WO2015015042A1 - Procédé pour la combustion d'un gaz en lit fixe avec un solide oxydé et installation associée - Google Patents

Procédé pour la combustion d'un gaz en lit fixe avec un solide oxydé et installation associée Download PDF

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WO2015015042A1
WO2015015042A1 PCT/ES2014/070633 ES2014070633W WO2015015042A1 WO 2015015042 A1 WO2015015042 A1 WO 2015015042A1 ES 2014070633 W ES2014070633 W ES 2014070633W WO 2015015042 A1 WO2015015042 A1 WO 2015015042A1
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stage
gas
reactor
temperature
solids
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PCT/ES2014/070633
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Spanish (es)
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Juan Carlos ABANADES GARCÍA
Jose Ramón FERNÁNDEZ GARCÍA
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Consejo Superior De Investigaciones Científicas (Csic)
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0442—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being placed in separate reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00176—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles outside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00327—Controlling the temperature by direct heat exchange
    • B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
    • B01J2208/00353—Non-cryogenic fluids
    • B01J2208/00371—Non-cryogenic fluids gaseous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling

Definitions

  • the present invention falls within the field of obtaining energy from combustible gases incorporating capture of carbon dioxide for use or permanent storage.
  • the present invention relates to cyclic processes of combustion of gases with oxidized solids (processes of "chemical looping") in fixed bed to solve the problem of temperature control in the combustion of gaseous fuels in fixed beds of metallic oxides operating at high pressures and temperatures.
  • CO2 is the main gas responsible for climate change and the increase in its concentration in the atmosphere is mainly due to the use of fossil fuels for the generation of energy.
  • the main objective of the CO2 capture and storage technologies is to obtain a gaseous current with high CO2 purity and this entails an energy penalty on the energy generation processes without CO2 capture already existing.
  • the interest in developing new technologies of capture of CO2 that can reduce the energy penalty and the cost of the necessary equipment with respect to the known processes is increasing.
  • This oxidation step is highly exothermic, yielding a metal (or CaS0 4) oxide and a stream of oxygen - depleted air at high temperature (and in many cases high pressure) that can be used for power generation or other energy applications quality.
  • the solid oxidizes the fuel in the reduction reactor or "fuel reactor", generating a mixture rich in CO2 and water vapor.
  • the oxide reduction is usually endothermic (except in some particular cases such as CuO reduction or when H 2 and / or CO are used as fuels), so it is necessary to provide external heat to carry it out.
  • the concept of "chemical looping" for the generation of energy from a hydrocarbon is described for example in patents US5447024A and US5509362. A recent review of the state of the art of this family of processes can be found in Adanez et al. (Progress in Energy and Combustion, 38, 215-282, 2012).
  • the solid bed contains a metal that is oxidized with air (21% O2), so that the front of the oxidation reaction proceeds faster than the gas / solid exchange front.
  • the combustible gas reaches the reaction front heated by the already oxidized solids, which have also been heated before the oxidation reaction front passes.
  • the bed material must contain only a small amount of active phase of the metal that is oxidized (normally less than 15% by mass), dispersed in an inert support ( alumina, silica, zirconia, etc.). In this way, the high heat flux evolved by the oxidation of the metal with air is used to raise the temperature of a large mass of inert solids present in the reactor.
  • patent EP2514516A1 describes a way to fill a fixed bed with particles of inert material (silica, glass, ceramic material) mixed with the oxygen carrier to carry out a process of "chemical looping" and avoid excessive peaks of temperature that lead to the sintering of the material.
  • the inert solids have a larger particle diameter than the oxygen carrier solid so that their inclusion in the bed does not excessively increase the pressure drop during the oxidation and reduction operation.
  • Patent EP2305366B1 discloses a power generation method that also makes use of fixed beds, where the heat evolved in the reduction of CuO with a combustible gas (exothermic reaction) is used for the calcination of CaCÜ3 (endothermic reaction) formed in a previous stage of absorption of a combustion gas or of reforming a carbonaceous fuel. This procedure makes it possible to carry out the regeneration of the CO2 sorbent efficiently, since both reactions occur in the same bed.
  • the control of the temperature in the reaction front during the necessary oxidation of the Cu to CuO (highly exothermic) is solved by recirculating part of the nitrogen obtained at the exit of the stage and cooling it before re-feeding it to the reactor.
  • a state-of-the-art technique relevant to the object of this invention is the known way of extracting or supplying large quantities of heat to fixed beds of solids through the use of gaseous streams that pass through the bed in a cyclic manner (heating-cooling), in systems commonly known as “regenerative beds” (see for example Zarrinehkafsh and Sadrameli, “Simulation of fixed bed regenerative heat exchangers for flue gas heat recovery, Applied Thermal Engineering", 24, 373-382, 2004).
  • the efficiency in the heat transfer between gaseous streams and these fixed beds of solids can be very high depending on the operating conditions and characteristics of the gases and the bed, forming clear fronts of heat exchange in a cross section of the bed perpendicular to the gas flow, where there is a jump of gas and solids temperatures in a very short space of bed.
  • These clear heat exchange fronts advance along the bed until all bed solids reach the gas inlet temperature, while the gas leaves the bed at the initial temperature of the solids until the heat exchange front it reaches the exit point of the reactor.
  • the present invention relates to a process for the combustion of a gas in a fixed bed with an oxidized solid, which takes place in several stages, with the aim of obtaining a separate stream of CO 2 during the combustion of a gaseous carbonaceous fuel in a of the stages and continuously supply a gas free of CO 2 at high pressure and at high temperature to a gas turbine to generate power.
  • the process requires several identical fixed-bed adiabatic reactors, but operated simultaneously and synchronously in different ways in the different stages.
  • the method of invention comprises:
  • the solids at high temperature allow rapid kinetics of the reaction of reduction of the solid with the fuel. Also, in the event that the reaction of reduction is endothermic, the sensible heat contained initially in the oxidized solids at high temperature of the bed is used to maintain a high temperature in the front of reduction reaction, which allows the advance of said reduction reaction front along the bed .
  • the first stage further comprises feeding a recycle of the gas product of the first stage together with the fuel gas fed during the first stage.
  • the feeding of this recycle of a part of the gases rich in CO 2 and H 2 0 (steam) generated in the first stage, once cooled and conditioned, allows to moderate the temperature jump in the reduction reaction front and to do more fast the advance of the heat exchange front.
  • the recycle flow is designed so that in no case the exchange front reaches the reaction front before the complete reduction of the bed of initially oxidized solids. When the solid reduction reaction is endothermic, this prevents the reaction from being quenched by lack of sensible heat in the bed solids.
  • control and instrumentation techniques necessary for the sequential and synchronized operation of the different stages are also considered part of the state of the art, through the controlled opening and closing of valves (which can be cooled and / or constructed of materials that withstand high temperatures). and pressures) to alternate the entry and exit of reactants to the reactors in their different stages. It may also be necessary to purge gas stages in the reactors ("rinse”) known in the state of the art.
  • Figure 1 Shows a schematic of the preferred configuration of the method of the invention, with a snapshot of the reduction reaction front (oxidized solids in the scratched area and reduced solids in white) and of the different temperature zones expected in the reactors, indicating with jumps of temperature the different fronts of gas-solid heat exchange.
  • Figure 2 Shows a schematic of another preferred configuration of the inventive method following the same notation as in Figure 1.
  • Figure 3. Shows a flowchart of the preferred configuration of the inventive method, using NiO / Ni as an oxygen transporter, according to Example 1.
  • Figure 4 Shows an example of conceptual design of a system with the preferred configuration of the invention method, using NiO / Ni as an oxygen transporter, according to Example 1, where on the abscissa the number of reactors is indicated .
  • Figure 5 Shows an example of a conceptual design of a system with the preferred configuration of the invention method, using ilmenite as an oxygen transporter, according to Example 2, where on the abscissa axis the number of reactors is indicated.
  • the first stage of the cycle (100) shown in Figure 1 comprises the oxidation of a gaseous fuel stream (10) in a fixed-bed adiabatic reactor (101) containing initially oxidized solids, with a part of them at high temperature (T1) and with another part of them at low temperature (T4) as a result of a previous oxidation stage of said solids (to be described later).
  • the high temperature solids (T1) are initially located near the fuel gas inlet to the reactor.
  • the reduction of the solid is usually endothermic, so to sustain the advance of the reaction front of solid reduction and gas combustion, it is necessary that the bed initially contains sufficient sensible heat, which is provided by the solids at high temperature ( T1).
  • a compressor (102) compresses and heats the fuel gas (10).
  • Said already compressed and heated gas (11) is passed through a heat exchanger (103) to adjust the temperature to that required to start the first stage (100), obtaining a current (12) at the outlet of the heat exchanger (103).
  • the first stage contains a gas recycle (16) of the gas stream to the outlet (14) of the reactor (101), where a blower or fan (104) pumps said gas recycle ( 16), rich in CO2 and H 2 0, to join it to the fuel stream (12) at the outlet of the exchanger (103).
  • the rate of advance of the reduction front depends on the composition of the fuel gas and the oxidized solid, the stoichiometry of the reaction, the flow of recycle gas (17) after the blower or fan (104), the fraction of metal oxide in the bed and the difference between the molecular weights of the gas and the solid.
  • This reduction front can be advanced at a higher speed than the two gas / solid exchange fronts (the first one marked by the transition between a gas temperature at the reactor inlet (T3) and a gas temperature after the exchange of heat with the solid bed (T2), which will be described next, and the second one marked by the transition between the temperature of the solids at high temperature (T1) and the temperature of the solids at low temperature (T4) in Figure 1).
  • the inlet stream (13) of the fuel gas enters the reactor at temperature T3 and exchanges heat with the solid bed to settle at the temperature of the gas after heat exchange with the solid bed (T2) resulting from the front. of reduction, which is at a higher temperature.
  • T1, T2, T3 and T4 Upon the exchange of heat between the gas and the solid bed in the fixed-bed adiabatic reactor (101), a first heat exchange front (marked as transition between T3 and T2 in Figure 1) is established which advances to the right as the first stage (100) proceeds. As the reaction front was faster (inferred scratched area / non-scratched area in Figure 1) said front moves at all times downstream of the first exchange front (transition between T3 and T2). In the reaction front there is also a temperature jump (between T1 and T2), whose magnitude is a function, among other factors, of the enthalpy of the reduction reaction.
  • the reduction reaction can be endothermic, where T1> T2 (as in Figure 1) or can be exothermic, where T2> T1, as it would be in the case of CuO reduction with methane or in some cases where the gaseous fuel is H 2 and / or CO.
  • the gas recycle stream (16) can be designed so that the arrival of the exchange front T1 -T4 at the end of the reactor (101) coincides with the arrival at the end of the reactor (101) of the reaction front. In this way, the gas stream at the outlet (14) of the reactor (101) leaves the reactor (101) at all times at T4.
  • the progressive approach between the reaction and exchange front T1 -T4 increases the temperature jump that occurs in the reduction front, that is, the difference between T1 and T2, which makes the initial temperature of the hot part of the bed or temperature of the solids at high temperature (T1) have to be high enough not to leave the bed already reacted too cold, at temperature T2 to start a second oxidation step which will be described below ().
  • the proper design of the inert gas recycle allows to separate the advance of the reaction and heat exchange fronts during the operation, achieving a better dissipation of the generated heat of reaction and avoiding the appearance of unwanted hot spots in the reduction front.
  • the process comprises a second stage (200) where the oxidation of part of the solids contained in a reactor (201), which have been previously reduced in the first stage (100), is carried out.
  • the reactor (201) is fed with a mixed stream of air and recycled nitrogen (23) so that it was the outlet of the first stage (100), so that the second stage (200) starts rusting solids at temperature T2.
  • the nitrogen resulting from the exothermic oxidation reaction progressively heats the solids downstream of the reaction front at temperatures above T2, leaving solids at temperature T4 above the reaction front, which is equal to that of the air mixture stream and of recycled nitrogen (23).
  • the oxidation of the bed solids (200) is a highly exothermic reaction and carried out with air could cause the appearance of very hot spots in the reaction front that entail unwanted reactions and the irreversible loss of solid activity. Therefore, the recirculation of part of the nitrogen obtained as a reaction product makes it possible to regulate the maximum temperature in said oxidation front.
  • the air (20) necessary for the second stage (200) once compressed in a compressor (202), is passed through a heat exchanger (203) to adapt its temperature to that required to carry out the second one. stage (200).
  • part of the output stream (24) of the reactor (201), composed mainly of nitrogen, is recirculated, as will be seen below, which it allows decreasing the oxygen content of the stream (23) to the reactor inlet (201).
  • the gas / solid exchange front marked as transition between T5 (will be described below) and T2 in Figure 1
  • advances ahead and more quickly than the reaction front marked as inferred striped area / white zone in the second stage (200).
  • the recycled stream of air and nitrogen (23) comes at the reaction front at the inlet temperature T4 at all times and is suddenly heated up to a maximum temperature (T5) that reaches the mixed stream of air and nitrogen recycled at the front of the reactor. reaction due to the exothermic oxidation reaction.
  • the heat generated in said reaction front is transported by the product gas (mainly nitrogen) from the reaction front and ends by heating the solids downstream of the bed (exchange fronts marked by the temperature jump T5-T2 and T2-T3).
  • product gas mainly nitrogen
  • T5-T2 and T2-T3 the product gas
  • the fraction of the recirculation stream of cold nitrogen (28) must have a low temperature, preferably T4, whereby the excess sensible heat of the output stream (24) of the reactor
  • the cold pressure nitrogen (25) at the outlet of the heat exchanger (204) is fed to a fan or blower (205).
  • the fraction of the nitrogen stream (26) not recirculated to the reactor (201) is fed to a reactor (301) operating in a third stage (300) described below.
  • the third stage (300) of the preferred embodiment of the method of invention is also shown in Figure 1.
  • the further oxidation of a part of the reduced solids in the first stage (100) is carried out with a mixture of air and recycled nitrogen (33), where the nitrogen stream produced (34) at high pressure and at the temperature T5 is fed to the gas turbine (303) of a combined cycle for power generation.
  • This stage starts with a reactor (301) partially oxidized (coming from the second stage 200) and without exchange fronts apart from the temperature jump from T4 to T5, which exists in the oxidation reaction front.
  • the air (30) required for the third stage (300) is compressed in a compressor (202), and passed through a heat exchanger (302) to adjust its temperature to T4.
  • the produced nitrogen stream (34) leaving the bed (301) at temperature T5 and under pressure is expanded and cooled in a combined cycle with a gas turbine (303) and a heat recuperator (304). It is interesting, in order to maximize the electricity generation efficiency in the combined cycle, to increase the temperature of the gas entering the turbine to typical input values of said turbine (1400-1450 ° C). The nature of the solids used in the state of the art as oxygen transporters does not allow such high operating temperatures. In this case a small additional amount of fuel (60) is burned with a fraction of the compressed air (64) for the product obtained (65) to raise the temperature of the gases fed to the turbine (35). This option means that a small part of the carbon contained in the additional fuel is not captured and is emitted as CO2 into the atmosphere in the exhaust gases (38) of the gas turbine (303).
  • the concentration of oxygen in the mixture of air and nitrogen must be reduced recycled (33) entering the reactor (301).
  • part of the output gas stream (37) of the combined cycle is recycled (61) and recompressed in a compressor (307).
  • An additional heat exchanger (308) is required so that the gas recycle stream after the compressor (307) is fed at temperature T4 to the reactor (301).
  • a system of valves (305, 306) allows to regulate at the output of the combined cycle the part of the gas stream of the combined cycle that is recycled (61) to maintain constant the mixture of air and recycled nitrogen (33) that enters the reactor (301), modifying the flow rate of the recycle nitrogen stream (63) after the exchanger (308) as a function of the flows of cold nitrogen streams under pressure (27, 53).
  • the oxidation is carried out in a reactor (401) of the final part of the solids reduced in the first stage (100) and not yet oxidized in the second and third stages (200, 300).
  • a mixture of a stream of compressed and cooled air (42) to T4 and a stream of recycled cold nitrogen (54) is fed to the reactor (401) and a stream (44) of nitrogen is generated at the outlet of the reactor.
  • reactor at temperature T5.
  • the reactor (401) is completely oxidized and is at the temperature of the inlet gas T4.
  • the fifth and final stage of the cycle (500) has the purpose of heating the bed of completely oxidized and cold solids, initially to T4, resulting from the end of the fourth stage (400), in order to restart a new cycle with the first stage (100 ).
  • the nitrogen stream (44) leaving the reactor (401) in the fourth stage (400) is cooled slightly in a heat exchanger (502) to the temperature T1 and fed to the reactor (501), which has totally oxidized solids and initially at temperature T4. These solids are heated progressively at temperature T1 as the exchange front advances, marked as transition between T1 and T4.
  • the cold nitrogen stream (51) leaving the reactor (501) at the initial temperature of the bed T4 is fed to a fan or blower (503) to compensate for the pressure drop suffered by the gas as it passes through the reactor (501).
  • Part of the stream (52) at the outlet of the fan or blower (503) is recirculated to the inlet of the reactor (401) as recycled cold nitrogen stream (54), reactor (401) which is operating at that time in the fourth step (400), where the rest of the non-recycled nitrogen (53) to the fourth stage (400), is fed to the reactor (301), which is operating at that time in the third stage (300).
  • the device described in the process steps of the present invention allows adjusting through the degree of recycling of recycled gases (CO2 and steam in the case of the first stage (100), and nitrogen in the second, third, fourth and fifth stages). (200), (300), (400) and (500) oxidation,), the speed of displacement of the reaction fronts and heat exchange inside the reactors in each of the stages.
  • the practical implementation of this procedure when using solids with high oxygen transport capacity requires an installation where at least eight are used adiabatic fixed-bed reactors operated simultaneously but in different phases of the five stages described above.
  • Example 1 Preferred embodiment of the method of the invention using a solid with a high oxygen transport capacity: NiO / Ni.
  • the conceptual design of the cyclic procedure represented in Figure 1 is carried out, which has as its object the combustion of a combustible gas (CH 4 in this example) with an oxide with a high oxygen transport capacity (NiO in this example) .
  • the example has been proposed for the continuous combustion of 10 kg / s (0.63 kmol / s) of pure CH 4 (10) in a first stage (100), carried out in a fixed-bed adiabatic reactor (101) to 20 pressure bar, in which is found a solid whose composition in percentage by weight is in this example: 60% NiO and 40% AI2O3.
  • gas piston flow and average thermal properties of the solid materials that make up the bed and of the inlet gases and the reaction products have been assumed for all stages.
  • the heat capacity of the gas varies between 2.20 kJ / kg K at the reactor inlet (101) and 1.75 kJ / kg K at the outlet, due to the change in temperature and composition experienced by the gas during the first stage (100)
  • the average heat capacity of the solids is initially 0.98 kJ / kg K and once the first stage (100) is 0.91 kJ / kg K.
  • the increase of gaseous moles in the NiO reduction reaction with CH 4 causes the gas / solid exchange front marked as transition between T1 and T4 to advance 1.46 times faster than that marked as T3-T2 transition and 0.9 times faster than in front of reduction.
  • the compressor (102) supplies the inlet stream (13) of the fuel gas at 20 bar and 150 ° C (T3 in Figure 1).
  • the recirculation of part of the reactor outlet stream (101) allows to decrease the concentration of CH 4 in the inlet stream (13) of the fuel gas and increase the mass flow of gas through the bed. In this way, the velocities of the reaction fronts and the gas / solid heat exchange are approximated.
  • the gas recycle (16) is designed so that the first stage (100) can be started with a part of the bed at low temperature (150 ° C, T4 in Figure 1) and that the arrival of the reaction front at the end of the reactor coincides with the arrival of the T1-T4 exchange front and not before.
  • Nickel is a thermally stable material with a high melting temperature (1453 ° C), which makes it possible to operate with it at very high temperatures without any loss of solid activity or agglomeration. This assumes a bed temperature of oxidized solids at T1 (see Figure 1) of
  • the recirculation of 52% of the product gas from the reactor (101), gas recycle (16), allows to carry out the complete reduction of the NiO starting from a bed with 45% of it at 1200 ° C (T1). in Figure 1) and 55% at 150 ° C (T4 in Figure 1).
  • the inlet stream (13) of the fuel gas, fed to the reactor (101) at 150 ° C (T3) and 20 bar, contains 2.72 kmol / s with a volume content of: 23% CH 4 , 26% CO2 and 51% of H 2 0.
  • the temperature jump resulting from the reduction of NiO with CH 4 is 550 ° C, so that the temperature T 2 is 650 ° C.
  • FIG. 3 the flow diagram of the process of the invention is represented when NiO / Ni is used as an oxygen carrier.
  • a first reactor (1) operates as a first stage (100).
  • a valve (615) at the entrance of the first reactor (1) remains open, while another valve (616) at the entrance of the first reactor (1) is closed, allowing to feed continuously the methane required for the first stage (100), avoiding the entry of air.
  • other valves (617, 623, 624, 625) remain closed, while another valve (618) remains open, as well as other valves (621, 626) that regulate the outlet of steam and CO2 from the system and recycle, respectively.
  • a compressor (202) feeds a flow of 1.86 kmol / s of air (20) through the exit point of the first stage (100), where there is higher temperature (650 ° C, T2 in Figure 1), which allows a clear oxidation front to be achieved from the start where the oxygen fed is completely converted and NiO is produced.
  • the oxidation enthalpy of Ni is ⁇ -452 kJ / mol O2
  • the composition of the air in the calculations of this example is considered 21% of O2 and 79% of N 2 (composition by volume)
  • the molecular weight of the air is 29 g / mol
  • the initial average molecular weight of the solids in the reactor (201) is 73 g / mol.
  • the heat capacity of the gas is maintained at around 1 .13 kJ / kg K and that of the solids is initially 0.91 kJ / kg K and once the second stage (200) is 0.98 kJ / kg K. Due to the high exothermicity of Ni oxidation with air, the temperature on the reaction front would quickly reach values well above 1200 ° C, which would cause the irreversible loss of activity of the nickel material.
  • reaction front (inferred gray / white), which advances from behind.
  • the exchange front marked as transition T3-T2 advances 1 .05 times faster than the front marked as transition T2-T5.
  • the output stream (24) of the reactor (201) corresponds to a flow of 7.27 kmol / s, of which 57% (by volume) does so at a temperature of 150 ° C (T3), corresponding to the time in that the first exchange front (T3 to T2) has not yet reached the exit, while the remaining 43% (in volume) does so at 650 ° C (T2), corresponding to the time in which the second exchange front (T2 to T5) is still inside the reactor (201).
  • T3 150 ° C
  • T2 the recirculation current of cold nitrogen
  • a second and a third reactor (2, 3) operate as two second stages (200).
  • the valves (628) and (639) at the entrance of the second and third reactors (2, 3) remain open, while other valves (627, 638) at the entrance of the second and third reactors ( 2, 3) are closed, which allows feeding the required air to the second and third reactor (2, 3), preventing the entry of methane to them.
  • valves (630, 641) remain open and other valves (629, 640) are closed, since in the second stages (200) no product gas is sent to the combined cycle.
  • valves (633) and (644) remain closed because during the second stages (200) no CO2 and water vapor are generated.
  • Another valve (634) is open to send the nitrogen product from the second reactor (2) not recirculated to a fourth reactor (4), which at that time operates as a third stage (300), while another valve (636) remains closed because it is not required to send nitrogen not recirculated to the third reactor (3), since this reactor (3) also operates as a second stage (200).
  • Other valves (635, 645, 646) are closed because no external nitrogen is needed for the second and third reactors (2, 3), while other valves (637, 648) remain open to pass the recycled N 2 taken to the output of the second and third reactors (2, 3), respectively.
  • Another valve (647) is open to send to the fourth reactor (4), which operates as a third stage (300), the nitrogen produced in the third reactor (3) and not recirculated.
  • the additional oxidation of a part of the solids reduced in the first stage (100) is carried out with air and with recycled N 2 , where the nitrogen produced in the reactor (301), goes out to high pressure and maximum oxidation temperature of 1200 ° C (T5 in Figure 1) and is fed to a gas turbine (303) of a combined cycle where it expands and cools producing power. For this, a flow of 2.98 kmol / s of compressor air (202) is fed.
  • the concentration of oxygen at the entrance of the reactor (300), must be 5% to not exceed 1200 ° C on the oxidation front (T5 in Figure 1)
  • part of the exhaust gases of the heat recovery (304) of the combined cycle are recirculated (61) and recompressed up to 20 bar in the compressor (307) and adjust its temperature to 150 ° C in the heat exchanger (308) before being mixed with the compressed air stream (32).
  • the total inflow in the third stage (300) is 12.26 kmol / s and that of the produced nitrogen stream (34) of 1 1.64 kmol / s.
  • the cold nitrogen streams at excess pressure of the rest of the steps that make up the present process (27, 53) are also fed back to the reactor inlet (301).
  • the excess gas stream (27) from the second stage (200) assumes a flow of 1.47 kmol / s, while the excess gas stream (53) from the fifth stage (500) is from 0.87 kmol / s.
  • a system of valves (305, 306) collected in the state of the art allows to regulate at the outlet of the combined cycle the gas recycle stream (61) to maintain the mixture of air and recycled nitrogen at all times. (33) a constant flow of 12.26 kmol / s with 5% O2.
  • a fourth, a fifth and a sixth reactor (4, 5, 6) operate as third stages (300).
  • some valves (650, 660, 672) remain open, while other valves (649, 660, 671) are closed, which allows to supply the required air to the fourth, fifth and sixth reactor (4, 5, 6), avoiding the entry of methane to them.
  • other valves (651, 661, 673) remain open and other valves (652, 662, 674) are closed, since in the third stages (300) all the product gas is sent to the combined cycle.
  • other valves 650, 660, 672
  • valves (655, 665, 677) remain closed because during the third stages (300) CO2 and water vapor are not generated.
  • Other valves (657, 669, 680) are open to allow the passage of the N 2 recompressed and fed back to the third stages (300), taken from the output of the combined cycle.
  • Other valves (658, 670, 681) are open to allow the passage of recirculated N 2 , while other valves (656, 666, 667, 668, 678, 679) remain closed.
  • valves (613, 614), represented in Figure 3 and corresponding to a methane and air line, respectively, remain open at all times.
  • the impacts of this addition of fuel gas on the recycle compositions and the inert gases accompanying the oxygen entering the reactor (301) during the third stage (300) are not discussed in this example, as evident.
  • the third stage (300) is where more useful energy is obtained from the system, because it is the only stage where the hot high pressure nitrogen generated in the reactor (301) expands and cools in a combined cycle.
  • the third stage must be interrupted before completing the oxidation of the bed and thus leave sufficient sensible heat to restart a new cycle with the first stage (100). Otherwise, the bed of solids would be completely oxidized and all the solids in the bed at the feed temperature of the air mixture and recycled nitrogen (33) (150 ° C), which would make it impossible to restart a new cycle with the first stage (100) endothermic.
  • the reactor (401) starts from an initial state with 80% of the oxidized solids.
  • the oxidation of 100% of the solids in the reactor (401) is completed using a mixture of air (1.1 kmol / s, stream 40) and recirculated nitrogen (54) (3.45 kmol / s), obtaining as a product a nitrogen stream (44) of 4.32 kmol / s at 1200 ° C (T5) and leaving a completely oxidized bed at 150 ° C (T4) upstream of the reaction front.
  • a seventh reactor (7) operates as a fourth stage (400).
  • one valve (683) remains open, while another valve (684) is closed, which allows to feed the seventh reactor (7) air and not methane.
  • Another valve (685) remains open, but other valves (684, 688) are closed because N 2 is not sent to the combined cycle nor is generated in the fourth stage (400) CO2 and water vapor.
  • Another valve (700) remains open to drive all the N 2 produced in the seventh reactor (7) to the eighth reactor (8), which operates as a fifth stage (500). Therefore, another valve (689) is closed.
  • Other valves (690, 691) remain open to allow the passage of part of the N 2 obtained in an eighth reactor (8), which is recirculated to the seventh reactor (7) to meet the balance of matter at the entrance of said reactor.
  • the reactor starts a fifth and final stage (500) destined to heat with the nitrogen coming from from the fourth stage (400) a part of the oxidized solids of the reactor (501) up to the temperature of 1200 ° C (T1 in Figure 1). Therefore, the heat exchanger (502) is not necessary for this example, with (44) and (50) being the same gas stream.
  • the temperature T5 has been matched to the temperature T1 set in the first stage (100). Therefore, the stream (50) is introduced into the oxidized reactor (501) and its sensible heat allows 45% of the fixed bed to be heated up to 1200 ° C, a fraction required to carry out a new first reduction stage (100) .
  • valves (692, 693) are closed.
  • a valve (695) remains open, but the other valves (694, 698) are closed because N 2 is not sent to the combined cycle nor is CO2 and water vapor generated in the fifth stage (500).
  • Another valve (699) remains open to allow passage of the N 2 leaving the eighth reactor (8) and being sent to other reactors that are operating in the third or fourth stage (300, 400).
  • Another valve (701) is closed and another valve (702) open, which allows to feed the N 2 obtained in the seventh reactor (7) to the eighth reactor (8).
  • Another valve (701) is closed and another valve (702) open, which allows to feed the N 2 obtained in the seventh reactor (7) to the eighth reactor (8).
  • the material balance indicates that a mass of solids (N ⁇ O + AI 2 O3) is required for the first stage (100). Approximately 100000 kg. Assuming that these solids are in the form of pellets with an average density of 1700 kg / m 3 and an equivalent diameter of 0.01 m, and considering a bed porosity of 0.5, a bed volume of solids of 58 m 3 is obtained. example, by similarity with the commercial reforming reactors, a length of 5 m is adopted for each reactor, which implies a reactor cross-sectional area of approximately 10 m 2. For this example, this area is compatible with the existence of a single reactor of reduction.
  • the second and third reactors (2, 3) are used in this example operating simultaneously and under identical conditions as reactor (201) in the second stage (200 ). Under these conditions, the gas passes at a maximum surface velocity of 2.3 m / s, causing a pressure drop of 0.85 bar. In the same way, to the third stage (300) 12.26 kmol / s are fed (5% in volume of O2) during 5 minutes until completing the same one. To limit the pressure drop of the gas to less than 1 bar during this stage, three reactors (4, 5, 6) which operate simultaneously under identical conditions as reactor (301) are considered.
  • the gas circulates at a maximum surface velocity of 2.4 m / s, causing a pressure drop at the outlet of each reactor of 0.95 bar.
  • 4.55 kmol / s (5% by volume of O2) are fed for 5 minutes.
  • a single reactor, in this case the seventh (7) is sufficient under the conditions of this example.
  • the gas circulates at a maximum surface velocity of 2.6 m / s, causing a head loss of 1 .10 bar.
  • the 4.32 kmol / s leaving the fourth stage (400) are fed to a single reactor, in this case the eighth reactor (8), which operates as a reactor (501) in the fifth stage (500).
  • Example 2 Preferred embodiment of the method of the invention using a solid with low oxygen transport capacity: Fe 2 Ti05 / FeT03 (ilmenite).
  • the conceptual design of the cyclic process represented in Figure 2 is carried out, which has as its object the combustion of a combustible gas (pure CH 4 in this example) with an oxide with low oxygen transport capacity (ilmenite in this example). ).
  • the illustrative example has been proposed for the combustion of 10 kg / s (0.63 kmol / s) of CH 4 (10) in a first stage (100), carried out in a fixed bed adiabatic reactor (101) at 20 bar of pressure, in which a solid is found whose composition as a percentage by weight is: 60% Fe 2 TiOs and 40% AI 2 O 3. It has been assumed for all stages that the gas flows in piston flow.
  • the reduction enthalpy of Fe 2 TiOs to FeT03 with CH 4 is 106.5 kJ / mol CH 4 and the oxidation of FeT03 to Fe 2 TiOs with oxygen is -454.4 kJ / mol O2.
  • Ilmenite is a thermally stable material with a high melting temperature (1365 ° C), which allows it to be operated at very high temperatures without any loss of solid activity or agglomeration.
  • the increase of gaseous moles in the reduction reaction of Fe 2 TiOs with CH 4 makes the gas / solid exchange front marked as transition between T1 and T4 advance 1.3 times faster than the marked as transition T3-T2 and 0.7 times with respect to the reduction front.
  • the Fe 2 T05 is a material moderately reactive with CH 4 , which makes the initial temperature of the hot part of the bed (T1 in Figure 2) have to be at least 750 ° C to guarantee a high reaction rate and a clear reduction front.
  • the inlet stream (13) of the fuel gas is fed at 20 bar and 400 ° C (T3 in Figure 2) after passing through the compressor (102) and the heat exchanger (103).
  • the recirculation of 67% of the output stream of the reactor (101) allows to approximate the speeds of the fronts of reduction and heat exchange gas / solid so that the complete reduction of the Fe 2 TiOs can be carried out starting from a bed with 30% of it at 755 ° C (T1 in Figure 2) and 70% at 400 ° C (T4 in Figure 2).
  • the input stream (13) of the fuel gas contains 4.46 kmol / s with a volume content of: 14% CH, 29% C0 2 and 57% H 2 0.
  • the Temperature jump resulting from the reduction of Fe 2 T ⁇ Os with CH 4 is 55 ° C, so the temperature T2 is 700 ° C.
  • 51% of the bed remains cold at the temperature T3 of the inlet gas (400 ° C), and the rest remains at a temperature T2 of 700 ° C (T1 -55 ° C).
  • a compressor (202) feeds an air flow of 5.95 kmol / s (21) at 20 bar and 400 ° C (T4 in Figure 2) through the exit point of the first stage (100). ), which is 700 ° C (T2), allowing achieved from the outset a front crisp oxidation FeT ⁇ 0 3 Fe2 T ⁇ Os where all oxygen fed reaches complete conversion.
  • the moderate exothermicity of the oxidation reaction of ilmenite with air causes the maximum temperature increase in the reaction front with a solid with the composition indicated in this example 2 (60% active phase) to be close to 400 ° C.
  • the recirculation (28) of around 25% of the output stream of the reactor (201), makes it possible to accelerate the advance of the exchange front T5-T4 and bring it closer to the oxidation front, which is ahead moving 5.3 times more fast (see Figure 2).
  • T5-T2 temperature increase in the reaction front
  • T5-T5 specifically 500 ° C, which means that for the initial conditions of the second stage (200) is reached a maximum temperature (T5) of 1200 ° C (limit value assumed in this example to ensure that the ilmenite does not suffer loss of activity or agglomeration phenomena).
  • the current air mixture recycle nitrogen (23) reactor inlet (201) resulting is 7.39 kmol / s, with a composition by volume of 17% O2 and 83% N2.
  • a swap front T3-T2 moves ahead of the oxidation front (201) and another swap front T5-T4, indicated above, moves behind it.
  • the number of moles in the gas phase decreases when the O2 fed is consumed, so that the T3-T2 exchange front advances slower, specifically for the conditions of this example 0.83 times the speed of the T5-T4 exchange front.
  • the output current (24) of the reactor (201) corresponds to a flow of 6.14 kmol / s, of which 12% (by volume) do so at a temperature of 400 ° C (T3 in Figure 2), which correspond at the time in which the first exchange front T3-T2 has not yet reached the exit, while the remaining 88% does so at 700 ° C (T2), corresponding to the time on the oxidation front still inside the reactor (201).
  • the excess sensible heat is extracted in an exchanger (204) and the resulting current (25) is introduced into a blower (205) to compensate for the pressure drop in the reactor (201).
  • the second stage (200) ends when the oxidation front reaches the end of the reactor (201), which implies that all the ilmenite present has been oxidized to Fe 2 T05.
  • the exchange front T5-T4 is still inside the reactor (201), which makes 53% of the bed remain at 1200 ° C
  • a flow of 10.05 kmol / s of nitrogen (33) is fed, which is a mixture of 4.70 kmol / s of the non recirculated gas stream (27) in the second stage (200) and of 5.35 kmol / s (stream 63), which is a part of the exhaust gases of the heat recovery unit (304) of the combined cycle, which have been recirculated and recompressed in a compressor (307) up to 20 bar.
  • stream 63 which is a part of the exhaust gases of the heat recovery unit (304) of the combined cycle, which have been recirculated and recompressed in a compressor (307) up to 20 bar.
  • the sensible heat excess of the output stream (44) of the fourth stage (400) is extracted in the heat exchanger (502) prior to being fed to the reactor (501) of the fifth stage (500).
  • the fifth stage (500) ends when 30% of the solids that make up the bed have been heated up to 755 ° C, a prerequisite for starting a new first stage (100) of reduction.
  • the reactor (201) is fed 7.39 kmol / s (17% by volume of O2) also for 5 minutes. Under these conditions, two reactors are used operating simultaneously and in identical conditions as reactor (201). The gas passes at a maximum surface velocity of 0.9 m / s, causing a pressure drop of 0.15 bar. In the same way, to the third stage (300) 10.05 kmol / s of nitrogen are fed during 5 minutes until completing it. A single reactor operates in this stage (300). Under the conditions of this example the gas circulates at a maximum surface velocity of 2.4 m / s, causing a pressure drop at the output of the reactor of 0.95 bar.
  • 13 kmol / s of nitrogen are fed to the reactor (401) for 5 minutes.
  • a single reactor operating as reactor (401) is sufficient under the conditions of this example.
  • the gas circulates at a maximum surface velocity of 3.1 m / s, causing a pressure drop of 1.6 bar.
  • the 13 kmol / s of nitrogen leaving the fourth stage (400) are fed to a single reactor that operates as a reactor (501) in the fifth stage (500). After 5 minutes, 30% of the solids in the bed are heated to 755 ° C, thus achieving the conditions required to restart a new cycle in the first stage (100).
  • the gas circulates at a maximum superficial velocity of 2.1 m / s, causing a loss of load at the outlet of 0.75 bar.
  • a number of 7 adiabatic reactors of 25 m 2 of cross-sectional area and 5 m of length operating in parallel is required (Figure 5): 2 in the first stage (100 ), 2 in the second oxidation stage (200), 1 in the third stage (300) of gas / solid heat exchange, which continuously produces hot gas under pressure for the combined cycle, 1 in the fourth stage (400 ) of heat exchange gas / solid and 1 in the fifth stage (500) conditioning its temperature to restart the cycle in the first stage (100).
  • the duration of a complete cycle is 35 minutes.
  • the number of reactors is lower (seven) than in Example 1 (eight), the total volume of solids required for the process using ilmenite as an oxygen carrier is almost double that in the case of using nickel oxide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé permettant l'obtention d'énergie à partir de gaz combustibles comprenant la capture du dioxyde de carbone afin de l'utiliser ou de le stocker de manière durable, et plus précisément, l'invention concerne des procédés cycliques de combustion de gaz avec des solides oxydés (procédés d'anaérocombustion) en lit fixe pour résoudre le problème de la régulation de la température lors de la combustion de combustibles gazeux en lits fixes d'oxydes métalliques fonctionnant à hautes pressions. L'invention concerne également une installation associée.
PCT/ES2014/070633 2013-08-02 2014-08-01 Procédé pour la combustion d'un gaz en lit fixe avec un solide oxydé et installation associée WO2015015042A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3724534A1 (de) * 1987-07-24 1989-02-02 Bayer Ag Verfahren und vorrichtung zur durchfuehrung exothermer chemischer reaktionen in der gasphase
US20050175533A1 (en) * 2003-12-11 2005-08-11 Thomas Theodore J. Combustion looping using composite oxygen carriers
US20100279181A1 (en) * 2009-05-01 2010-11-04 Massachusetts Institute Of Technology Systems and methods for the separation of carbon dioxide and water
EP2515038A1 (fr) * 2011-04-21 2012-10-24 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Combustion en boucle chimique de lit fixe

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3724534A1 (de) * 1987-07-24 1989-02-02 Bayer Ag Verfahren und vorrichtung zur durchfuehrung exothermer chemischer reaktionen in der gasphase
US20050175533A1 (en) * 2003-12-11 2005-08-11 Thomas Theodore J. Combustion looping using composite oxygen carriers
US20100279181A1 (en) * 2009-05-01 2010-11-04 Massachusetts Institute Of Technology Systems and methods for the separation of carbon dioxide and water
EP2515038A1 (fr) * 2011-04-21 2012-10-24 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Combustion en boucle chimique de lit fixe

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