WO2011022653A2 - Système de combustion à récupération - Google Patents

Système de combustion à récupération Download PDF

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WO2011022653A2
WO2011022653A2 PCT/US2010/046174 US2010046174W WO2011022653A2 WO 2011022653 A2 WO2011022653 A2 WO 2011022653A2 US 2010046174 W US2010046174 W US 2010046174W WO 2011022653 A2 WO2011022653 A2 WO 2011022653A2
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oxygen
cycle
heat
oxy
combustion
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PCT/US2010/046174
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WO2011022653A3 (fr
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Timothy J. Reilly
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Reilly Timothy J
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
    • F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
    • F23L7/007—Supplying oxygen or oxygen-enriched air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C9/00—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/14—Combined heat and power generation [CHP]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

Definitions

  • the methods and systems described herein relate to a recuperative combustion system that recuperates energy from fuel combustion that would otherwise be lost.
  • the recuperative combustion system minimizes or eliminates the need for an air separator unit through the use of a clean water splitter section, consisting of a thermochemical cycle or high-temperature electrolysis. Water is split into its component hydrogen and oxygen, primarily with process heat from the combustion process. The oxygen produced by the water splitter provides oxygen necessary for oxy-fuel combustion, thereby reducing or eliminating the need for the power intensive air separator unit and/or external oxygen source, significantly increasing the efficiency of the oxy-fuel combustion cycle.
  • Hydrogen produced by the water splitter may be used for a variety of industrial uses, or combined with carbon dioxide (captured from the flue gases produced by said combustion process) to produce methanol.
  • Methanol can further be refined in a methanol to gasoline reactor to produce dimethyl ether, olefins or high grade gasoline. Described herein are methods and systems that 1) increase oxy-fuel combustion efficiency, 2) produce hydrogen for a suite of industrial/energy uses, and 3) capture carbon dioxide and convert it to high value hydrocarbons.
  • a method for oxy-fuel combustion comprising: providing a system comprising a combustion chamber arranged and disposed to receive fuel, oxygen and recycled flue gas and combust said fuel, oxygen and recycled flue gas to produce heat;
  • a method for oxy-fuel combustion comprising:
  • a system comprising a combustion chamber arranged and disposed to receive coal/water slurry, oxygen and recycled flue gas, wherein the chamber is arranged and disposed to receive said oxygen from an air separator unit and/or external oxygen source, and/or a water splitter, and combust said coal/water slurry, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide; one or more heat exchangers arranged and disposed to capture heat from said heated flue gas and transfer a portion of the captured heat to a water splitter; a water splitter using a 4-step hybrid copper-chlorine thermochemical cycle for the conversion of heat and/or electricity into hydrogen gas and oxygen gas, arranged and disposed to transfer the oxygen gas to the combustion chamber for use in said oxy-fuel combustion;
  • provided herein is a method for the reaction of hydrogen produced by a water splitter and carbon dioxide obtained from combustion flue gas to form methanol and water.
  • an oxy-fuel combustion system comprising: a combustion chamber arranged and disposed to receive fuel, oxygen and recycled flue gas and combust said fuel, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide;
  • one or more heat exchangers arranged and disposed to capture heat produced by the oxy-fuel combustion and transfer said heat to a water splitter;
  • a water splitter for the conversion of heat and electricity into hydrogen gas and oxygen gas.
  • an oxy-fuel combustion system comprising: a combustion chamber arranged and disposed to receive coal/water slurry, oxygen and recycled flue gas, wherein the chamber is arranged and disposed to receive said oxygen from an air separator unit and/or external oxygen source, and/or a water splitter, and combust said coal/water slurry, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide; one or more heat exchangers arranged and disposed to capture heat from said heated flue gas and transfer a portion of the captured heat to a water splitter; and
  • a water splitter using a 4-step hybrid copper-chlorine thermochemical cycle for the conversion of heat and electricity into hydrogen gas and oxygen gas arranged and disposed to transfer the oxygen gas to the combustion chamber for use in said oxy-fuel combustion.
  • FIG 1 depicts the recuperative combustion process described herein, further
  • Figure 2 depicts a recuperative combustion system Integrated with an 875 MWTH
  • HHV ISOTHERM PWR System
  • Figure 3 depicts a flow diagram of a methanol synthesis plant (modified from Ushikoshi et al. 2000).
  • Figure 4 depicts a recuperative combustion system compared to an archetypal
  • Figure 5 depicts the steps of the four-step copper chlorine thermochemical cycle (Wang et al. 2009).
  • Figure 6 depicts an overview of the sulfur-iodine thermochemical cycle (Brown et al. 2003).
  • Figure 7 depicts an archetypal convective recuperator (Bureau of Energy Efficiency 2004).
  • Figure 8 depicts an archetypal radiation/convective recuperator (Bureau of Energy Efficiency 2004).
  • Figure 9 depicts an archetypal regenerator (Bureau of Energy Efficiency 2004). Detailed Description of the Invention
  • a method for oxy-fuel combustion comprising: providing a system comprising a combustion chamber arranged and disposed to receive fuel, oxygen and recycled flue gas and combust said fuel, oxygen and recycled flue gas to produce heat; capturing heat produced by the oxy-fuel combustion; using a portion of the heat to power a water splitter, thereby generating hydrogen gas and oxygen gas; and transferring the oxygen gas from the water splitter to the combustion chamber for use in said oxy-fuel combustion.
  • Oxy-fuel combustion for the production of electricity can occur in a variety of combustion systems.
  • combustion systems include: circulating fluidized bed boiler, pulverized coal boiler, and combustors.
  • Combustible materials including, but not limited to coal, coal/water slurry, petroleum products including oil, methane and natural gas, biomass, and plasma fuels (Fig. 1-3), may undergo oxy-fuel combustion.
  • the primary products of oxy-fuel combustion include heat and flue gas rich in carbon dioxide (Fig. 1-23). A portion of the flue gas is recycled, as described herein (Fig. 1-13).
  • the oxy-fuel comprises any combustible material. In another embodiment, the oxy-fuel comprises any hydrocarbon-based fuel. In yet another embodiment, the oxy-fuel comprises coal/water slurry. In still another embodiment, the oxy-fuel comprises oil.
  • Pressurized oxy-fuel combustion systems have the potential for better performance when compared to conventional atmospheric oxy-fuel combustion power cycles such as the ITEA ISOTHERM® pressurized oxy-fuel system (Hong et al, 2008).
  • oxy-fuel combustion at high pressures may increase the burning rate of char and the heat transfer rates in the convective sections of the heat transfer equipment.
  • the pressurized oxy-fuel system can recover more thermal energy from the flue gases and eliminate the bleeding from the high-pressure and the low- pressure steam turbines. Consequently, the cycle efficiency for the pressurized oxy-fuel system may be superior to the atmospheric system.
  • a high pressure deaerator and a flue gas acid condenser can be used.
  • the acid condenser may be modified to work at a high pressure level with flue gas composition seen in oxy-combustion. (Hong et al. 2008).
  • the system comprises a water splitter arranged and disposed to provide oxygen to the combustion chamber for use in oxy-fuel combustion.
  • the system further comprises an air separator unit arranged and disposed to provide oxygen to the combustion chamber for use in oxy- fuel combustion.
  • the normal source of oxygen for oxy-fuel combustion is an air separator unit (ASU) (Fig. 1-5).
  • ASU air separator unit
  • Fig. 1-5 The selection and implementation of air separator units will be well known to those skilled in the art.
  • oxygen is produced in the ASU through a cryogenic distillation process.
  • the production of oxygen from an ASU requires 15-20% of the gross power output of an industrial facility.
  • the need for an ASU for oxygen generation may be reduced or eliminated through the use of a water splitter.
  • Candidate water splitters include a hybrid copper-chlorine thermochemical Cycle (CuCl Cycle), sulfur-iodine thermochemical cycle, hybrid sulfur thermochemical cycle (HyS Cycle) and/or high temperature electrolysis (HTE).
  • Other candidate water splitters include volatile metal oxide thermochemical cycles (e.g., zinc/zinc oxide, hybrid calcium), and non-volatile metal oxide cycles (e.g., iron oxide, cerium oxide) thermochemical cycles.
  • volatile metal oxide thermochemical cycles e.g., zinc/zinc oxide, hybrid calcium
  • non-volatile metal oxide cycles e.g., iron oxide, cerium oxide
  • Other water-splitting thermochemical cycles are available, and known to those skilled in the art. Water splitters use thermal or electrical energy in order to convert water (Fig. 1-17) to hydrogen gas (Fig. 1-15) and oxygen gas (Fig. 1-11). In the recuperative combustion process described herein, the water splitter is powered by excess process heat provided by oxy-fuel combustion (Fig. 1-7), and by electricity (Fig. 1-17).
  • thermochemical cycle or HTE offsets reduces or eliminates the need for an ASU, or external oxygen source, for oxy-fuel combustion, thereby increasing combustion efficiency.
  • the thermochemical cycle or HTE unit employed in the system also produces hydrogen as a product of water splitting.
  • the hydrogen may be used for a variety of purposes, including reaction with the carbon dioxide produced by oxy-fuel combustion to yield methanol and water (Fig. 1-25).
  • the system further comprises an air separator unit, wherein the combustion chamber is arranged and disposed to receive oxygen from the air separator unit and/or the water splitter.
  • a water splitter to produce oxygen results in a reduction, or elimination, of the need for an air separation unit (ASU), or other oxygen source, to supply oxygen for oxy-fuel combustion.
  • ASU air separation unit
  • the scaling of the water splitter determines if an ASU output is either reduced or eliminated.
  • the employment of a water splitter may significantly reduce, or eliminate, the cost of an ASU unit and, correspondingly, reduce the power penalty resulting from the operation of an ASU. Captured process/waste heat, some of which may be upgraded by chemical heat pumps, may be used to supply additional power needs by the water splitter as well.
  • the combustion chamber is arranged and disposed to receive oxygen from the air separator unit and/or external oxygen supply, and/or the water splitter.
  • the oxygen purity delivered from the water splitter and/or ASU may be 95% (mol %) and delivered at 200 0 C; oxygen content in the recycled flue gas may be about 3% (mol %).
  • the oxygen delivery temperature to the combustor is controlled to prevent the acid condensation when mixed with the recycled flue gases.
  • the flue gases contain acid gases, such as SO 3 , SO 2 , nitrogen oxides, and HCl produced during combustion.
  • the recycled flue gases, state 2-19 are mixed with the oxygen stream from the water splitter, state 2-13, which may be colder, depending on the ASU or water splitter technology employed.
  • the oxygen delivery temperature needs to be carefully controlled to nearly 200 0 C.
  • the 200 0 C delivery temperature target is achieved by using a two-stage oxygen compressor with an intercooler.
  • the mass flow rate of the oxygen stream is determined such that the raw flue gases exiting the combustor have 3% oxygen on a molar basis (Hong et al. 2008)
  • the amount of oxygen required from the air separator unit and/or external oxygen supply is reduced or eliminated in proportion to the amount of oxygen provided by the water splitter.
  • the amount of oxygen that is required from the air separator unit, and/or another oxygen source, and/or the water splitter may be determined by methods taught herein (see, for example, the section of Algorithms and Formulae), or by methods known to those of skill in the art.
  • the water splitter produces hydrogen gas and oxygen gas by means of a thermochemical cycle. In still another embodiment, the water splitter produces hydrogen and oxygen gas by means of a hybrid
  • thermochemical/electrochemical cycle
  • thermochemical or hybrid thermochemical/electrochemical cycles, apparatus and procedures for use in the methods and systems described herein will be well known to those skilled in the art.
  • thermochemical cycles and hybrid are thermochemical cycles and hybrid
  • thermochemical/electrochemical cycles include sulfur cycles (e.g., hybrid sulfur and sulfur- iodine thermochemical cycles), low temperature cycles (e.g., hybrid copper- chlorine thermochemical cycle), volatile metal oxide cycles (e.g., zinc/zinc oxide, hybrid calcium), and non-volatile metal oxide cycles (e.g., iron oxide, cerium oxide) thermochemical cycles.
  • sulfur cycles e.g., hybrid sulfur and sulfur- iodine thermochemical cycles
  • low temperature cycles e.g., hybrid copper- chlorine thermochemical cycle
  • volatile metal oxide cycles e.g., zinc/zinc oxide, hybrid calcium
  • non-volatile metal oxide cycles e.g., iron oxide, cerium oxide
  • thermochemical cycle is selected from: a hybrid copper- chlorine cycle; a sulfur-iodine cycle; and a hybrid sulfur cycle.
  • thermochemical cycle is a hybrid copper-chlorine cycle.
  • the copper-chlorine cycle is selected from: a 3-step cycle, a 4- step cycle, and a 5-step cycle.
  • the hybrid copper-chlorine cycle is the 4-step cycle.
  • the 4-step cycle of the hybrid copper chlorine cycle may be represented by the following steps:
  • Step I CuCs) + 2HCl(g) ⁇ 2CuCl(molten) + H 2 (g)
  • Step II 4CuCl (s) ⁇ 2Cu(s) + 2CuCl 2 ( ⁇ ?) + HCl (aq)
  • Step III CuCl 2 ( ⁇ ?) + UyH 2 O(Q ⁇ CuOCuCl 2 W + 2HCl(g) + (n / -l)H 2 0(g)
  • Step IV CuOCuCl 2 (s) ⁇ 2CuCl(molten) +0.5O 2 (g)
  • n f is 5-30.
  • Three-step, four-step and five-step versions of the copper-chlorine (Cu-Cl) hybrid electrochemical-thermochemical cycle are described in Wang et al. (2009). While the five-step version requires less heat than the three-step version of the hybrid Cu-Cl cycle, it is more complex from equipment and process engineering standpoints.
  • a hybrid Cu-Cl Cycle using the four-step process is described by Chukwu et al. (2008). Step III of the four-step process is an electrochemical step, requiring the input of electricity. Chukwu et al. provides reaction- specific thermodynamic data and Aspen Plus heat/mass balance modeling of the four-step hybrid Cu-Cl cycle.
  • the four-step process ( Figure 5) consists of three thermal reactions in which H 2 , O 2 and HCl are generated, and an electrochemical step in which CuCl is
  • the water splitter operates at a temperature 450 0 C for Step I; 30-80 0 C for Step II; 375 0 C for Step III; and 530 0 C for Step IV.
  • the heat required to produce 1 mole of O and 1 mole of H 2 is about 554.7 kJ/mol.
  • the hybrid Cu-Cl four-step cycle receives process heat in adequate supply from oxy-fuel combustion through a heat exchanger system.
  • the hybrid Cu-Cl four-step cycle is sized to accommodate oxygen requirements for oxy-fuel combustion within the fossil fuel combustor or boiler. This sizing is based on either a partial or complete replacement of the air separator unit (ASU), depending on a number of pre-existing, technical and economic factors unique to an industrial/power plant, or other site of combustion.
  • ASU air separator unit
  • Hydrogen production rates for various downstream hydrogen uses are also an important aspect of sizing the four-step hybrid Cu-Cl thermochemical cycle reactor.
  • thermochemical cycle is a sulfur-iodine (S-I) cycle.
  • sulfur-iodine cycle may be represented by the following steps:
  • Step I 2 H 2 O + SO 2 + I 2 ⁇ H 2 SO 4 + 2 HI
  • Step II H 2 SO4 ⁇ H 2 O + SO 2 + V 2 O 2
  • Step III 2 HI ⁇ H 2 + I 2 Heat and mass balances associated with the S-I Cycle can be found in Brown et al. (2003).
  • the gross heat needed per mole H 2 (and 0.5 mole O 2 ) is 674.9 kJ/mole H 2 with net heat requirements is 391.3 kJ/mol H 2 (full HI gasification), 432.9 kJ/mol H 2 (no HI gasification), as compared with 554.7 kJ/H 2 gross heat and 322.7 kJ/H 2 net heat required for the Cu-Cl cycle (Wang et al. 2009).
  • a major difference between the Cu-Cl and S-I thermochemical cycles is the substantially lower temperatures that the Cu-Cl cycle operates at relative to the S-I cycle, allowing almost 30% of the heat needed for the Cu-Cl process to come from low grade heat (i.e., heat at temperatures lower than 343 K).
  • HyS cycle is a hybrid electrochemical-thermochemical cycle (Bilgen 1988). It consists of splitting sulfuric acid into water and sulfur trixode
  • Step I H 2 SO 4 -» H 2 O + SO 3 (>450°C)
  • Step II SO 3 -> SO 2 + ViO 2 (>850°C with catalyst; 1150 0 C without catalyst)
  • Step III 2H 2 O + SO 2 -» H 2 SO 4 + H 2 (electrolysis, 80 0 C)
  • the water splitter produces hydrogen gas and oxygen gas by means of high-temperature electrolysis.
  • Hydrogen and Oxygen can be produced via the classical electrolysis of water at low temperature or, alternatively, by using the different fuel cell technologies. These technologies are based on (i) proton-exchange membrane fuel cells (PEMFCs) (referring to the solid polymeric electrolyte membrane), (ii) fuel cells using solid oxide proton conductors, and (iii) fuel cells with a solid oxide ion (O 2- ) conductor (SOFCs).
  • PEMFCs proton-exchange membrane fuel cells
  • fuel cells using solid oxide proton conductors ii) fuel cells using solid oxide proton conductors
  • SOFCs solid oxide ion
  • the operating temperatures of fuels cells vary widely, from around 80-120 0 C for PEMFCs to 700-1000 0 C for SOFCs.
  • the free energy required for the reaction ( ⁇ G) decreases with increasing temperature whereas the free enthalpy ( ⁇ H) remains almost constant.
  • This thermodynamic relation in principle unfavorable for the fuel cell mode at high temperatures, explains the particular interest in performing electrolysis at high temperatures. Since the SOFCs achieve competitive (chemical- to-electrical) energy conversion efficiencies despite the less favorable
  • thermodynamic conditions one can a priori expect that high-temperature
  • HTE electrolysis
  • the free energy of the reaction AG decreases from -1.23 eV (237 kj mol "1 ) at ambient temperature to -0.95 eV (183 kj mol "1 ) at 900 0 C, while the free enthalpy term remains essentially unchanged (AH ⁇ 1.3 eV or 249 kj mol "1 at 900 0 C).
  • Part of the energy required for an ideal (loss-free) HTE can thus be provided by heat.
  • Increasing ohmic and/or reaction losses in a real HTE system increase the demand for electrical energy and decrease the demand for an external heat supply until, finally, the reaction becomes exothermic.
  • three modes of operation are distinguishable in HTE:
  • thermoneutral, endothermic, and exothermic HTE operates at thermal equilibrium (the thermoneutral mode) when the electrical energy input equals the enthalpy of the reaction. In that case, the entropy necessary for water splitting equals the heat generated by the loss reactions, and the energy conversion efficiency is 100%.
  • the electric energy input exceeds the AH term, which corresponds to efficiency below 100%.
  • the electric energy input remains below the enthalpy term. Therefore, heat must be supplied to maintain the cell temperature. This mode means that energy conversion efficiencies of the cell or the stacks are above 100%.
  • An HTE system can be operated with and without an external heat supply.
  • thermoneutral mode that is, to limit the thermal losses to a value required to compensate for the endothermic reaction. This leaves a wide margin for cell overvoltages and, therefore, for an increase in the current density or a lowering of the temperature.
  • the goal is to reduce the overvoltages as far as possible to allow for a significant uptake of heat. This implies, at least with present cell technology, operation under higher temperatures (800 0 C or above) and lower electrode overvoltages (i.e., current densities somewhat lower than those achieved in thermoneutral operation).
  • the system further comprises one or more heat exchangers for the capture and transfer of heat from the oxy-fuel combustion to the water splitter.
  • Heat exchangers are required for transferring process heat from the heated flue gas to endothermic reactions within the water splitter section. For example, in the Cu-Cl Cycle, sufficient heat must be transferred from the flue gas coming from the boiler/combust or to the chlorination step (Step I), oxychlorination step (Step (III) and decomposition step (Step IV) ( Figure 5).
  • heat exchangers Numerous types of heat exchangers are available for the adequate transfer of heat to the water splitter. Specific choice of heat exchanger is dependent on a number of factors, including, but not limited to: the nature or quality of the flue gases, the temperature of primary process flue gases, matching heat demand of the secondary (i.e., water splitting) process with the heat supply from the primary process, matching timing of the heat supply for the primary process and the heat demand in the secondary process, and placement of primary and secondary heating equipment.
  • the system further comprises one or more heat exchangers for the capture and transfer of heat from the heated flue gas to the water splitter.
  • said one or more heat exchangers are selected from: a convective recuperator, a radiation/convective recuperator, a ceramic recuperator and a regenerator.
  • said one or more heat exchangers are selected from appropriately scaled heat exchangers which function within specified heat ranges (i.e., heat ranges specified herein or known to those of skill in the art). Other suitable heat exchangers are available, and known to those of skill in the art.
  • recuperator In a recuperator, heat exchange takes place between the flue gases and the air through metallic or ceramic walls. Ducts or tubes carry the air or other gas to be heated; the other side contains the waste heat stream.
  • a common configuration for recuperators is called the tube type or convective recuperator. As seen in the Figure 7, the hot gases are carried through a number of parallel small diameter tubes, while the incoming air/gas to be heated enters a shell surrounding the tubes and passes over the hot tubes one or more times in a direction normal to their axes. If the tubes are baffled to allow the gas to pass over them twice, the heat exchanger is termed a two-pass recuperator; if two baffles are used, a three-pass recuperator, etc.
  • Shell and tube type recuperators are generally more compact and have a higher effectiveness than radiation recuperators, because of the larger heat transfer area made possible through the use of multiple tubes and multiple passes of the gases.
  • Radiation/convective Recuperator For maximum effectiveness of heat transfer, combinations of radiation and convective designs are used, with the high-temperature radiation recuperator being first followed by convection type. These are more expensive than simple metallic radiation recuperators, but are less bulky.
  • a Convective/radiative Hybrid recuperator is shown in Figure 8.
  • Ceramic Recuperator The principal limitation on the heat recovery of metal recuperators is the reduced life of the liner at inlet temperatures exceeding 1100 0 C.
  • ceramic tube recuperators have been developed whose materials allow operation on the gas side to 1550 0 C and on the preheated air side to 815°C on a more or less practical basis.
  • Early ceramic recuperators were built of tile and joined with furnace cement, and thermal cycling caused cracking of joints and rapid deterioration of the tubes. Later
  • Regenerator are rechargeable storage batteries for heat.
  • a regenerator ( Figure 9) is an insulated container filled with metal or ceramic shapes that can absorb and store relatively large amounts of thermal energy.
  • process exhaust gases flow through the regenerator, heating the storage medium. After a while, the medium becomes fully heated (charged).
  • the exhaust flow is shut off and cold combustion air enters the unit. As it passes through, the air extracts heat from the storage medium, increasing in temperature before it enters the burners.
  • the heat stored in the medium is drawn down to the point where the regenerator requires recharging. At that point, the combustion air flow is shut off and the exhaust gases return to the unit. This cycle repeats as long as the process continues to operate.
  • regenerator For a continuous operation, at least two regenerators and their associated burners are required.
  • One regenerator provides energy to the combustion air, while the other recharges.
  • An alternate design of regenerator uses a continuously rotating wheel containing metal or ceramic matrix. The flue gases and combustion air pass through different parts of the wheel during its rotation to receive heat from flue gases and release heat to the combustion air.
  • Regenerators may be preferable for large capacities and have been very widely used in glass and steel melting furnaces. Important relations exist between the size of the regenerator, time between reversals, thickness of brick, conductivity of brick and heat storage ratio of the brick. In a regenerator, the time between the reversals is an important aspect. Long periods would mean higher thermal storage and hence higher cost. Also long periods of reversal result in lower average temperature of preheat and consequently reduce fuel economy.
  • a method for oxy-fuel combustion comprising: providing a system comprising a combustion chamber arranged and disposed to receive coal/water slurry, oxygen and recycle flue gas, wherein the chamber is arranged and disposed to receive said oxygen from an air separator unit and/or a water splitter, and combust said coal/water slurry, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide; one or more heat exchangers arranged and disposed to capture heat from said heated flue gas and transfer a portion of the captured heat to a water splitter; a water splitter using a 4-step hybrid copper-chlorine thermochemical cycle for the conversion of heat and/or electricity into hydrogen gas and oxygen gas, arranged and disposed to transfer the oxygen gas to the combustion chamber for use in said oxy-fuel combustion;
  • the amount of oxygen that the combustion chamber requires from an air separator unit and/or external oxygen supply is reduced or eliminated in proportion to the amount of oxygen received from the water splitter results in increased efficiency.
  • the increased efficiency is measured in terms of increased gross power output of the combustion process.
  • the gross power output of the combustion process is increased by 1-20%.
  • the gross power output of the combustion process is increased by 1-10%.
  • the gross power output of the combustion process is increased by 10-20%.
  • the gross power output of the combustion process is increased by 15-20%.
  • the oxy-fuel combustion products further comprise heated flue gas containing carbon dioxide.
  • Oxy-fuel combustion yields flue gases consisting of predominantly carbon dioxide (Fig. 1-23) and condensable water, whereas conventional air-fired combustion flue gases are nitrogen-rich with only about 15% (by volume) of carbon dioxide (Hu et al. 2008; IEA, 2008).
  • the high carbon dioxide concentration (up to 95%) and the significantly lower nitrogen concentration in the oxy-fuel raw flue gases is a unique feature that lowers the energy and capital costs of oxy-fuel carbon dioxide capture when compared to alternatives (Buhre et al 2005).
  • decreasing relative recycled flue gas input increases combustion, and flue gas, temperatures, and may be a mode for increasing heat grade for secondary water splitting processes.
  • oxy-fuel combustion using a pressurized coal combustor, occurs at 1400 to 1600 0 C; however, stoichiometric combustion of coal in pure oxygen reaches up to 3500 0 C. Optimization of oxygen/recycled gas content with respect to high grade heat production and oxygen/hydrogen yields requires additional research.
  • Oxy-fuel combustion involves the burning of fuel in an oxygen-rich, nitrogen- lean and carbon dioxide-rich environment, which is achieved by feeding the combustor or boiler with an oxygen-rich stream and recycled flue gases.
  • Oxy-fuel combustion produces a flue gas stream containing mostly CO 2 , which can be directly purified and compressed for conversion to useful materials or for carbon sequestration purposes.
  • the CO 2 concentration in the flue gas is greatly increased by using a mixture of recirculated flue gas and pure oxygen instead of air for firing coal. Recirculation of flue gas is necessary to provide sufficient mass flow of flue gas for cooling the flame and also heat capacity and flue gas velocity for convective heat transfer in the boiler.
  • CO 2 purity is mainly influenced by (a) where the flue gas is recycled in the process (the cleaning that has been done up to this point), (b) the sealing of boiler and other components to prevent air ingress, (c) the purity of the oxygen from the Air Separation Unit (ASU) (or alternative oxygen source), (d) the performance of all air quality control system equipment (e.g., SCR, FGD, and ESP), and (e) additional CO 2 purification during/after compression (Wu et al. 2009).
  • ASU Air Separation Unit
  • Oxy-fuel combustion involves using a mixture of recirculated flue gas and pure oxygen, instead of air, for firing the fuel. Oxy-fuel combustion may take place at 1400 to 1600 0 C. The stoichiometric combustion of coal in pure oxygen may reach up to 3500 0 C.
  • the primary outputs of the recuperative combustion process include the following:
  • H 2 and O 2 from the water splitter i.e., Cu-Cl, S-I, or HyS thermochemical cycles
  • the secondary outputs from the downstream portions of the process include: methanol from the methanol reactor (Fig. 1-25), dimethyl ether (DME), olefins, and gasoline (mainly C5-C9) from methanol to gasoline conversion (Fig. 1-35), and water, as a by-product of methanol and other hydrocarbon production. This water may be treated, as necessary, and recycled to the water splitter (Figs. 1-31 and 1-41).
  • the secondary outputs of the recuperative combustion process described herein are valuable products on the global market (Fig. 1-39).
  • the hydrogen from the water splitter is used directly or indirectly in a subsequent process. In another embodiment of the method, the hydrogen from the water splitter is used directly in a subsequent process.
  • the hydrogen from the water splitter and the carbon dioxide from the combustion flue gas are reacted to form methanol and water.
  • a method for the reaction of hydrogen produced by a water splitter and carbon dioxide obtained from combustion flue gas to form methanol and water is provided herein.
  • the carbon dioxide is purified and compressed prior to reacting with hydrogen.
  • the hydrogen and carbon dioxide are both produced by the recuperative combustion system.
  • the products of the reaction further comprise waste heat.
  • Carbon dioxide purification involves the removal of contaminants from the flue gas, including nitrogen oxides, sulfur oxides, and mercury, generally under pressurized conditions. While numerous strategies for removal of these contaminants already exist at modern fossil fuel power plants, including flue gas desulfurization (FGD) for sulfur oxides, selective catalytic reduction (SCR) for nitrogen oxides compounds and activated carbon or sorbents for mercury, these are capital-intensive technologies that do not result in a comprehensive removal of impurities from, and separation of, carbon dioxide from flue gas.
  • FGD flue gas desulfurization
  • SCR selective catalytic reduction
  • a host of developing technologies for increasing carbon dioxide purity are currently under development (e.g., see White and Fogash 2009; Hong et al., 2008; and Shah 2006). Specific technologies employed for contaminant removal in the carbon dioxide stream depends on the end use of carbon dioxide (i.e., for methanol production, enhanced oil recovery (EOR) or sequestration).
  • the high-concentration carbon dioxide flue gas that is produced by the oxy-fuel combustion process may be hydrogenated in a fluidized bed reactor with hydrogen gas at 200-300 0 C at a pressure of 50-100 bar in a catalytically-mediated reaction
  • heterogeneous catalyst includes, but is not limited to: Cu/ZnO/ZrO 2 / Al 2 O 3 /SiO 2 ), yielding methanol, water and substantial heat (Figs. 1-25, 1-21 and 1-31). The following three reactions are controlled in the methanol reactor to maximize methanol synthesis (Hirotani et al. 1998):
  • the methanol reactor may be of several types, including a modified test methanol synthesis reactor from Ushikoshi et al. (2000).
  • Figure 3 shows a flow diagram of the test plant, which is designed with facilities for recycling unreacted gases.
  • the gases (mixture of CO 2 , CO and H 2 ) supplied from the CO 2 purification and compression unit (mainly CO 2 ) and the water splitter (H 2 ) (Figs. 3-1, 3-2, 3-3, 3-4) are compressed (Figs. 3-5, 3-6, 3-7) along with recycled gases (Fig. 3-23), and then fed into the reaction tube (Figs. 3-8, 3-13) through a pre-heater (Fig. 3-9).
  • the reactor (Fig.
  • the temperature profile along the bed is measured by means of eight thermocouples situated at the central axis of the reactor.
  • the temperature difference along the reactor is less than 2 0 K.
  • the pressure is controlled within 0.1 MPa by changing the total flow rate of the make-up gas, in which the H 2 /CO/CO 2 ratio is adjusted with the flow controllers.
  • the flow rate of the inlet gas to the reactor is controlled by the flow controller placed just after the recycle gas compressor. Reaction products are cooled down (Figs. 3-18, 3-19), and then the mixture of methanol and water is separated at the gas-liquid separator (Figs. 3-20, 3-21) from unreacted gases. Unreacted gases and gaseous products, such as CO, methane and so on, excluding small amounts of purge gas, are recycled back to the reactor (Figs. 3-22, 3-23)). The mixture of methanol and water is subjected to separation (see below) then stored in a container (Figs. 3-25, 3-26, 3-27).
  • Control of temperature in the methanol reactor for pre -reaction reduction of the catalyst (in the presence of heat and hydrogen and nitrogen gases) as well as during methanol synthesis is controlled by a preheater, oil heater and oil cooler system with (Figs. 3-9, 3- 10, 3-11, 3-12, 3-13, 3-14, 3-15, 3-16 and 3-17).
  • the make-up gas, the inlet and outlet gases of the reactor and the recycle gas are analyzed with an on-line gas chromatograph.
  • Gas chromatography is employed for analysis of the reaction products; H 2 , CO and CO 2 are analyzed by thermal-conductivity detector; methanol, dimethyl ether, methyl formate and hydrocarbons are analyzed by the flame ionization detector.
  • Excess heat produced by exothermic methanol reaction may be recuperated and recirculated for use in the water splitter (Fig. 3-32) (through heat upgrading using chemical heat pumps) (Fig. 3-31).
  • the methanol may be used as is, or used as an industrial feedstock (e.g., for conversion to dimethyl ether, olefins, gasoline and a spectrum of other industrial applications) using a variety of industrial processes such as the Mobil Methanol to Gasoline process.
  • the byproduct water is filtered and re -used in the in the water splitter.
  • CHPs Chemical Heat Pumps
  • a salt/ammonia chemical heat pump consists of salts that are able to
  • the ammonia vapor pressure is a function of temperature for two different salts, designated by LTS (low- temperature salt) and HTS (high-temperature salt).
  • LTS low- temperature salt
  • HTS high-temperature salt
  • the desorption reaction is endothermic. Heat must be supplied to the gas/solid reactor to release ammonia vapor from the LTS. When this ammonia vapor flows to the HTS, it is absorbed and heat is released in an exothermic reaction.
  • the pair of salts is MnSCVNH 3 (LTS) and
  • NiCl 2 '2NH 3 + 4NH 3 ⁇ NiCl 2 '6NH 3 + Q out ; ⁇ H -55.3 kJ/mol (NH 3 )
  • This chemical heat pump could be used as a "bottoming cycle” to upgrade waste heat to an intermediate stage, before another CHP upgrades further to higher temperatures. It is anticipated that equipment performance and reaction kinetics would become unfavorable if a single CHP attempts to operate over an excessively large temperature range. Therefore, a magnesium oxide (MgO)/vapor chemical heat pump, which operates at temperatures above the salt/ammonia CHP may be useful in increasing the grade of heat further.
  • MgO magnesium oxide
  • the MgO/Vapor CHP is described by the following chemical reaction:
  • the rightward reaction is exothermic MgO hydration.
  • the kinetics of the reaction have been reported by Kato et al. (1996).
  • the operation consists of heat storage and heat supply modes, with solid products from each reactor supplied as solid feed to the other.
  • Magnesium hydroxide (Mg(OH) 2 ) is initially charged into a gas/solid reactor. Heat is added, after which solid MgO and water vapor are formed. The heat of condensation is recovered from the steam and the resulting water is stored as a liquid. In the heat supply mode, the stored water is then vaporized by another separate heat input. The vapor is supplied to an exothermic solid/gas reactor for hydration of MgO.
  • a conceptual framework of coupled CHPs and a Cu-Cl thermochemical cycle may be advantageous.
  • an exothermic step within the Cu-Cl cycle (or Methanol Reactor Section) could supply heat into the MgO/vapor CHP, to be subsequently upgraded to a higher temperature that is then used by the endo thermic hydrolysis step in the Cu-Cl cycle.
  • the lower temperature endothermic step of copper oxychloride decomposition could then be supplied separately from the salt/ammonia CHP.
  • Input power is needed to drive compressors in the CHPs.
  • electricity generated from waste heat could be supplied directly to the CHPs, thereby potentially making the CHPs and Cu-Cl cycle solely driven by process/waste heat from industrial or power plants (Naterer 2008).
  • thermal energy from exothermic processes of the method is captured by one or more chemical heat pumps. In another embodiment, said thermal energy is transformed to another temperature. In yet another embodiment, said thermal energy is used in endothermic processes of the method. In certain embodiments, thermal energy from the water splitter cycle and/or the methanol reactor is captured, transformed to another temperature, and used in endothermic processes of the method.
  • an oxy-fuel combustion system comprising: a combustion chamber arranged and disposed to receive fuel, oxygen and recycled flue gas and combust said fuel, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide; one or more heat exchangers for capturing heat produced by the oxy-fuel combustion and transferring said heat to a water splitter; and a water splitter, for the conversion of heat and electricity into hydrogen gas and oxygen gas.
  • the water splitter is arranged and disposed to provide oxygen to the combustion chamber for use in oxy-fuel combustion.
  • system further comprises an air separator unit arranged and disposed to provide oxygen to the combustion chamber for use in oxy-fuel combustion.
  • the system further comprises an external oxygen supply.
  • system further comprises an air separator unit, wherein the combustion chamber is arranged and disposed to receive oxygen from the air separator unit and/or external oxygen supply and/or the water splitter.
  • one or more heat exchangers serve as the means to capture the heat produced by the oxy-fuel combustion and to transfer said heat to the water splitter.
  • said one or more heat exchangers captures heat from the heated flue gas.
  • said one or more heat exchangers are selected from: a convective recuperator, a radiation/convective recuperator, a ceramic recuperator and a regenerator.
  • said one or more heat exchangers are selected from appropriately scaled heat exchangers which function within specified heat ranges (i.e., heat ranges specified herein or known to those of skill in the art).
  • the amount of oxygen required from the air separator unit and/or external oxygen supply is reduced or eliminated in proportion to the amount of oxygen provided by the water splitter.
  • the amount of oxygen that is required from the air separator unit, and/or another oxygen source, and/or the water splitter may be determined by methods taught herein (see, for example, the section of Algorithms and Formulae), or by methods known to those of skill in the art.
  • the oxy-fuel combustion products further comprise heated flue gas containing carbon dioxide.
  • the oxy-fuel comprises any combustible material. In another embodiment, the oxy-fuel comprises any hydrocarbon-based fuel. In yet another embodiment, the oxy-fuel comprises coal/water slurry. In still another embodiment, the oxy-fuel comprises oil.
  • the water splitter produces hydrogen gas and oxygen gas by means of high-temperature electrolysis.
  • the water splitter produces hydrogen gas and oxygen gas by means of a thermochemical cycle.
  • the thermochemical cycle is selected from: a hybrid copper-chlorine cycle; a sulfur-iodine cycle; and a hybrid sulfur cycle.
  • the thermochemical cycle is a sulfur-iodine cycle.
  • the sulfur-iodine cycle may be represented by the following steps: Step I: 2 H 2 O + SO 2 + I 2 ⁇ H 2 SO 4 + 2 HI
  • Step III 2 HI ⁇ H 2 + I 2
  • thermochemical cycle is a hybrid copper- chlorine cycle.
  • hybrid copper-chlorine cycle is selected from: a 3-step cycle, a 4-step cycle, and a 5-step cycle.
  • the hybrid copper-chlorine cycle is the 4-step cycle.
  • the 4-step hybrid copper chlorine cycle may be represented by the following steps:
  • Step I CuCs) + 2HCl(g) ⁇ 2CuCl(molten) + H 2 (g)
  • Step II 4CuCl (s) ⁇ 2Cu(s) + 2CuCl 2 (aq) + HCl (aq)
  • Step III CuCl 2 ( ⁇ ) + UyH 2 O(Q ⁇ CuOCuCi 2 (V) + 2HCl(g) + (n r l)H 2 0(g)
  • Step IV CuOCuCi 2 (V) ⁇ 2CuCl(molten) +0.5O 2 (g)
  • n f is 5-30.
  • the water splitter operates at a temperature 450 0 C for Step I; 30-80 0 C for Step II; 375 0 C for Step III; and 530 0 C for Step IV.
  • the heat required to produce 1 mole of O and 1 mole of H 2 is about 554.7 kJ/mol.
  • the hydrogen from the water splitter is used directly or indirectly in a subsequent process. In another embodiment of the system, the hydrogen from the water splitter is used directly in a subsequent process.
  • the hydrogen from the water splitter and the carbon dioxide from the combustion flue gas are reacted to form methanol and water.
  • an oxy-fuel combustion system comprising: a combustion chamber arranged and disposed to receive coal/water slurry, oxygen and recycled flue gas, wherein the chamber is arranged and disposed to receive said oxygen from an air separator unit and/or external oxygen source, and/or a water splitter, and combust said coal/water slurry, oxygen and recycled flue gas to produce heat and heated flue gas containing carbon dioxide; one or more heat exchangers arranged and disposed to capture heat from said heated flue gas and transfer a portion of the captured heat to a water splitter; a water splitter using a 4-step hybrid copper- chlorine thermochemical cycle for the conversion of heat and electricity into hydrogen gas and oxygen gas, arranged and disposed to transfer the oxygen gas to the combustion chamber for use in said oxy-fuel combustion.
  • a method for converting a non-oxy-fuel combustion system into a recuperative oxy-fuel combustion system comprising:
  • Providing a system comprising an air separator unit and/or external oxygen source; one or more heat exchangers; a thermochemical and/or electrochemical water splitter; and a flue gas converter; and converting a non-oxy-fuel combustion system into a recuperative oxy-fuel combustion system.
  • the non-oxy-fuel combustion system comprises a combustion chamber.
  • the water splitter is arranged and disposed to provide oxygen to the combustion chamber for use in oxy-fuel combustion.
  • System scaling is based on the maximum mass flow rate of the fuel (e.g., coal) used in the boiler or combustor, which in turn is based on the gross cumulative power produced by the entire power plant (MWg), not considering the power penalty incurred by equipment at the plant.
  • MWg gross cumulative power produced by the entire power plant
  • Fuel flow rate is calculated based on a plant' s gross cumulative power (MWg), heat rate and fuel properties (heating value). The relationship in the equation below can be used to determine the fuel flow rate required to generate the desired (or actual) gross power, given the fuel properties and gross heat rate.
  • MWg gross cumulative power
  • heat rate heat rate
  • fuel properties heat rate
  • MW g gross cumulative power produced by the entire power plant; this does not consider power used by equipment in the power plant (MW)
  • HR steam heat rate of the steam cycle, which excludes the effects of the boiler efficiency (Btu/kWh)
  • HHVcoai higher heating value of the coal on a wet basis (Btu/lb) ii. Calculate oxygen requirement to meet this fuel flow rate
  • the maximum rate of oxygen produced by the water splitter is determined as follows:
  • This oxygen flow should replace the oxygen that would have been produced by the Air Separation Unit (ASU) in a normal oxy-fuel system. iii. Considerations for sizing the water splitter to meet the oxygen flow rate
  • the water splitter i.e., Cu-Cl or S-I or HyS thermochemical cycles; or HTE
  • the water splitter is sized to produce the maximum oxygen flow rate, thereby replacing the ASU. Sizing the water splitter such that oxygen flow rate is lower than the maximum flow rate for the facility may result in the need to supplement oxygen production with another source (e.g., an ASU).
  • the water splitter is sized based on stoichiometric oxygen output from particular water splitter reactions to meet the O 2 flow rate determined above.
  • niFG flue gas mass flow rate
  • %ash fuel ash content, mass fraction
  • miimpurities mass of impurities removed during CO2 purification (i.e., NOx, SOx and
  • the hydrogen flow rate is determined stoichiometrically based on the following equation:
  • the methanol to gasoline reactor system shall be sized to accommodate maximum methanol flow, based, in turn, on maximum fuel and carbon dioxide flow rates, respectively.
  • Methanol to gasoline reactor sizing is based on stoichiometric considerations of the following overall reactions: 2CH 3 OH ⁇ » CH 3 OCH 3 + H 2 O
  • the dimethyl ether product is then further dehydrated over a zeolite catalyst (preferred zeolites may include ZSM-5, ZSM-I l, ZSM-12, ZSM-35, and ZSM-48) to give a gasoline with 80% C5+ hydrocarbon products. Conversion efficiencies for methanol to gasoline conversion shall also be considered when sizing the reaction system.
  • the Methanol to Gasoline Section produces substantial amounts of heat which may be recuperated and transferred through chemical heat pumps and/or other heat exchangers to the Water Splitter Section to power endothermic reactions. Therefore, these Sections should be sized and positioned in a manner which facilitates waste heat recuperation and transfer.
  • IPCC Intergovernmental Panel on climate Change
  • FIG. 1 provides a system schematic of the integration of the recuperative combustion system with the ISOTHERM® oxy-fuel (coal) combustion process.
  • Table 1 provides the temperature and mass data from each process, and includes a description of each step numerically keyed to the process step numbers in Figure 2.

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Abstract

La présente invention a trait à des procédés et à des systèmes concernant un système de combustion à récupération qui récupère l’énergie provenant de la combustion du combustible qui serait autrement perdue. Le système de combustion à récupération permet de minimiser ou de supprimer l’emploi d’une unité de séparateur d’air grâce à l’utilisation d’une partie de séparation d’eau claire, constituée d’un cycle thermochimique ou d’une électrolyse à haute température. L’eau est divisée en hydrogène et en oxygène, principalement au moyen de la chaleur industrielle provenant du processus de combustion. L’oxygène produit au moyen de la partie de séparation d’eau fournit l’oxygène nécessaire à la combustion oxygaz, ce qui permet de réduire ou de supprimer l’utilisation de l’unité de séparateur d’air de grande puissance et/ou la source d’oxygène extérieure, ce qui augmente de façon significative l’efficacité du cycle de combustion oxygaz. L’hydrogène produit au moyen de la partie de séparation d’eau peut être utilisé pour une variété d’applications industrielles ou combiné au dioxyde de carbone (capturé à partir des gaz de combustion produits par ledit processus de combustion) afin de produire du méthanol. Le méthanol peut en outre être raffiné dans un réacteur méthanol-essence afin de produire de l’éther diméthylique, des oléfines ou de l’essence de première qualité. La présente invention a trait à des procédés et à des systèmes qui 1) augmentent l’efficacité de la combustion oxygaz, 2) produisent de l’hydrogène pour un ensemble d’applications industrielles/énergétique et 3) capturent le dioxyde de carbone et le convertissent en hydrocarbures de grande valeur.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014043052A1 (fr) * 2012-09-17 2014-03-20 Phillips 66 Company Procédé permettant la capture de carbone à partir de processus de combustion existants
CN104676578A (zh) * 2015-03-24 2015-06-03 杭州美宝炉窑工程有限公司 一种生物燃料燃烧炉的二次燃烧补气装置
CN113586376A (zh) * 2021-09-02 2021-11-02 四川合众精准科技有限公司 一种基于内燃式清洁燃料的温差气动发电***及方法

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9067186B2 (en) 2009-02-20 2015-06-30 Marine Power Products Incorporated Stability control of a hydrogen generating system and method
US10145015B2 (en) 2012-12-05 2018-12-04 Marine Power Products Incorporated Hydrogen generating system and method using geothermal energy
US11214486B2 (en) 2009-02-20 2022-01-04 Marine Power Products Incorporated Desalination methods and devices using geothermal energy
US9415363B2 (en) 2009-02-20 2016-08-16 Marine Power Products Corporation Method and apparatus for efficient on-demand production of H2 and O2 from water using waste heat and environmentally safe metals
US9206043B2 (en) 2009-02-20 2015-12-08 Marine Power Products Incorporated Method of and device for optimizing a hydrogen generating system
FR2977089A1 (fr) * 2011-06-17 2012-12-28 Laurent Jean Serge Zibell Stockage et restitution de masse d'electricite sous forme chimique comprenant des etapes d'electrolyse, de methanisation et d'oxycombustion.
FR2982272B1 (fr) * 2011-11-04 2014-03-07 Commissariat Energie Atomique Procede de conversion thermochimique d'une charge carbonee en gaz de synthese contenant majoritairement h2 et co
GB201202791D0 (en) * 2012-02-20 2012-04-04 Simpson Robert Methods and system for energy conversion and generation
WO2013138349A1 (fr) * 2012-03-13 2013-09-19 Marine Power Products Incorporated Système et procédé d'utilisation sur site d'un excès de chaleur pour convertir des émissions de co2 en hydrocarbures
EP2650401A1 (fr) * 2012-04-10 2013-10-16 Siemens Aktiengesellschaft Système de méthanation basée sur une centrale électrique
FR2989366B1 (fr) * 2012-04-13 2015-08-14 Commissariat Energie Atomique Production de dihydrogene par une transformation de gaz de tete issus d'une synthese
WO2013188479A1 (fr) 2012-06-13 2013-12-19 Saudi Arabian Oil Company Production d'hydrogène au moyen d'une cellule électrolytique intégrée et d'un réacteur de gazéification d'hydrocarbure
DE102012013258A1 (de) * 2012-07-03 2014-01-09 Etogas Gmbh Verfahren zum katalytischen Methanisieren und Methanisierungsanlage
US20140065559A1 (en) * 2012-09-06 2014-03-06 Alstom Technology Ltd. Pressurized oxy-combustion power boiler and power plant and method of operating the same
CA2891185C (fr) * 2012-11-09 2021-11-09 University Of Ontario Institute Of Technology Systemes, procedes et dispositifs pour la capture et l'hydrogenation de dioxyde de carbone avec des cycles thermochimiques cu-cl et mg-cl-na/k-co2
US9464010B2 (en) * 2012-11-09 2016-10-11 University Of Toronto Institute Of Technology Systems, methods and devices for the capture and hydrogenation of carbon dioxide with thermochemical Cu—Cl and Mg—Cl—Na/K—CO2 cycles
DK3019582T3 (en) * 2013-07-09 2017-12-11 Mitsubishi Hitachi Power Systems Europe Gmbh Flexible power plant and method for operating it
FR3009308B1 (fr) * 2013-08-01 2015-09-11 Commissariat Energie Atomique Procede de conversion thermochimique d'une charge carbonee en gaz de synthese contenant majoritairement h2 et co.
US10316419B2 (en) 2013-10-12 2019-06-11 Newco2Fuels Ltd. System for utilizing excess heat for carrying out electrochemical reactions
CN103711534B (zh) * 2013-12-18 2015-03-25 文安县天澜新能源有限公司 一种二甲醚生产***低温余热的回收方法
FR3015635B1 (fr) * 2013-12-23 2019-05-31 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede integre d'oxycombustion et de production d'oxygene
FR3015637B1 (fr) * 2013-12-23 2016-01-22 Air Liquide Procede et installation de combustion avec recuperation d'energie optimisee
DE102014112580B4 (de) * 2014-09-01 2019-01-24 Mitsubishi Hitachi Power Systems Europe Gmbh Industrielle Produktionsanlage mit minimalem Treibhausgasausstoß, insbesondere Kohlendioxidausstoß, und Verfahren zum Betrieb desselben
NO20150411A1 (en) * 2015-04-09 2016-10-10 Aker Solutions As Method and plant for oxygen generation
US9845667B2 (en) * 2015-07-09 2017-12-19 King Fahd University Of Petroleum And Minerals Hybrid solar thermal enhanced oil recovery system with oxy-fuel combustor
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US20180335205A1 (en) * 2017-05-17 2018-11-22 Gas Technology Institute Pressurized fluidized bed combustor with fuel cell co2 capture
WO2018232060A2 (fr) * 2017-06-15 2018-12-20 Sabic Global Technologies B.V. Production de méthanol à partir d'un procédé de dissociation de l'eau
EP3766831A1 (fr) * 2019-07-18 2021-01-20 Linde GmbH Procédé de fonctionnement d'un four chauffé et agencement comprenant un tel four
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CN114109548B (zh) * 2021-11-24 2023-02-28 西安热工研究院有限公司 一种基于氨燃料化学链燃烧的超临界二氧化碳发电***及方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138747A1 (en) * 2002-01-08 2003-07-24 Yongxian Zeng Oxy-fuel combustion process
US20050223891A1 (en) * 2002-01-08 2005-10-13 Yongxian Zeng Oxy-fuel combustion process
US20080016868A1 (en) * 2005-12-28 2008-01-24 Ochs Thomas L Integrated capture of fossil fuel gas pollutants including co2 with energy recovery
US20080302107A1 (en) * 2007-06-08 2008-12-11 Foster Wheeler Energy Corporation Method of and power plant for generating power by oxyfuel combustion

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108014A1 (fr) * 2006-03-20 2007-09-27 Cri Ehf Procédé de production de carburant liquide à partir de dioxyde de carbone et d'eau
US8366902B2 (en) * 2008-03-24 2013-02-05 Battelle Energy Alliance, Llc Methods and systems for producing syngas
US8628725B2 (en) * 2008-11-25 2014-01-14 University Of Ontario Institute Of Technology Production of hydrogen from water using a thermochemical copper-chlorine cycle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138747A1 (en) * 2002-01-08 2003-07-24 Yongxian Zeng Oxy-fuel combustion process
US20050223891A1 (en) * 2002-01-08 2005-10-13 Yongxian Zeng Oxy-fuel combustion process
US20080016868A1 (en) * 2005-12-28 2008-01-24 Ochs Thomas L Integrated capture of fossil fuel gas pollutants including co2 with energy recovery
US20080302107A1 (en) * 2007-06-08 2008-12-11 Foster Wheeler Energy Corporation Method of and power plant for generating power by oxyfuel combustion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014043052A1 (fr) * 2012-09-17 2014-03-20 Phillips 66 Company Procédé permettant la capture de carbone à partir de processus de combustion existants
US9664385B2 (en) 2012-09-17 2017-05-30 Phillips 66 Company Process for enabling carbon-capture from existing combustion processes
CN104676578A (zh) * 2015-03-24 2015-06-03 杭州美宝炉窑工程有限公司 一种生物燃料燃烧炉的二次燃烧补气装置
CN113586376A (zh) * 2021-09-02 2021-11-02 四川合众精准科技有限公司 一种基于内燃式清洁燃料的温差气动发电***及方法

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