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    • 专利摘要:
    PROCESS AND INSTALLATION OF COMBUSTION IN CHEMICAL CIRCUIT WITH INDEPENDENT CONTROL OF THE SOLID CIRCULATION. The present invention relates to an improved chemical circuit combustion installation and process of at least one hydrocarbon charge with control independently of the circulation of solid particles of active mass between the reaction zones in fluidized layer, by means of one or several non-mechanical L-type valves.
    公开号:BR112012000975B1
    申请号:R112012000975-3
    申请日:2010-06-30
    公开日:2020-10-13
    发明作者:Thierry Gauthier；Ali HOTEIT；Ann Forret
    申请人:Total S.A.；IFP Energies Nouvelles；
    IPC主号:
    专利说明:

    Domain of the invention
    [0001] The present invention concerns the domain of combustion in a chemical circuit. Following the text, the CLS (Chemical Looping Combustion) combustion method is understood as an oxide-reduction method in a circuit over active mass. It should be noted that, in general, the terms oxidation and reduction are used in relation to the respectively oxidized or reduced state of the active mass. The oxidation reactor is one in which the oxide-reducing mass ("active mass" or "oxygen carrier") is oxidized and the reduction reactor is the reactor in which the oxide-reducing mass is reduced. When reducing the oxide-reducing mass, the fuel can be either fully oxidized, producing CO2 and H2O, or partially oxidized, producing CO and H2 synthesis gas.
    [0002] The oxidation of the active masses can be done in air, or in the presence of a gas that can give oxygen under the conditions of the method, such as, for example, the water value. In this case, the oxidation of the active masses makes it possible to produce a gaseous effluent rich in hydrogen.
    [0003] Preferably, the active masses are metal oxides.
    [0004] More particularly, the invention relates to an improved installation and methods of combustion in a chemical circuit of a hydrocarbon cargo, by means of one or more non-mechanical L-type valve. LIST OF FIGURES
    [0005] Figure 1 represents a sectional view of a non-mechanical valve called "L-shaped valve", as described by Knowiton, Tm>, "Standpipes and Nnmmechanical VBalves", Handbook of Fluidization and Fluid-Particle Systems, Wen -Ching Yang, editor, pp. 571- 597.Marcel Dekker, Inc. New York, 2003.
    [0006] Figures 2 and 3 also represent sectional views of the same L-shaped valve, including a schematic representation of the flow of solids and gas, with gas flow down (A) and gas flow up (B) .
    [0007] Figure 4 represents a schematic view of a layered method that circulates using the L valves (Prior art).
    [0008] Figure 5 represents a schematic view of a method of combustion in a circulating layer boiler (prior art).
    [0009] Figure 6 represents a schematic view of a catalytic cracking method of the FCC (Fluid Catalytic Cracking) type, in which a valve with a paddle (SLIDE valve) or with a plug ("plug valve") is used to control the circulation between the different compartments (prior art).
    [0010] Figure 6 represents a schematic view of a chemical loop combustion method of the Chemical Looping (CLC) type (prior art).
    [0011] Figure 8 represents a schematic view of a combustion method in a chemical circuit with control of the circulation of solids, according to the invention, in which the device comprises an ascending duct for transporting particles between the reaction zones " lift ", variant, 1).
    [0012] Figure 9 represents a schematic view of a combustion method in a chemical circuit with control of the circulation of solids, decoding, without upward conduit for the transport of particles between the reaction zones (variant 2).
    [0013] Figure 10 represents a schematic view of a combustion method in a chemical circuit, according to the invention using a regulation of the gas injected into the L-shaped valves (variant 3).
    [0014] Figure 11 represents a schematic view of the model described in the example.
    [0015] Figure 12 is a graph that represents the head loss in an upward transport lift channel as a function of the circulating solid flow.
    [0016] Figure 13 represents a graph that symbolizes the relationship between the aeration flow in each L-shaped valve and the flow of solid that circulates in the installation. EXAMINATION OF THE PREVIOUS TECHNIQUE
    [0017] Thanks to the injection of gas, upstream of a curve, non-mechanical valves allow the particles to circulate in a pipe. This type of equipment is well known and described in the literature (Knowiton, TM, "Standpipes and Nonmechanical Valves", Handbook of Fluidization and Fluid-particle Systems, Wen-Ching Yang, editor, pp.571-597, Marcel Dekker, Inc. New York, 2003).
    [0018] Thus, in figure 1, an L-shaped valve is described. The L-shaped valve consists of a vertical pipe fitted at its base with a 90 ° curve. If the vertical channel is filled with particles, the injection of a gas, positioned upstream of this curve in the vicinity of the change of direction allows the circulation of particles in the channel. Depending on the pressure conditions imposed on the system terminals, a part of the injected gas descends into the conduit, passes the curve and favors the transport of the particles (figures 2 and 3, configurations A and B). A portion of the injected gas can also rise against the counter flow of the particles (figure 3, configuration B). The proportion of injected gas that rises is adjusted according to the pressure conditions at the valve terminals.
    [0019] L-shaped valves allow to control the circulation of solid, when the flow in the vertical pipe upstream of the gas injection point is non-fluidized (that is, the difference in speed between the flow of the gas and the flow of the particles remains less than the minimum fluidization speed of the particles under conditions). These valves are particularly suitable for the use of group B particles of the Geldart classification, which have a minimum fluidization speed high enough to allow a high flow of particles.
    [0020] Knowiton (Knowiton, TM, "Standpipes and Nonmechanical Valves", Handbook of Fluidization and Fluid-particle Systems, Wen- Ching Yang, editor, pp.571-597, Marcel Dekker, Inc. New York, 2003) describes a circulating layer system using L-shaped valves (figure 4). A circulating fluidized layer (CFB), in which the gas injected underneath ("Gas In") allows the particles to be transported, drives the gas and particles up to a C cyclone. Particle-free gases exit the cyclone through a conduit (" Gas Out ") and the separated particles are reintroduced in the layer that circulates through an L-shaped valve (" L-Valve). This system allows to decouple the internal circulation of solid inside the gas flow circuit in the layer that circulates, the pressure available for the transport of particles in the circulating layer, depending on the amount of aeration gas injected (aeration) in the L-shaped valve (which allows the pressure recovery to be varied in the vertical part of the L-shaped valve).
    [0021] In the classical industrial methods of circulating fluidized layer combustion, however, the applied technologies do not allow to independently control the internal circulation of solid in the circuit. In figure 5 (Nowak et al., IFSA 2008, Industrial Fluidization South Africa, pp. 25-33. Edited by T. Hadley and P. Smit Johannesburg: South Africa Institute of Mining and Metallurgy, 200 *), a layered boiler rolling stock is represented. The combustion air is introduced at the base of the circulating layer and transports the coal and sand particles to a cyclone. The particles are then recycled in the fluidized layer that circulates through a return leg. The return leg is dimensioned to favor the recycling of solid, but does not allow the control of the circulation of solids. It is not equipped with L-shaped valves. Sometimes, siphons are positioned on this return leg to prevent gas rising in the return leg. However, in these systems, the circulation of solid within the circuit is entirely subject to the amount of combustion air introduced into the circulating layer.
    [0022] There are other ways to control the circulation of solids. When conditions permit, mechanical valves on solids can be used. Thus, in the fluidized layer catalytic cracking method (Fluid Catalytic CRaking: FCC), a method that operates at temperatures below 800-850 C, slide valve or plug valve are used to control circulation between different compartments (Figure 6, Gauthier, IFSA 2008, Industrial Fluidization South Africa, pp. 35 - 87. Edited by T.Hadley and P. Smit Johannesburg: South Africa Institue of Mining and Metallurgy, 2008).
    [0023] In figure 6, the following elements that allow the application of the FCC method are represented: R1: regenerator n ° 1 R2: regenerator n ° 2 PV1: mechanical valve with plug (plug valve n ° 1) PV2: mechanical valve with shovel n 01 (slide valve n ° 1) RSV1: mechanical valve with shovel n ° 1 (slide valve n ° 1) RSV2: mechanical valve with shovel n ° 1 (slide valve n ° 2) L: upward transport duct (lift ) Fl: feed injection Q = Quench RR: riser reactor RS: stripper reactor
    [0024] These valves operate on fluidized flows and have the characteristic of controlling the flow, modifying the passage section, the head loss of these valves remaining, in general, constant and dependent only on the fluidization conditions of the particles upstream of the valve. These valves are particularly adapted to the operation on particles of group A of the classification of Geldart. Unfortunately, the operation of these valves on group B particles is more delicate. In effect, it is impossible to keep the group E particles fluidized, forming large gas bubbles that disturb the flow. In addition, the moving parts of these valves exposed to flow cannot be exposed to very high temperatures (> 900 ° C).
    [0025] Combustion by chemical circuit is a technique that allows partial or total combustion of gaseous, liquid or solid hydro-carbonate charges, by contact with an active mass such as, for example, a metal oxide at high temperature. The metal oxide then yields a part of the oxygen it contains, which participates in the combustion of hydrocarbons. Therefore, it is no longer necessary to put the hydrocarbon in contact like air, as in classical methods. In this way, combustion fumes mostly contain carbon oxides, water and eventually hydrogen, undiluted by nitrogen in the air. Therefore, it is possible to produce smoke that is mostly nitrogen-free and contains high CO2 levels (> 90% vol), making it possible to consider uptake, then CO2 storage. The metal oxide that participated in the combustion is then transported to another reaction composition where it is placed in contact with the air to be oxidized. If the particles coming from the combustion zone are free of fuel, the gases from that reaction zone will be mostly free of C02 - which is then only present in the trace state, for example, at concentrations below 1 - 2% by volume) - and consist essentially of oxygen-depleted air as a result of the oxidation of metallic particles.
    [0026] The application of a chemical circuit combustion method requires quantities of active masses, for example, considerable metal oxides in contact with the fuel. Metal oxides are generally contained, either in mineral particles or in particles resulting from industrial treatments (waste from the steel or mining industry, catalysts from the chemical or refining industry used). Synthetic materials can also be used, such as, for example, alumina or silica alumina substrates on which metals that can be oxidized (nickel oxide, for example) will have been deposited. From one [metallic oxide to another], the amount of theoretically available oxygen varies considerably and can reach high values close to 30%. According to the materials, however, the maximum oxygen capacity actually available does not generally exceed more than 20% of the oxygen present. The capacity of these materials to yield oxygen does not therefore exceed more than a few percent by weight of the particles overall and varies considerably from one oxide to another, usually from 0.1 to 10%, and often between 0.3 to 1 % by weight. Use in a fluidized layer is therefore particularly advantageous for conducting combustion. In effect, the finely divided oxide particles circulate more easily in the reaction reduction and oxidation compartments, and between these compartments, if the particles are given the properties of a fluid (fluidization).
    [0027] Combustion by chemical circuit allows to produce energy, in the form of steam or electricity, for example. The heat of combustion of the charge is similar to that found in classical combustion. This corresponds to the sum of the reduction and oxidation heats in the chemical circuit. The distribution between the reduction and oxidation heaters depends a lot on the active masses (notably metal oxides) used to conduct combustion by chemical circuit. In certain cases, the exotherm is divided between oxidation and reduction in active mass. In other cases, oxidation is very exothermic and the reduction is endothermic. In all cases, the sum of the oxidation and reduction heats is equal to the combustion heat of the fuel. The heat is extracted by exchangers located inside, on the wall or in the appendix of the combustion and / or oxidation compartments, over the smoke lines, or over the metal oxide transfer lines.
    [0028] chemical circuit combustion principle is currently well known (Mohammad M. Hossain, Hugo I. de lasa, Chemicallooping combustion (CLC) for in he rente CO2 separations - a review, Chemical Engineering Science 63 (2008) 4433 - 4451; LyngfeltA., Johansson M., and T. Mattison, "Chemical Looping Combustion, status of development", in CFB IX, J.Werther, W.Nowak, K.-E. Wirth and E.-U. Hartge (Eds), Tutech Innovation, Hamburg (2008, figure 7) In figure 7, the "air" reactor (1) is represented schematically, in which metal oxides are oxidized, a cyclone (2) allowing the gas particles to separate , and the "fuel" reactor or combustion reactor (3), home of the reduction of metallic oxides.The use of the chemical circuit in a continuous installation is still the object of numerous investigations and developments.
    [0029] In a classic combustion installation in a circulating layer, the internal circulation of solids in the circulation circuit is dependent on the flow of air introduced into the circulating layer.
    [0030] In a CLC combustion method by chemical circuit, combustion control is, on the contrary, dependent on the amount of solid particles fed in contact with the fuel. The circulation of particles of active mass circulating in the combustion compartment conditions the amount of oxygen available for combustion and the final oxidation state of the active mass at the end of combustion. Once combustion has taken place, the active mass (metal oxides most often) must be oxidized again in contact with air in a separate compartment. The circulation between the two compartments will condition: - the oxygen exchange between the reduction reactor and the oxidation reactor; - the heat exchange between the fuel reactor and the oxidation reactor; - the passage of gas between one of these compartments and which must be minimized.
    [0031] Therefore, it is important to be able to control the circulation of solids in the air reactor and in the combustion reactor, regardless of the flow of gases that circulate, and which conditions the transport of particles within each of these compartments (air in the oxidation reactor) , steam, hydrocarbons or combustion fumes in the fuel reactor).
    [0032] The different methods proposed until today do not allow an independent control of the oxide circulation. Thus, Johannsonn et al. (2006) propose a combustion method in a chemical circuit in which the oxidation of the metallic oxide is done in a circulating layer. The oxides are separated in a cyclone that discharges the fuel reactor in which combustion takes place. The metal oxide is then recycled in the oxidation reactor. This system does not allow to control the circulation of metal oxides regardless of the air flow in the oxidation reactor. The flow of metal oxide circulating in the combustion reactor can only be modified by changing the air flow in the air reactor.
    [0033] Another device is described in patent FR2850156. In this case, the two combustion and oxidation reactors are circulating layers. Furthermore, the circulation between the two reactors depends on the gas flow introduced in each of the compartments. In both cases, siphons are positioned over the transfer lines, allowing the transport of metal oxides. These siphons ensure the tightness of the gas phases between the two compartments, preventing gas from the oxidation reactor to circulate to the combustion reactor, through the transfer lines and vice versa. These siphons do not allow to control and modify the circulation of metal oxides.
    [0034] In addition, the chemical circuit combustion method is preferably applied at high temperature (between 800 and 1200 ° C, typically between 900 ° and 1000 °). It is therefore not possible to control the circulation of metal oxides, using mechanical valves classically used in other methods such as the FCC.
    [0035] The object of the invention is, therefore, to propose a new installation in a new method that allows a control of the circulation of solids in the chemical circuit, regardless of the flow of gases circulating in the oxidation combustion (reduction) compartments. OBJECT OF THE INVENTION
    [0036] An object of the present invention is a combustion method in a chemical circuit, allowing the complete or partial combustion of gaseous, liquid or solid hydrocarbons.
    [0037] Another object of the invention is a combustion plant in a chemical circuit, allowing the complete or partial combustion of gaseous, liquid or solid hydrocarbons.
    [0038] The method, according to the invention, is applied in a facility that comprises at least two fluidized reaction zones, one placing solid particles of active mass (such as metal oxides, for example) in contact with air to oxidize the particles, the other putting the hydrocarbons in contact with the active mass to carry out the combustion reactions, the combustion oxygen being supplied by the reduction of the active mass particles.
    [0039] In the method and installation, according to the invention, the circulation of solids (particles of active mass, playing the role of oxygen carriers) between the different reaction zones is controlled by non-mechanical L-type valves, each consisting of a substantially vertical channel, after a substantially horizontal channel, a control gas being injected upstream of the curve.
    [0040] The present invention also refers to the use of this combustion method in a chemical circuit with control of the circulation of solids for the production of heat, for the production of synthesis gas or for the production of hydrogen. DESCRIPTION OF THE INVENTION Summary of the invention
    [0041] The invention relates to a chemical circuit combustion method of at least one hydrocarbon charge in at least one reduction reaction zone (i) and at least one oxidation reaction zone (i + 1) in a separate fluidized layer , in which the circulation of solid particles of active mass is controlled between each or a part of the reaction zones by means of one or more non-mechanical valves constituted, each of a substantially vertical channel part, of a substantially horizontal channel part , and a curve connecting the two parts, transporting the solid particles between two successive reaction zones by: - introducing the solid particles from the reaction zone (i) or (i + 1) through the upper end of the substantially vertical channeling part of that valve; - injection of a control gas with an aeration flow determined upstream of the curve of this valve; - control of the differential pressure conditions on the terminals of the non-mechanical valve (s) to regulate the flow of solid particles in the substantially horizontal channeling part of this valve, depending on the aeration flow; - feeding of the successive reaction zone (i + 1) or (i) of the circuit by the solid particles coming out of the non-mechanical valve (s).
    [0042] Each reaction zone may consist of a set of one or more fluidized reactors arranged between them.
    [0043] Several non-mechanical valves can be positioned in parallel between two successive reaction zones.
    [0044] In an embodiment of the method, according to the invention: - in addition, it is introduced between (at least) two successive reaction zones ie (i + 1) and downstream of the valve (s) non-mechanic (s) a transport gas in an ascending transport conduit ("lift"), this conduit being fed by the solid particles coming out of the non-mechanical valve (s); - the solid particles are transported from zone (i) to zone (i + 1) by passing fluidized particles through the non-mechanical valve (s) located between zones (i ) and i + 1), then by transporting the solid particles by means of at least one transport gas injected into the upstream transport duct, and the solid particles are separated from the transport gas, thanks to gas - solid separation means located in the exit of the ascending duct to feed the zone (i + 1) in solid particles; - the solid particles are transported at the exit from the zone (i + 1) to the zone (i) by passing the fluidized particles in the non-mechanical valve (s) located between the zones (i +1) and (i), then by transporting the solid particles by means of at least one carrier gas injected into the upstream transport conduit, and the carrier gas particles are separated, thanks to gas - solid separation means located at the exit of the ascending duct to feed the zone (i) in solid particles.
    [0045] In another embodiment of the method, according to the invention, a reaction zone (i + 1) is partly at least above the previous reaction zone (i) and: - the solid particles of the zones are transported (i + 1) to zone (i) by gravity flow through the non-mechanical valve (s) ^) located between zones (i + 1) and (i); - the solid particles are transported from zone (i) to zone (i + 1) by passing fluidized particles through the non-mechanical valve (s) located between zones (i ) and (i + 1), then by transporting the solid particles by means of at least one transport gas injected in an upward transport duct, and the solid particles are separated from the transport gas, thanks to separation means gas-solid, located at the exit of the ascending duct to feed the zone (i + 1) in solid particles.
    [0046] Another object of the invention is a chemical circuit combustion plant of at least one hydrocarbon charge in the presence of solid particles of active mass, comprising at least one reaction zone of reduction in fluidized layer (i), at least one zone fluidized layer oxidation reaction (i + 1), at least one ascending circulation medium (6) of these particles of that reaction reduction zone (i) and this reaction oxidation zone (i + 1), these particles being dragged in the middle upward circulation by a carrier gas (19), at least one gas-solid separation medium (7) located at the outlet of that upward circulation medium and connected to that reaction oxidation zone (i + 1) by a conduit (8) , at least a first valve to control the circulation of these particles between the reaction zone of oxidation (i + 1) and the reaction zone of reduction (i) and at least a second valve to control the circulation of these particles between the reaction zone of reduction (i) and the ascending circulation medium (6), these valves comprising at least one means of injecting a control gas (11, 4) with a determined aeration flow.
    [0047] In a variant of the invention, the installation may further comprise: - at least a second ascending means (12) of circulation of these particles of that reaction oxidation zone (i + 1) and that reaction reduction zone (i), these particles being entrained in the ascending circulation medium by a second transport gas (20), this second ascending circulation medium being placed between that first control valve and this reaction reduction zone (i); and - at least one second gas-solid separation means (13) located at the outlet of that second upward circulation medium (12) and connected to that reaction reduction zone (i).
    [0048] It is possible to control the circulation by subjecting the aeration flow of the control gas of the non-mechanical valves to level measurements in the fluidized reactors and / or pressure losses in the transport pipelines, carried out in the reaction zones.
    [0049] Thus, the aeration flow of the control gas (4) can be controlled by a regulating valve (21) subject (23) to the level measurement (25) in at least one fluidized layer of the reaction reduction zone ( 1) and this aeration flow of the control gas (11) can be controlled by a regulating valve (22) subject (24) to the pressure loss measure (26) in the upstream particle transport duct to the first reaction zone (12).
    [0050] Advantageously, a length of the horizontal part of the non-mechanical valve (s) Lh is chosen between 1 and 20 times the diameter of the horizontal duct part Dh, preferably between 3 and 7 times Dh .
    [0051] Advantageously, the diameter of the vertical duct part Dv is greater than or equal to the diameter of the horizontal duct part Dh of the non-mechanical valve (s).
    [0052] Preferably, the diameter of the vertical duct part DV and the diameter of the horizontal duct part Dh of the non-mechanical valve (s) are substantially identical.
    [0053] Advantageously, the control gas injection point is positioned upstream of the curve at a distance x (difference between the height of the injection point in the vertical part and the lowest point of the non-mechanical valve) of the order of 1 at 5 times the diameter of the vertical duct part Dv.
    [0054] Preferably, solid particles of active mass belong to group B of the Geldart classification.
    [0055] Most preferably, solid particles of active mass are metal oxides.
    [0056] The invention also refers to the use of the method, according to the invention, for the production of hydrogen, for the production of synthesis gas, or for the production of heat. Detailed description of the invention
    [0057] Combustion in a chemical circuit allows heat, synthesis gas, hydrogen to be generated by circulating solid particles, containing active masses that act as oxygen carriers, such as metallic oxides, between various reaction zones, in which the oxide thallic is successively exposed to contact with an oxidizing medium (for example, air), then a reducing medium (for example, a gaseous, liquid or solid hydrocarbon).
    [0058] In order to facilitate circulation and contact, the invention refers to a method in which the reaction zones are constituted of reactors in each fluidized one.
    [0059] In terms of heat production, particles of active mass (for example, particles of metal oxide) are advantageously placed in contact with air in a fluidized layer, in which metal oxides are oxidized, then they are transported by pipelines in a fluidized layer, in which metallic oxides are placed in contact with hydrocarbons, for example, methane, natural gas, a heavy fuel containing petroleum distillation residues, coal or petroleum coke. The oxide is then reduced to the contact of the hydrocarbons and this burns to the contact of the oxygen provided by the particles. The fumes in the combustion zone essentially contain the products resulting from partial or total combustion (CO, H2, CO2, H20, SOx ...) in the absence of nitrogen, the layer can be fluidized by combustion fumes, water vapor, for example. example. In this way, the fumes are then easily treated to refer, if necessary, to the CO2 or the synthesis gas produced (water condensation, smoke desulphurisation), which makes capturing CO2 or using the synthesis gas easy. it's interesting. Combustion heat can be recovered by heat exchange inside the reaction zones to produce the value or any other use.
    [0060] In terms of hydrogen production, it is also possible to integrate other reaction zones in the method, in which, for example, particles containing metal oxides reduced to a hydrocarbon or water vapor are exposed.
    [0061] The conditions under which the reduction and oxidation reactions are made by contact with metal oxides are severe. The reactions are usually carried out between 800 and 1200 ° C, typically between 900 and 1000 ° C. Energy production methods operate advantageously at a pressure as close as possible to atmospheric pressure. The methods for the production of synthesis gases or hydrogen operate preferably at higher pressures that allow the application downstream of methods using reaction products to minimize the energy consumption linked to the compression of the gases produced, typically between 20 and 50 bariums, for example, 30 bariums when using synthesis gas as a filler for a Fischer Tropsch synthesis method.
    [0062] The reaction times required to carry out the oxidation and reduction reactions depend on the nature of the treated charges and the metal oxides used and vary from a few seconds to a dozen minutes or so. Combustion reactions of liquid and solid charges generally require the longest reaction times, for example, in the order of several minutes. Nature of solid particles of active mass
    [0063] The installation and method, according to the invention, can be used with any type of active mass. Preferably, the particles of active mass are particles of metal oxides.
    [0064] The application of a combustion method in a chemical circuit requires important amounts of active mass in contact as fuel.
    [0065] Preferably, these solids are packaged in powder form, with a Sauter diameter between 30 and 500 microns, and with a grain density between 1400 and 8000 kg / m3, preferably between 1400 and 500 kg / m3 .
    [0066] Depending on the particle size, the flow properties of the particles vary (Geldart, 1973). Thus, the finer Group A particles of the Geldart classification are characterized by lower fluidization speeds and low speed fluidization characteristics, allowing for dense fluidized transport. The thicker Group B particles of the Geldart classification are characterized by higher fluidization speeds and fluidization characteristics that allow considering a dense non-fluidized transport in pipes between two reaction compartments.
    [0067] In the event that the active mass consists of metallic oxides, these are generally contained in mineral particles (Fe, Ti, Ni, Cu, MG, Mn, Co, V oxides, used alone or in mixture) , whether in particles resulting from industrial treatments (waste from the steel or mining industry, catalysts from the chemical or refining industry used). It is also possible to use synthetic materials, such as, for example, alumina or silica alumina supports on which metals that can be oxidized (nickel oxide, for example) will have been deposited.
    [0068] From one metallic oxide to another, the amount of theoretically available oxygen varies considerably and can reach high values close to 30%. According to the materials, however, the maximum oxygen capacity actually available does not, in general, exceed more than 20% of the oxygen present. The ability of these materials to yield oxygen therefore does not exceed, overall, more than a few percent by weight of the particles and varies considerably from one oxide to another, generally from 0.1 to 15%, and often between 0.3 and 1% by weight. Use in a fluidized layer is therefore particularly advantageous for leading to combustion. In fact, the finely divided oxide particles circulate more easily in the reaction compartments of combustion and oxidation and, between these compartments, if the particles are given the properties of a fluid (fluidization). Circulation of solids between reaction zones
    [0069] The control of the circulation of solid particles that play the role of active mass (or oxygen carriers), such as particles of metal oxides, for example, is essential for the proper functioning of the method in chemical circuit. Indeed, the transport of particles between the compartments conditions the transport of oxygen, an essential reagent for the proper functioning of the method and the heat exchanges between the different zones and, therefore, the temperature level, at which each zone will operate. depending on the temperature in other areas. The particle transport must also be studied as a gas exchange vector between the different zones, the particles in flow in the transfer zones that can drag gases from one reaction zone to another.
    [0070] At the temperature levels considered, mechanical valves cannot be used to control the circulation of solids between two reaction zones, unless the flow is cooled before contact with the valve, an energetically penalizing and technologically complex solution. Thus, the object of the invention is to apply a method using non-mechanical valves of the L-valve or "L-type" type, consisting of a substantially vertical duct, a substantially horizontal duct, a control gas being injected upstream of the curve formed by the two pipes.
    [0071] The particles coming from the first reaction zone enter the L-shaped valve through the upper end of the substantially vertical flue, feeding the valve by means of stretching (cone, inclined channeling, stretching wells ...) well known to the technician.
    [0072] They then flow vertically in granular flow, the difference in real speed between the particles and the gas being less than the minimum fluidization speed.
    [0073] The control gas injected into the L-shaped valve can be mounted against the counterflow of the particles that descend in the vertical duct, or flow down with the particles and favor the flow of the particles in the horizontal part of the valve.
    [0074] The distribution between upstream and downstream gas depends on the differential pressure conditions at the L valve terminals. If the pressure upstream of the valve increases in relation to the pressure downstream of the valve, for example, then it will be possible usually find that the proportion of upstream gas will decrease. The flow of solid in the horizontal part depends on the amount of gas descending and circulating with the particles in the horizontal part. L-valve design
    [0075] The diameter of the duct of the vertical part of the valve in L shall be recorded with Dv and with the diameter of the duct in the horizontal part with Dh, the length of the horizontal pipe and Lv the length of the vertical pipe, and with xa distance between the elevation of the control gas injection point in the vertical part and the lower part of the L-shaped valve.
    [0076] The height Lv depends on the relative position of the two reaction compartments and pressure gains or losses to be compensated for circuiting the pressure balance of the method. This height will therefore result from the installation sizing the case by case by the technician.
    [0077] Advantageously, the horizontal channel length should be limited to ensure a stable flow of particles. This length Lh will preferably be between 1 and 20 Dh, preferably between 3 and 7 Dh. The operation of the L-shaped valve will be favored, if the diameters Dv and Dh are substantially identical. In all cases, it is preferable that the diameter of the horizontal part Dh is greater than or equal to Dv.
    [0078] Finally, the position of the control gas injection point upstream of the curve will be positioned in the vicinity of it, preferably at a distance X close to the order of 1 to 5 Dv, the typical values being close to C = 2 - 3 Dv.
    [0079] Between two reaction zones, it is possible to position one or more L-shaped valves in parallel. Operation of the installation and method according to the invention
    [0080] Figure 8 below describes a first embodiment of the invention. The applied method is a combustion method, using the chemical circuit principle.
    [0081] A first reaction reduction zone (1) allows contact between a gaseous, liquid or solid hydrocarbon (15) and particles of active mass (in the case of metal oxide) to effect the fuel. The reaction zone can be a simple reactor in a fluidized layer consisting of a gas distribution box over the section, the fluidized layer and means of dedusting the gaseous effluents (16) constituted in the present case of concentrated smoke in CO2 or a combination fluidized layers, or circulating fluidized layers with internal or external particle recycling.
    [0082] In this reaction zone, at least part of the contact zone between the hydrocarbons and the metal oxide are stretched from the first reaction zone (1), this stretch feeding a vertical duct (3), ending with a horizontal duct (5) which constitutes an L-shaped valve. A control gas (eg nitrogen, water vapor or smoke) is injected into this L-shaped valve through a conduit (4). The solid circulates in the L-shaped valve and feeds a transport lift (6) fed by a transport gas (19). At the exit of the lift (6), separation means (7), such as cyclones, allow the transport gas to be separated from the particles. These particles are then transported by a conduit (8) to the second reaction zone (2), in which the oxidation reactions of the oxide particles are carried out by contact with the air that feeds the second reaction zone through a conduit (17) . The reaction zone can be a simple reactor in a fluidized layer consisting of a gas distribution box over the section, the fluidized layer and means of dedusting the gaseous effluents (18) constituted, in the present case, of depleted air, or a combination of fluidized layers, or circulating fluidized layers with internal or external particle recycling. In this reaction zone, at least a part of the contact zone between hydrocarbons and metal oxide consists of a dense fluidized phase. The metal oxide particles are stretched from the second reaction zone (2), this stretch feeding a vertical duct (9) that ends with a horizontal duct (10) that a L-shaped valve. A control gas (for example, nitrogen, water vapor, or air) is injected into this L-shaped valve (11). The circulation of solid in the L-shaped valve (9-10) depends on the amount of gas injected through the conduit (11). The particles leave the L-shaped valve (9-10) and feed a transport lift (12) fed by a transport gas (20). At the exit of the lift, separation means (13), such as cyclones, allow the transport gas to be separated from the particles that are transported by a conduit (14) to the first reaction zone (1), in which the combustion reactions take place.
    [0083] Figure 8 describes a method and an installation with two reaction zones, but it is possible to consider a chain of three or several reaction zones arranged sequentially as in figure 8.
    [0084] In the application of the method, according to the invention, the transfer of particles between the reaction zones depends only on the amount of control gas injected into the L-shaped valves. Thus, it is possible to vary the circulation of metal oxides, modifying the flow of control gas injected into the L-shaped valves, all other fluids (15, 17, 19, 20) being kept constant.
    [0085] In L valves, the flow of particles in the vertical part (3, 9) is a dense non-fluidized granular flow, the particles flowing with a relative speed in relation to the circulating gas in these conduits below the minimum fluidization speed. The method will be applied preferably with particles belonging to group B of the Geldart classification. The gas injected into the L-shaped valves (4, 11) generally represents a small proportion (<1%) of the gas required to ensure transportation (19, 20), the minimum fluidization speed of these materials being very low, compared to the particle transport.
    [0086] The transport gas used in the upward transport ducts (lifts) (6, 12) can, therefore, consist of steam, recycled smoke, air or inert, and, depending on your choice, may allow create a buffer zone avoiding the mixing of the entrained gases from one reaction zone to the other.
    [0087] In the configuration described in figure 8, the L-shaped valve feeds a transport duct (lift) allowing the transport of particles. The lift is equipped at the exit of separation means, allowing the release of the transport gas. It is, therefore, possible to introduce a gas between the two reaction compartments (1) and (2) for the transport of particles, this gas penetrating neither the compartment (1) nor the compartment (2), thanks to the separation means located at the exit of the transport lift. This configuration is particularly advantageous when it is desired to seal the gases between the reaction compartments. In effect, the gas that serves to control the circulation in the L-shaped valve and the transport gas in the lift can be composed of inert gases (water vapor, nitrogen, carbon dioxide ...) that will seal the area. reaction zone (1), in which gas phase hydrocarbons can be found and the reaction zone (2) in which gas phase oxygen is found. The quantities of gases entrained from the reaction zones (1) or (2) to the L-shaped valves are zero or very small. They depend on the elevations of the respective compartment pressures and the flow of circulating particles. These small amounts will be diluted by the lift transport gas (for example, an inert) and evacuated from the unit via the gas outlets of the separators (7, 13) located at the outlet of the transport lifts. It is seen, therefore, that the configuration constituted by the arrangement of L-shaped valves and lift between the reaction zones allows not only to control the circulation, but also to ensure the gas tightness between the reaction zones.
    [0088] Figure 9 represents another possible arrangement, different simply from the configuration shown in figure 8, in that the reaction oxidation zone (2) is partly at least above the reduction-combustion zone (1). It is then possible to transport the oxide particles from zone (2) to zone (1), without using a transport lift. A simple L-shaped valve (9, 10, 11) then allows the transfer of particles from zone (2) to zone (1). The transfer from zone (1) to zone (2) is done using an L-shaped valve (3, 4, 5), an upward transport duct (6) and means of separating (7) the metal oxides and the transport gas.
    [0089] It is possible to control the circulation of solids in the method between the different compartments thanks to a regulation of the gas injected into the L-shaped valves. Figure 10 resumes the method described in figure 8. If a valve regulates the gas injection in the valve in L, it will be possible to subject the amount of gas injected into the L-valve to level measurements in a fluidized layer in a dense phase or to an indirect measurement of the flow in circulation, such as pressure drop in a transport lift. Thus, in figure 10, the gas injection (4) is controlled by a regulating valve (21) subject (23) to the level measurement (25) in a fluidized layer of the reaction compartment (1) and the gas injection ( 11) is controlled by a regulating valve (22) subject (24) to the pressure drop (26) in the lift (12). Other subjection strategies are possible. EXAMPLE
    [0090] In order to illustrate the operation of the invention, an example of a circulation circuit sized according to the main characteristics of the invention, used in ambient conditions without reaction, is given below.
    [0091] The model (figure 11) consists mainly of two identical fluidized layers R1 and R2 of 10 cm in diameter, linked together by two so-called circulating circuits. Each circuit consists of a lift (upward transport conduction) of 20 mm in diameter and 2.5 m in length, powered by an L-shaped valve, also known as an L-shaped leg, consisting of a vertical section and a horizontal section of same diameter (16 mm) in which an aeration gas is injected at an elevation of 30 mm, in relation to the bottom of the L-shaped valve. The particles are stretched from the fluidized layer (R1 or R2) at the top of the vertical part (Vv1 or Vv2) of the L-shaped valve. They flow in the vertical part, then in the horizontal (Vh1 or Vh2) part of the L-shaped valve. They are then transported in a lift (L1 or L2) at the end of which a cyclone (C1 or C2) separates the lift transport gas from the particles. The particles are reinjected into the fluidized layer (R2 or R1) through a return leg and a siphon (S1 or S2).
    [0092] The particles used in this test are particles of sand with an average diameter of 205 microns and a grain density equal to 2500 kg / m3. In the fluidized layers R1 and R2, the particles are fluidized at a surface speed of 0.08 m / s. This gas velocity is higher than the minimum fluidization velocity (Umf), which is in the order of 0.03 m / s. The particles of the solid descend from the first reactor called R1 in the vertical leg Vv1, then their circulation in the horizontal leg Vh1 is ensured by the injection of a control gas (aeration flow) introduced upstream of the change in the flow direction in the L-shaped valve. It is by regulating the aeration flow that the solid flow is controlled. In the lift, a constant flow of transport gas is maintained. This transport gas is introduced at the bottom of the lift and differs from the aeration gas introduced in the L-shaped valve.
    [0093] In order to ensure a satisfactory particle transport, the UL1 or UL2 gas velocity in the L1 or I2 lifts is kept constant and equal to 8 m / s. Downstream of the lift, the suspension circulates on a horizontal T1 or T2 transport line that feeds a cyclone C1 or C2 that allows the separation between the particles and the gas. The gas leaves the cyclone at the top of the cyclone and the solid is sent to a S1 or S2 trap and then sent to the second reactor (R2 or R1).
    [0094] The amount of control gas (aeration gas) injected into the L-shaped valve is taken to the passage section on the vertical part of the e4m L valve (diameter = 16 mm). It is thus possible to calculate the surface velocity in empty body of the aeration in this section. By the sequence, the aeration in the valve in L1 will be expressed by its surface speed in empty body Uv1 and the aeration in the valve in L2 will be expressed by its surface speed in empty body Uv2.
    [0095] The quantities of gases sent in the L-shaped valves, which correspond to the Uv1 and Uv2 speeds, respectively, allow controlling the flow of solid sent to reactor R2 via lift L1 (figure 12) and to reactor R1 via lift R2.
    [0096] In the circuit, it is possible to estimate the solid flows, thanks to non-stationary operations during which the variations of level as a function of time in the compartments allow the measurement of the instantaneous solid flows. These flows of solids are then correlated to the head losses in the transport lifts. In fact, it is known that for a fixed gas volume flow, the pressure drop in a lift increases when the solid flow increases. In this example, the increase in this head loss is substantially linear as a function of the solid flow, as shown in figure 12, the two lifts showing similar head losses (their geometry and the imposed transport speed are identical).
    [0097] Once these previous calibrations are done, continuous operation in the installation is established, imposing an aeration flow of the identical control gas in each of the two L-valves. When the injected control gas valve corresponds to a gas velocity in each of the L valves (Uv1 and Uv2) equal to 0.15 m / s, stable operation is observed, the levels in each of the compartments remaining constant over time. The pressure drop measured under these conditions in each of the lifts is approximately 5 mbaria, which corresponds to a flow of solid in each of the lifts of approximately 60 kg / hour (figure 12).
    [0098] The aeration flow in each of the L-shaped valves is then increased to reach a surface speed (Uv1 and Uv2) of 0.175 m / s. The solid circulation then passes to approximately 80 kg / h (load loss highlighted in the lifts equal to 6 mb). Thereafter, the aeration flow rate in the L valves is reduced to 0.13 m / s, the circulation of solids decreases at approximately 48 kg / h (pressure drop in the lifts equal to 4 mb).
    [0099] It stands out from this example that the circulation of solid in the installation depends only on the aeration imposed by the control gas in the L-shaped valves. Figure 13 shows the relationship between the aeration flow in each L-shaped valve and the flow of solid circulating in the installation.
    权利要求:
    Claims (16)
    [0001]
    1. Chemical circuit combustion method of at least one hydrocarbon charge in at least one reaction zone of reduction (i) and at least one reaction zone of oxidation (i + 1) in different fluidized layers, characterized by the fact that it is controlled the circulation of solid particles of active mass between each or a part of the reaction zones by means of one or more non-mechanical valves each consisting of a substantially vertical channel part, a substantially horizontal channel part, and a curve that connects the two parts, transporting the solid particles between two successive reaction zones by: - introducing the solid particles from the reaction zone (i) or (i + 1) through the upper end of the substantially vertical channeling part of that valve, the flow of the particles in the vertical line part of the valve being a dense, non-fluidized granular flow; - injection of a control gas with an aeration flow determined upstream of the curve of this valve; - control of the differential pressure conditions at the terminals of the non-mechanical valve (s) to regulate the flow of solid particles in the substantially horizontal channeling part of this valve, depending on the aeration flow; - feeding of the successive reaction zone (i + 1) or (i) of the circuit by the solid particles coming out of the non-mechanical valve (s).
    [0002]
    2. Chemical circuit combustion method according to claim 1, characterized by the fact that each reaction zone consists of a set of one or more fluidized reactors arranged between them.
    [0003]
    3. Chemical circuit combustion method according to claim 1 or 2, characterized by the fact that several non-mechanical valves are positioned in parallel between two successive reaction zones.
    [0004]
    4. Chemical circuit combustion method according to any one of claims 1 to 3, characterized by the fact that: - in addition, it is introduced between (at least) two successive reaction zones (i) and (i + 1) and downstream of the non-mechanical valve (s) ^) a transport gas in an upward transport conduit, that conduit being fed by the solid particles coming out of the non-mechanical valve (s); - the solid particles are transported from zone (i) to zone (i + 1) by passing fluidized particles through the non-mechanical valve (s) located between zones (i ) and (i + 1), then by transporting the solid particles by means of at least one transport gas injected into the upstream transport conduit, and the solid particles are separated from the transport gas, thanks to gas-solid separation means , located at the exit of the ascending duct to supply the zone (i + 1) with solid particles; - the solid particles are transported at the exit from the zone (i + 1) to the zone (i) by passing the fluidized particles in the non-mechanical valve (s) located between the zones (i ) and (i + 1), then by transporting the solid particles by means of at least one transport gas injected into the upstream transport duct, and the solid particles are separated from the transport gas, thanks to gas-solid separation means , located at the exit of the ascending duct to supply the zone (i + 1) with solid particles.
    [0005]
    Chemical circuit combustion method according to any one of claims 1 to 3, characterized in that a reaction zone (i + 1) is located at least partly above the previous reaction zone (i) and: - are transported solid particles from zone (i + 1) to zone (i) by gravity flow through the non-mechanical valve (s) located between zones (i + 1) and (i ); - the solid particles are transported from zone (i) to zone (i + 1) by passing fluidized particles through the non-mechanical valve (s) located between zones (i ) and (i + 1), then by transporting the solid particles by means of at least one transport gas injected in an upward transport duct, and the solid particles are separated from the transport gas, thanks to separation means solid gas, located at the exit of the ascending duct to supply the zone (i + 1) with solid particles.
    [0006]
    6. Chemical circuit combustion method according to any of claims 1 to 5, characterized by the fact that the circulation of solids is controlled by subjecting the aeration flow of the control gas of the non-mechanical valves to level measurements in the reactors fluidized and / or pressure losses in the transport pipelines, carried out in the reaction zones.
    [0007]
    7. Chemical circuit combustion method according to claim 6, characterized by the fact that the aeration flow of the control gas (4) is controlled by a regulating valve (21) subject (23) to the level measurement ( 25) in at least one fluidized layer of the reaction reduction zone (1) and this aeration flow of the control gas (11) is controlled by a regulating valve (22) subject (24) to the pressure drop measurement (26) in the upstream particle transport duct to the first reaction zone (12).
    [0008]
    8. Chemical circuit combustion method according to any one of claims 1 to 7, characterized in that the length of the horizontal part of the non-mechanical valve (s) Lh is chosen between 1 and 20 times the diameter of the horizontal duct part Dh, preferably between 3 and 7 times Dh.
    [0009]
    9. Chemical circuit combustion method according to any one of claims 1 to 8, characterized in that the diameter of the vertical duct part Dv is greater than or equal to the diameter of the horizontal duct part of the valve (s) ( s) non-mechanical (s).
    [0010]
    10. Chemical circuit combustion method according to claim 9, characterized in that the diameter of the vertical duct part Dv and the diameter of the horizontal duct part Dh of the non-mechanical valve (s) appreciably identical (s).
    [0011]
    11. Chemical circuit combustion method according to any one of claims 1 to 10, characterized by the fact that the control gas injection point is positioned upstream of the curve at a distance x (difference between the height of the control point injection in the vertical part and the lowest point of the non-mechanical valve) of the order of 1 to 5 times the diameter of the vertical duct part Dv.
    [0012]
    12. Chemical circuit combustion method according to any one of claims 1 to 11, characterized in that the solid particles of active mass belong to group B of the Geldart classification.
    [0013]
    13. Chemical circuit combustion method according to any one of claims 1 to 12, characterized in that the solid particles of active mass are metallic oxides.
    [0014]
    14. Use of the method as defined in any of claims 1 to 13, characterized by the fact that it is for the production of hydrogen.
    [0015]
    15. Use of the method as defined in any of claims 1 to 13, characterized by the fact that it is for the production of synthesis.
    [0016]
    16. Use of the method as defined in any of claims 1 to 13, characterized by the fact that it is for the production of heat.
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    同族专利:
    公开号 | 公开日
    RU2012105342A|2013-08-27|
    RU2529300C2|2014-09-27|
    CA2767073A1|2011-01-20|
    CN102612625B|2014-12-24|
    PL2454525T3|2017-02-28|
    FR2948177B1|2011-08-05|
    CA2767073C|2017-04-25|
    JP2012533049A|2012-12-20|
    CN102612625A|2012-07-25|
    US20120148484A1|2012-06-14|
    US8771549B2|2014-07-08|
    ES2605231T3|2017-03-13|
    FR2948177A1|2011-01-21|
    EP2454525B1|2016-08-24|
    BR112012000975A2|2016-03-15|
    KR20120061825A|2012-06-13|
    AU2010272467A1|2012-02-09|
    AU2010272467B2|2016-06-16|
    WO2011007055A2|2011-01-20|
    EP2454525A2|2012-05-23|
    WO2011007055A3|2011-05-19|
    KR101571203B1|2015-11-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1408888A|1971-11-12|1975-10-08|Exxon Research Engineering Co|Manufacture of combustible gases|
    US3969089A|1971-11-12|1976-07-13|Exxon Research And Engineering Company|Manufacture of combustible gases|
    GB1523500A|1975-10-21|1978-09-06|Battelle Development Corp|Method of operating a fluidized bed system|
    ZA859561B|1984-12-20|1986-08-27|Trw Inc|Fluidization aid|
    JP2922210B2|1989-02-06|1999-07-19|富士石油株式会社|Hydrodealkylation method|
    RU2028543C1|1990-10-22|1995-02-09|Всероссийский теплотехнический научно-исследовательский институт|Circulating fluidized-bed furnace|
    JPH06134287A|1992-10-26|1994-05-17|Tsukishima Kikai Co Ltd|Two-tower circulation type fluidized beds|
    US5341766A|1992-11-10|1994-08-30|A. Ahlstrom Corporation|Method and apparatus for operating a circulating fluidized bed system|
    US5540894A|1993-05-26|1996-07-30|A. Ahlstrom Corporation|Method and apparatus for processing bed material in fluidized bed reactors|
    US5735682A|1994-08-11|1998-04-07|Foster Wheeler Energy Corporation|Fluidized bed combustion system having an improved loop seal valve|
    JPH0960813A|1995-08-28|1997-03-04|Babcock Hitachi Kk|Fluidized medium circulation apparatus for fluidized layer|
    JPH10300020A|1997-04-25|1998-11-13|Hitachi Ltd|Power generation system|
    JP3670824B2|1997-11-18|2005-07-13|三菱重工業株式会社|Fluidized bed height control method for pressurized fluidized bed boiler|
    JP2002286216A|2001-03-28|2002-10-03|Chugai Ro Co Ltd|Operation method for circulated fluidized bed|
    US6572761B2|2001-07-31|2003-06-03|General Electric Company|Method for efficient and environmentally clean utilization of solid fuels|
    FR2850156B1|2003-01-16|2005-12-30|Alstom Switzerland Ltd|COMBUSTION INSTALLATION WITH CO2 RECOVERY|
    JP4076460B2|2003-03-18|2008-04-16|中外炉工業株式会社|L valve type loop seal for circulating fluidized bed incinerator|
    JP4274124B2|2005-01-11|2009-06-03|株式会社Ｉｈｉ|Method and apparatus for measuring fluid circulation rate of circulating fluidized bed combustion apparatus|
    FR2889248B1|2005-07-29|2007-09-07|Inst Francais Du Petrole|NOVEL OXYDO-REDUCTIVE ACTIVE MASS FOR A LOOP OXYDO-REDUCTION PROCESS|
    RU56559U1|2005-12-21|2006-09-10|Открытое акционерное общество "Всероссийский дважды ордена Трудового Красного Знамени теплотехнический научно-исследовательский институт" |INSTALLATION FOR COMBUSTION OF GAS-FUEL IN CHEMICAL CYCLE WITH SEPARATION OF CARBON DIOXIDE WHEN USING PARTICLES OF OXIDE CARRIERS OF OXYGEN OXYGEN|
    FR2895413B1|2005-12-27|2011-07-29|Alstom Technology Ltd|PETROLEUM HYDROCARBON CONVERSION INSTALLATION WITH INTEGRATED COMBUSTION FACILITY COMPRISING CAPTURE OF CARBON DIOXIDE|
    DE112007000518A5|2006-03-16|2009-01-22|Alstom Technology Ltd.|Plant for the production of electricity|
    US7824574B2|2006-09-21|2010-11-02|Eltron Research & Development|Cyclic catalytic upgrading of chemical species using metal oxide materials|
    US8374709B2|2008-03-03|2013-02-12|Alstom Technology Ltd|Control and optimization system|
    IT1393168B1|2008-09-08|2012-04-11|Senneca|PLANT AND PROCESS FOR "LOOPING" TYPE COMBUSTION OF CARBON SOLIDS|
    PL2273192T3|2009-06-12|2013-09-30|General Electric Technology Gmbh|System for converting fuel material|FR2936301B1|2008-09-23|2010-09-10|Inst Francais Du Petrole|OPTIMIZED CHEMICAL LOOP COMBUSTION METHOD AND DEVICE ON LIQUID HYDROCARBON LOADS|
    TWI447329B|2008-09-26|2014-08-01|Univ Ohio State|Conversion of carbonaceous fuels into carbon free energy carriers|
    PL2251454T3|2009-05-13|2014-12-31|Sio2 Medical Products Inc|Vessel coating and inspection|
    US9458536B2|2009-07-02|2016-10-04|Sio2 Medical Products, Inc.|PECVD coating methods for capped syringes, cartridges and other articles|
    US9545360B2|2009-05-13|2017-01-17|Sio2 Medical Products, Inc.|Saccharide protective coating for pharmaceutical package|
    WO2011031755A1|2009-09-08|2011-03-17|The Ohio State University Reseach Foundation|Integration of reforming/water splitting and electrochemical systems for power generation with integrated carbon capture|
    ES2656144T3|2009-09-08|2018-02-23|The Ohio State University Research Foundation|Production of synthetic fuels and chemical products with CO2 capture in situ|
    AU2011326127B2|2010-11-08|2017-04-20|Particulate Solid Research, Inc.|Circulating fluidized bed with moving bed downcomers and gas sealing between reactors|
    US9878101B2|2010-11-12|2018-01-30|Sio2 Medical Products, Inc.|Cyclic olefin polymer vessels and vessel coating methods|
    CN102183014B|2011-03-10|2012-05-02|东南大学|Method for separating CO2 through chemical looping combustion in coal pressure high-density circulating fluidized bed|
    US9272095B2|2011-04-01|2016-03-01|Sio2 Medical Products, Inc.|Vessels, contact surfaces, and coating and inspection apparatus and methods|
    EP3584426B1|2011-05-11|2021-04-14|Ohio State Innovation Foundation|Oxygen carrying materials|
    EP2707350A4|2011-05-11|2015-12-23|Ohio State Innovation Foundation|Systems for converting fuel|
    FR2978450B1|2011-07-28|2014-12-26|IFP Energies Nouvelles|CHEMICAL LOOP COMBUSTION PROCESS USING PYROLUSITE AS OXYDO-REDUCTIVE MASS|
    EP2776603B1|2011-11-11|2019-03-06|SiO2 Medical Products, Inc.|PASSIVATION, pH PROTECTIVE OR LUBRICITY COATING FOR PHARMACEUTICAL PACKAGE, COATING PROCESS AND APPARATUS|
    US11116695B2|2011-11-11|2021-09-14|Sio2 Medical Products, Inc.|Blood sample collection tube|
    FR2983489B1|2011-12-02|2013-11-15|IFP Energies Nouvelles|CHEMICAL LOOP COMBUSTION PROCESS WITH DILUTE PHASE REMOVAL OF ASHES AND FINESS IN OXIDATION AREA AND INSTALLATION USING SUCH A METHOD|
    US8888899B2|2012-04-12|2014-11-18|Kellogg Brown & Root Llc|Transfer line for the primary cyclone of a gasifier|
    US9740214B2|2012-07-23|2017-08-22|General Electric Technology Gmbh|Nonlinear model predictive control for chemical looping process|
    FR2997318A1|2012-10-31|2014-05-02|IFP Energies Nouvelles|CHEMICAL LOOP COMBUSTION PROCESS USING OXYDO-REDUCTIVE MASS COMPRISING PYROLUSITE ENRICHED WITH NICKEL OXIDE|
    JP6509734B2|2012-11-01|2019-05-08|エスアイオーツー・メディカル・プロダクツ・インコーポレイテッド|Film inspection method|
    WO2014078666A1|2012-11-16|2014-05-22|Sio2 Medical Products, Inc.|Method and apparatus for detecting rapid barrier coating integrity characteristics|
    US9764093B2|2012-11-30|2017-09-19|Sio2 Medical Products, Inc.|Controlling the uniformity of PECVD deposition|
    CN105705676B|2012-11-30|2018-09-07|Sio2医药产品公司|Control the uniformity of the PECVD depositions on injector for medical purpose, cylindrantherae etc.|
    JP6197044B2|2012-11-30|2017-09-13|サウジ アラビアン オイル カンパニー|Stepwise chemical looping process with integrated oxygen production|
    EP2953892A4|2013-02-05|2016-11-16|Ohio State Innovation Foundation|Methods for fuel conversion|
    US20160015898A1|2013-03-01|2016-01-21|Sio2 Medical Products, Inc.|Plasma or cvd pre-treatment for lubricated pharmaceutical package, coating process and apparatus|
    US9937099B2|2013-03-11|2018-04-10|Sio2 Medical Products, Inc.|Trilayer coated pharmaceutical packaging with low oxygen transmission rate|
    KR102167557B1|2013-03-11|2020-10-20|에스아이오2 메디컬 프로덕츠, 인크.|Coated Packaging|
    US9616403B2|2013-03-14|2017-04-11|Ohio State Innovation Foundation|Systems and methods for converting carbonaceous fuels|
    WO2014144926A1|2013-03-15|2014-09-18|Sio2 Medical Products, Inc.|Coating method|
    GB2512334A|2013-03-26|2014-10-01|Gas Recovery & Recycle Ltd|Materials for use in chemical looping combustion|
    WO2015131117A1|2014-02-27|2015-09-03|Ohio State Innovation Foundation|Systems and methods for partial or complete oxidation of fuels|
    EP3693493A1|2014-03-28|2020-08-12|SiO2 Medical Products, Inc.|Antistatic coatings for plastic vessels|
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    法律状态:
    2019-01-15| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 13/10/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR09/03.502|2009-07-16|
    FR0903502A|FR2948177B1|2009-07-16|2009-07-16|CHEMICAL LOOP COMBUSTION PROCESS WITH INDEPENDENT CONTROL OF SOLIDS CIRCULATION|
    PCT/FR2010/000476|WO2011007055A2|2009-07-16|2010-06-30|Method and installation for chemical looping combustion with independent control of the circulation of solids|
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