst 15, wherein the catalyst has a high activity on the captured CO 2 The invention is resistant to contaminants present in the feed stream, natural gas, biogas or other gaseous feed streams.

[0314] 24. The catalyst according to the above further process and catalyst 15, wherein the catalyst does not form carbon via coking or forms nominal carbon via coking.

[0315] 25. A catalyst according to the above further process and catalyst 15, wherein CH4 When present in CO 2 / H 2 The mixture is efficiently converted into synthesis gas.

[0316] 26. A catalyst according to the above further process and catalyst 15, wherein C 2 -C 7 When hydrocarbons are present in CO 2 / H 2 The mixture is efficiently converted into synthesis gas.

[0317] 27. The catalyst according to the above further process and catalyst 15, when O 2 Added to CO 2 , H 2 , CH 4 , and C 2 -C 5 The invention is used to efficiently produce synthesis gas when a selected mixture of hydrocarbons is used.

[0318] 28. A process according to further process and catalyst 15 above, wherein the synthesis gas is fed to other catalytic reactors to produce fuels and / or chemicals.

[0319] 29. The process according to the above further process and catalyst 15, wherein a heat exchanger is used to reduce the temperature from the first catalyst to the operating temperature of the second catalyst of 400-475°F.

[0320] 30. A process according to further process and catalyst 28 above, wherein the cooled synthesis gas is fed to a second catalyst, and wherein such second catalyst comprises from about 2 parts by weight to about 50 parts by weight of cobalt and from about 0.1 parts by weight to about 10 parts by weight of at least one metal selected from the group consisting of cerium, ruthenium, lanthanum, platinum, palladium and rhenium per 100 parts by weight of a carrier selected from the group consisting of silica, alumina and combinations thereof; thereby producing diesel fuel.

[0321] 31. A process according to the above further process and catalyst 29, wherein the second catalyst produces C 1 -C 5 Gas phase hydrocarbons; C 5 -C 23 Liquid hydrocarbons; CO, H 2 , C 1 -C 5 Hydrocarbons, CO 2 Exhaust gas composed of 2 O; and C 24 + Hydrocarbons.

[0322] 32. The process according to the above further process and catalyst 30, comprising introducing the product stream from the second reactor system into a separator, wherein the separator separates the C 24 + Hydrocarbons are separated from other products.

[0323] 33. A process according to the above further process and catalyst 30, wherein the C 24 + hydrocarbons with the C 5 -C 23 Distribution of hydrocarbons.

[0324] 34. A process according to further process and catalyst 31 above, wherein the remaining liquid product stream is condensed into two fractions, wherein the top fraction comprises liquid hydrocarbon fuel and the bottom fraction comprises water.

[0325] 35. A process according to further process and catalyst 33 above, wherein the liquid hydrocarbon fuel is separated from water.

[0326] 36. A process according to further process and catalyst 34 above, wherein the liquid hydrocarbon fuel is used directly in off-road diesel engines and vehicles.

[0327] 37. A process according to further process and catalyst 34 above, wherein the liquid hydrocarbon fuel is blended with petroleum diesel fuel and used in on-road diesel engines and vehicles.

[0328] 38. The process according to further process and catalyst 34 above, wherein the synthetic liquid fuel is distilled to produce No. 1 diesel fuel; No. 2 diesel fuel; jet fuel; blending type refined gasoline; and a small fraction (less than about 5% by volume) of heavy (C 24 +) hydrocarbons.

[0329] 39. The process according to further process and catalyst 37 above, wherein the blended refined gasoline is blended with petroleum gasoline fuel and used in spark ignition engines and vehicles.

[0330] 40. A process according to further process and catalyst 37 above wherein No. 1 diesel (kerosene) is used for kerosene heaters and furnaces.

[0331] 41. A process according to further process and catalyst 37 above, wherein No. 1 diesel (kerosene) is used for jet engines and turbines.

[0332] 42. The process according to further process and catalyst 37 above, wherein the pure or blended synthetic fuel reduces standard engine emissions by at least 2% compared to petroleum based fuels.

[0333] 43. The process according to further process and catalyst 37 above, wherein the pure or blended synthetic fuel improves one or more fuel properties by at least 2% compared to petroleum-based fuels.

[0334] 44. The process according to further process and catalyst 37 above, wherein the pure or blended synthetic fuel reduces greenhouse gas emissions by at least 2% compared to petroleum based fuels.

[0335] 45. A process according to the above further process and catalyst 34, wherein some of the tail gas is recycled back to catalyst #2 for production of additional products.

[0336] 46. ​​A process according to further process and catalyst 34 above, wherein some of the tail gas is converted to additional synthesis gas by partial oxidation with oxygen (e.g. ATR conversion) or by autothermal reforming (ATR) generated from electrolysis.

[0337] 47. The process according to further process and catalyst 45 above, wherein the heated synthesis gas is added to the H before being fed to the first catalyst. 2 / CO 2 In the material flow.

[0338] 48. A process according to further processes and catalysts 1-28 above, wherein the synthesis gas is fed to other types of catalytic processes to produce fuels and / or chemicals.

[0339] 49. A process according to further process and catalyst 47 above, wherein the second catalyst is a Fischer-Tropsch type catalyst formulation that produces wax that is then converted to fuels and / or chemicals using conventional wax hydroreforming and hydroprocessing methods.

[0340] 50. The process according to further process and catalyst 47 above, wherein the second catalyst produces methanol, ethanol and / or other alcohols.

[0341] 51. A process according to further process and catalyst 47 above, wherein the second catalyst is used to produce methanol which is then converted to gasoline using additional conventional catalysts and processes as described in the prior art.

[0342] 52. The process according to further process and catalyst 47 above, wherein the synthesis gas is used to generate power using generator sets, gas turbines and other established gas to power equipment.

[0343] 53. A process according to further process and catalyst 47 above, wherein the syngas is used as a burner fuel to generate heat.

[0344] 54. A process according to further process and catalyst 47 above, wherein the second catalyst is used to produce ammonia.

[0345] Example

[0346] This illustrative example describes the CO from an oxyfuel combustion power plant. 2 As mentioned above, the use of these improved catalysts and processes to convert CO 2 Direct production of liquid fuels can be accomplished using CO2 from, but not limited to, conventional power plants, oxy-combustion power plants, ethanol fuel production plants, cement plants, ambient air, 2 Capture systems, geothermal power plants and other CO 2 CO obtained from emission sources 2 .

[0347] The main differences between these sources are the cost of obtaining relatively pure CO2 and the cost of the power used to generate H2 by water electrolysis. Since oxy-combustion power plants have the potential to generate CO2 directly at little or no cost and to generate H2 at reasonable cost, 2 Produces supply power, thus from CO 2 The direct conversion rate of the produced liquid fuels is a key embodiment described herein.

[0348] Oxyfuel combustion is the process of burning hydrocarbon fuels in an environment of nearly pure oxygen rather than air. Although coal has been tested in oxyfuel combustion plants, the combustion of coal produces large amounts of particulate matter (fly ash) and sulfur oxides (such as SO, SO 2 and SO 3 ). Therefore, the preferred hydrocarbon fuel is natural gas.

[0349] One of the most promising oxyfuel combustion processes utilizes the Allam cycle (Allam et al., 2017). This system uses a semi-closed loop, high pressure, low pressure ratio recuperative Brayton cycle that uses supercritical CO 2 As a working fluid, the cycle greatly reduces energy losses compared to cycles based on steam and air. In conventional cycles, impurities from low concentrations of combustion sources (such as CO 2 ) results in large additional capital costs and increased parasitic power, which can increase the cost of electricity by 50% to 70%. The compelling economic benefits of the Allam cycle are driven by the capture of nearly 100% of the CO at pipeline pressure with low projected capital and O&M costs. 2At the same time, the high target efficiency of 59% net natural gas (LHV basis) is driven. In addition, for a small performance reduction, the cycle can be operated essentially waterless. The system uses only a single turbine, utilizes a small equipment footprint, and requires smaller and fewer components than traditional hydrocarbon-fueled systems.

[0350] Figure 5 shows the main processes for the Allam oxyfuel combustion process and the integration of the direct liquid fuel production process with the Allam oxyfuel combustion process. A cryogenic air separator 501 is used to separate oxygen 503 from ambient air 502. Oxygen 503 is mixed with natural gas 504 at high pressure (about 320 bar) and high temperature (about 720°C) 20 in the presence of heated supercritical carbon dioxide.

[0351] Combustion produces additional carbon dioxide, water, and significant amounts of heat 506. Depending on the oxygen to natural gas ratio, combustion pressure and temperature, and power load at gas turbine conditions, some CO may be produced (Wang and Stiegel, 2017). However, when the combustion system is operated at or very near stoichiometric conditions (O 2 / fuel = 1.00), CO formation is very low.

[0352] The hot, high pressure mixture then passes through a gas turbine generator 507 where it rotates a shaft to generate electricity. Most of the power is distributed to the grid 508, and the remainder is used in the direct liquid fuel production process 510. The pressure of the gas stream 511 leaving the gas turbine is reduced to about 30 bar at about 720°C.

[0353] Gas stream 511 is passed through heat exchanger 512 which reduces the temperature of the gas stream to 43°C while maintaining a pressure of 30 bar. Cooler 513 and moisture separator 514 remove moisture from CO 2 Water is removed from the stream 515. The water contains small amounts of sulfates, which are derived from the combustion of sulfur in natural gas. The sulfates, other particulates and dissolved contaminants in the water are removed by the direct liquid fuel production process 510.

[0354] CO 2 Some CO in 516 2 used by direct liquid fuel production facilities, and the remaining CO 2 517 is compressed 518 and heated 512 to about 320 bar and 720°C, conditions that produce supercritical CO 2 519. Any excess CO 2 520 can be used for other purposes, such as producing dry ice.

[0355] Therefore, the process produces no emissions. The heat transfer in the process is so efficient that for every unit of energy captured in the natural gas; the cycle produces 0.8 units of electricity (compared to 0.6 units for a state-of-the-art natural gas power plant).

[0356] This example describes a method for extracting CO 2 An innovative process for the direct production of liquid fuels using an innovative catalytic converter and process integrated with a 300MW Allam circulating oxy-combustion plant.

[0357] The direct liquid fuel production facility is designed to produce 91,000 metric tons / year of CO 2 , 78.06MW of power and condensate from the oxygen-combustion power plant to produce approximately 450 bbl / d of ready-to-use synthetic liquid fuel.

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Claims

1. A process for converting carbon dioxide into liquid fuel, wherein the process comprises the following steps: a) Producing hydrogen and oxygen from the electrolysis of water; b) introducing the hydrogen in combination with carbon dioxide into a first catalytic reactor using a first catalyst, wherein the output from the first catalytic reactor is synthesis gas, and wherein the first catalyst is a transition metal solid solution catalyst, wherein the transition metal solid solution catalyst comprises Ni2Mg; c) introducing the synthesis gas into a second catalytic reactor, wherein the second catalytic reactor uses a second catalyst to produce tail gas, water and liquid fuel; d) directing the tail gas from the second catalytic reactor to a tail gas conversion system which utilizes oxygen from the electrolyzer to produce additional synthesis gas.

2. The process of claim 1 wherein the tail gas conversion system is a partial oxidation.

3. The process of claim 1, wherein the tail gas conversion system is autothermal reforming.

4. The process of claim 1 wherein the first catalytic reactor and the second catalytic reactor are operated at pressures within 50 psi of each other.

5. The process of claim 1, wherein the syngas is introduced into a heat exchanger to reduce the temperature of the syngas prior to introducing the syngas into the second catalytic reactor.

6. The process of claim 1, wherein the carbon dioxide introduced into the first catalytic reactor is obtained from a source, wherein the source is selected from the group consisting of: an oxy-combustion power plant, an ambient air CO2 capture system, a natural gas wellhead, a chemical production facility, and a secondary oil recovery process.

7. The process of claim 6, wherein the source is an ethanol production facility.

8. The process of claim 1, wherein the hydrogen is generated using electrolysis, wherein the power for the electrolysis is generated from a renewable or low carbon source, and wherein the renewable or low carbon source is selected from the group of sources consisting of wind power, solar power, geothermal power, hydropower, ocean currents, biomass, flare gas, nuclear power, off-peak power from fossil fuel plants, and power produced by oxy-combustion plants.

9. The process of claim 1 wherein the second catalytic reactor is operated at a pressure of 50 psi to 300 psi.

10. The process of claim 1 wherein the second catalytic reactor is operated at a pressure of 50 psi to 250 psi.

11. The process of claim 1 wherein the second catalytic reactor is operated at a pressure of 50 psi to 200 psi.

12. The process of claim 1 wherein the second catalytic reactor is operated at a pressure of 50 psi to 150 psi.

13. The process of claim 1 wherein the second catalytic reactor is operated at a pressure of 50 psi to 100 psi.

14. The process of claim 1, wherein the transition metal solid solution catalyst is an impregnated metal-coated spinel comprising 2 to 25 parts by weight of a catalyst having a surface area greater than 50 m 2 / g of magnesium, wherein the first catalyst further comprises 2 wt % to 20 wt % of nickel.

15. A process for producing a liquid fuel, wherein the process comprises the following steps: a) Separating oxygen from ambient air using a cryogenic air separator; b) mixing the oxygen with natural gas in the presence of heated supercritical carbon dioxide at high pressure and temperature, thereby combusting the natural gas to produce combustion gas comprising carbon dioxide and water and heat; c) passing the combustion gases through a gas turbine generator, thereby generating electricity for at least two purposes, and wherein the at least two purposes are distribution to a grid and use in a process to produce liquid fuels, and allowing the combustion gases to exit the gas turbine generator; d) further passing the combustion gases through a heat exchanger, wherein the heat exchanger reduces the temperature of the combustion gases; e) removing water from said combustion gases to provide carbon dioxide; f) introducing a portion of the carbon dioxide together with hydrogen, or a mixture of the portion of the carbon dioxide with hydrogen and light hydrocarbons, into a first catalytic reactor in a catalytic conversion system to produce synthesis gas, wherein the first catalyst is a Ni2Mg solid solution catalyst, and compressing any remaining carbon dioxide while heating to provide supercritical carbon dioxide; g) introducing the synthesis gas into a second catalytic reactor in the catalytic conversion system to produce tail gas, water and liquid fuel, wherein the second catalyst comprises 2 to 25 parts by weight of an element selected from the group consisting of cobalt, iron, magnesium, manganese, calcium, barium, copper and zinc, and 0.1 to 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 carrier selected from the group consisting of silica, alumina and combinations thereof, thereby producing liquid fuel, tail gas and water; h) separating the liquid fuel, tail gas and water from one another, thereby producing the liquid fuel.

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