KR20160045737A - Burner for a hydrocarbon and alcohol reforming system, hydrocarbon and alcohol reforming system comprising it and associated process - Google Patents

Abstract

A burner for a hydrocarbon and alcohol reforming system integrated within a fuel cell that can operate as a liquid fuel and a gaseous fuel is disclosed. The incoming fuel is the cathode residue of the fuel cell, and the liquid fuel portion and the gaseous fuel portion are separately introduced. The comburent is the anode residue of the fuel cell mixed with the recirculated after-combustion gas. The burner includes a tilted inlet port for imparting turbulence to the gas passing therethrough, thereby ensuring a uniform mixture of fuel and combustibles and thus providing a uniform post-combustion gas shear. Also disclosed is a hydrocarbon and alcohol reforming system comprising the burner as an essential element of the system.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a burner for a hydrocarbon and alcohol reforming system, a hydrocarbon and alcohol reforming system including the burner, and a related method, and a related method. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention may be included in the art of a hydrocarbon and alcohol reforming system, preferably an ethanol (bioethanol) reforming system, for future supply to fuel cells used in naval or marine applications.

More specifically, the present invention may be incorporated into the art of burners incorporated into the hydrocarbon and alcohol reforming systems.

A variety of burners in the form incorporated into hydrocarbon and alcohol reforming systems are known in the art. In general, in certain applications of premix burners, the fuel and the oxidizer are mixed in sections prior to ignition and flame development zones.

A disadvantage of these burners is the risk of flash-back. This phenomenon occurs when the flame speed is greater than the flow rate of the fuel-oxidant mixture. This causes premature deterioration of premixed regions.

Another method known in the prior art is a combustion system that uses a diffusion burner without premixing. In the system described above, the fuel and oxidant are injected independently into the ignition zone in such a way that mixing is created by diffusion in the area where combustion is expected. The most important problem associated with this type of burner is that it can not guarantee a uniform mixing of the gases to be burned, and the resulting post-combustion gas does not form a uniform front.

Burners that are integrated with a reformer are known in the art. These burners include a collector for receiving and distributing the starting fuel flow, a collector for receiving and distributing the oxidizing gas flow, and a collector for receiving and distributing the fuel flow of the burner, And includes a distribution tube. The outlet of the burner fuel delivery line is introduced into the inlet of the oxidant delivery line. The starter fuel delivery line also includes at least one opening associated with at least a portion of the burner fuel delivery line. Generally, these burners use natural gas and do not consider the use of liquid fuels.

Procedures for manufacturing a mixture of gases containing hydrogen and carbon monoxide by partial oxidation of a hydrocarbon source using a burner have also been discussed. To this end, the burner comprises a plurality of orifices and has a coaxial tube through which the hydrocarbon flows towards the burner. The burner includes a duct through which the hydrocarbon flows and a duct through which the oxidizing gas flows and the pipe through which the regulating gas flows is separated.

However, none of the patents known to date disclose a burner that can provide a uniform post-combustion gas front. This is particularly important when the burner is integrated with other components of the alcohol and alcohol reforming system, such as, for example, a reformer.

Various types of hydrocarbon and alcohol reforming systems for later fueling a fuel cell, such as those described above, incorporating a burner are also known in the prior art.

An example of this type of system is disclosed in International Patent Application No. WO0100320 (A1) for an ethanol reforming process and an apparatus for producing H ₂ using the process, the process being carried out at a temperature in the range of 300 ° C. to 800 ° C. Reforming the ethanol with steam, which requires the presence of oxygen in a ratio of 2/3 to the molar concentration of ethanol. It also discloses a system comprising a refinery using an ethanol and water treatment unit, a reformer and a water-gas shift (WGS) reactor and a CO selective (PrOX) oxidation unit, It is very small, approximately 37 kW.

In addition, patent US 7 442 217 (B2) relates to an integrated fuel reformer with rapid start-up and operation control, which includes a refinery equipped with ethanol and water treatment devices, reformers and WGS and PrOX reactors, To reduce to below ppm, the anode exhaust gas is fed back to the combustor as a fuel supplement, while the cathode exhaust gas is fed back to the combustor as an O ₂ supplement. The treatment carried out with a reactant to achieve a concentration of 20 ppm or less is not specified in this patent.

In addition, national polity Application No. WO2012066174 (A1) discloses the ethanol reforming system having a purification unit for purifying a stream having a high H ₂ concentration obtained using the ethanol and the water treatment apparatus, the reformer and the WGS and PrOX reactor . Ethanol is vaporized by the heat of the reformate gas entering the first of the three PrOX reactors and by the heat of the combustion gases from the exhaust gas of the overhead battery system. The water is preheated by the continuous steps in the PrOX reactor by the heat of the reformed gas and is evaporated by the heat of the reformed gas discharged from the reformer and the heat of the post-combustion gas from the combustion of the exhaust gas of the fuel cell system. In addition, the cathode exhaust gas is fed back to the combustor as a fuel supplement, while the anode exhaust gas is fed back to the combustor as an O ₂ supplement to reduce the CO concentration to below 20 ppm. The power extracted from the fuel cell is not specified in the above international application.

The ethanol reforming system disclosed in WO2012066174 (A1) also requires a purification step wherein CO ₂ methanization, or CO methane to avoid H ₂ losses due to secondary reactions such as the reverse reaction of WGS, The stream having a high H ₂ concentration is purified by a highly selective methanation reactor for oxidation.

The present invention proposes a burner which is incorporated in a hydrocarbon and alcohol reforming apparatus for supplying fuel to a fuel cell. The proposed burner uses liquid bioethanol in the start-up phase and uses the cathode exhaust gas of the fuel cell (a gas stream which is basically formed of H ₂ , CH ₄ , CO ₂ and H ₂ O) during the normal operating phase.

If the use of the cathode exhaust gas is not sufficient to obtain the required energy in the burner, an additional amount of liquid ethanol is added to the normal operating phase, which, when mixed with the cathode exhaust gas, evaporates (as the cathode exhaust gas enters the high temperature) And is used as a gaseous fuel.

The fuel cell anode exhaust gas (a gas stream which is basically formed of O ₂ and H ₂ O) is used as an oxidant, which is preferably an afterburn gas which is recycled to dilute the O ₂ concentration before the anode exhaust gas is introduced into the burner Mixed. This makes it possible to lower the temperature of the adiabatic flame (the flame produced when mixing the oxidizer with the fuel) to the required level so that it can be supported by the constituent material of the burner.

During the start-up of the burner, when the fuel cell cathode exhaust gas is not yet available, pure O ₂ mixed with the recirculated combustion gas is used as the fuel. In the initial startup phase, the gas after recirculation combustion is not yet available and pure O ₂ is mixed with CO ₂ . The CO ₂ is present in the hydrocarbon and alcohol reforming system because it remains after performing the purge prior to performing this pre-start.

A very important advantage of the burner of the present invention is that the product obtained when burning the fuel with the oxidizing agent is a water-soluble substance. This advantage is important in applications requiring alternate gas discharge methods other than emissions to the atmosphere.

The disclosed burner can simultaneously treat the cathode exhaust gas and the anode exhaust gas of the fuel cell incorporated in the hydrocarbon and alcohol reforming system in which the burner is mounted.

The present invention discloses a burner that produces a uniform fuel-oxidant mixture to produce a uniform flame that produces a uniform post-combustion gas tip. This makes it possible to obtain a uniform temperature distribution at every point of the hydrocarbon and alcohol reforming system in which the burner is incorporated. In one embodiment, the system includes a reformer having a reformer, wherein the burner is integrated. The difference between the high and low temperatures in the reformer is less than 10% of the average reformer operating temperature. Preferably, the temperature difference is less than 5% of the average temperature.

The burner includes a fuel and oxidant inlet duct that is divided into a first section and a second section. In the first section, the fuel and oxidant inlet ducts comprise an inner tube for the passage of the liquid fuel and an outer tube for the introduction of the gaseous fuel.

A fuel distribution plate is in the second section, a sprayer is disposed in the center of the distribution plate, and a primary orifice (primary inlet) is disposed throughout the inlet duct of the second section, through which the oxidant flows into the inlet duct.

The burner also includes a third section with an oxidant distribution plate having a secondary orifice forming a secondary inlet for the introduction of oxidant. The oxidant distribution plate is coupled to the inlet duct at the end of the second section and is coupled with the sleeve through which the fuel-oxidant mixture circulates.

In one embodiment, a tertiary orifice (tertiary inlet) configured for passage of the gas after recirculation combustion is disposed at the end of the sleeve. In another embodiment, the gas flows directly into the combustion chamber.

The end of the sleeve is inserted into a concentric tube which is part of the burner combustion chamber. The inlet for the gas after recirculation combustion is disposed at the end of the sleeve. The combustion chamber has a double shell surrounding the combustion chamber, through which the combustion gas is circulated to lower the surface temperature of the combustion chamber.

In a preferred embodiment of the present invention, the liquid fuel is liquid bio-ethanol, and the gaseous fuel is the cathode exhaust gas of the fuel cell to which the hydrocarbon and alcohol reforming system to which the burner is incorporated is connected. As described above, the liquid fuel is used in the starting phase of the hydrocarbon and alcohol reforming system, since the cathode exhaust gas for use as fuel at this point has not yet been generated in the fuel cell.

When the cathode exhaust gas can not achieve sufficient energy while the burner is in operation, liquid bio-ethanol, which is a liquid fuel supplied with the cathode exhaust gas, is added and evaporated when mixed with the cathode exhaust gas in the inlet duct, The mixture is introduced as gaseous fuel.

The inner tube through which the liquid fuel circulates is connected to a sprayer located in the center of the fuel distribution plate. In order to carry out the atomization of the liquid fuel, a spraying gas is required, which in the preferred embodiment is a mixture of O ₂ or O ₂ and the gas after recirculation.

The atomizer includes a first orifice of the atomizer that is inclined with respect to the axis of the inner tube so that the liquid fuel swirls and flows therethrough and circulates clockwise.

The inner tube also includes a second duct concentrically disposed in the first duct and having a larger diameter. This second duct terminates in the atomizer nozzle, and more particularly in the second orifice of the atomizer, which is inclined with respect to the axis of the inner tube, causing the gas to vortex and flow counterclockwise as the atomizer gas flows therethrough .

Preferably, the first orifices of the atomizer are distributed radially and equidistantly with respect to one another.

The outer tube is connected to a fuel distribution plate which contains a straight line fuel orifice, that is to say its axis is parallel to the axis of the outer tube. Also, the primary orifice (primary inlet), which is a tangential orifice, is disposed in the inlet duct of the second section, parallel to the direction of the fuel circulating through the inlet duct. That is, these orifices have a specific slope with respect to the axis of the outer tube, so that the oxidant rotates as it passes through the orifice formed by the primary inlet.

In the third section, an oxidant distribution plate is arranged which contains a secondary orifice (secondary inlet) for the distribution of the oxidizing gas. The secondary orifice has a specific angle that imparts rotational motion to the oxidizer and the flame (produced when the fuel and the oxidizer are mixed together), which is beneficial for mixing the fuel and the oxidizer. Specifically, they are inclined in the tangential direction and also in the axial direction. The flame generated in the burner is a flame rotating around the axial direction of the burner sleeve.

That is, the burner causes a swirling effect in the fuel-oxidant mixture due to the rotational component that occurs when the oxidant enters through the secondary inlet, which is advantageous for rapid and uniform mixing of fuel and oxidant. This fuel and oxidant stream with a swirling effect causes recirculation at the inlet of the burner.

The burner sleeve in the third section is inserted into a concentric tube which is part of the combustion chamber. Inside the combustion chamber, there is an oxidant inlet for the oxidant diluted with the previously recycled after-burn gas to reduce the surface temperature of the dual shell of the combustion chamber.

In a preferred embodiment, the burner further comprises an insulating case that prevents the creation of a hotspot (where the temperature is above 200 DEG C) on the outer surface. This feature is particularly important when the burner is used where it is classified as an explosion hazard area, since the creation of hot spots on the surface suggests the appearance of an ignition source. In addition, the presence of the insulating case contributes to minimizing heat loss to the outside.

The fuel and oxidant inlet to the burner is disposed in the combustion chamber. The cathode exhaust gas used as the fuel may come from cooling some components of the bioethanol processing system, for example, a reformed gas purification step, and thus may arrive at a high temperature (generally above 300) It can come directly, in this case, at a low temperature (approx. 60 ° C).

In one embodiment, the case includes two inlets for gaseous fuel (hot gaseous fuel and low temperature gaseous fuel), including an inlet for the oxidant and an auxiliary inlet for the liquid fuel (bioethanol). In yet another embodiment, more preferably, one inlet for the gaseous fuel is disposed. Convergence of the cold and hot currents of the cathode exhaust gas occurs outside the burner case, and therefore only one gas fuel inlet is required. Thus, the burner has one or two inlets, depending on the other elements in the system in which the burner is mounted.

Throughout the specification, the term bioethanol is used because it is not based on fossils, but one of ordinary skill in the art will appreciate from this description that the proposed burner can act as all ethanol.

The burner of the present invention is coupled to a combustion chamber having a double shell that surrounds it for insulation and to prevent the formation of hot spots.

In a preferred embodiment of the present invention, the burner is integrated with a reforming reactor. Also, in a more preferred embodiment, the integration of the burner and the reformer assembly constitutes a compact model. When the present invention is incorporated into, for example, a submarine, the burner and the reformer assembly can be easily extracted through the hatch of the submarine during the maintenance operation. In embodiments where the burner and the reformer are integrated, the function of the burner is to provide sufficient heat to maintain the isothermal conditions of the reformer.

That is, the burner may generate sufficient heat to maintain the desired temperature distribution within the reformer. The burner produces this energy within the reformer to allow heat of 500 ° C to 800 ° C. Preferably, in one embodiment, the temperature should be between 700 [deg.] C and 750 [deg.] C. Thus, the energy requirement of the endothermic reaction occurring inside is ensured.

Because the reformer is fully integrated within the combustion chamber within the dual shell, the burner and the reformer assembly are compact models. In this way, the energy generated in the combustion process is used to maintain the required temperature inside the reformer.

In one embodiment of the present invention, the reformer incorporated in the burner is multi-tubular. The integration of the burner and the reformer, which is carried out using the burner of the present invention, ensures a uniform temperature distribution in the reformer pipe where the reforming reaction takes place.

Another important advantage of the burner of the present invention is that it can treat the cathode and anode exhausts of fuel cells of hydrocarbon and alcohol reforming systems in which the burner is incorporated at all stages, such as operation and start-up, normal stop and emergency stop operation .

In one embodiment, the proposed burner is capable of handling all the vents of the hydrocarbon and alcohol reforming system itself, where at its ends the relief of the safety valve of the components of the hydrocarbon and alcohol reforming system is connected to the various burner inlets . In addition, the burner can treat the fuel cell purge gas during the start and stop phases.

In addition, hydrocarbon and alcohol reforming systems, including burners disclosed as essential elements, also form part of the present invention.

The system can reduce the CO level to a level of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less, which requires a purification step of the vapor having a high H ₂ concentration based on the methanation reactor It is possible to extract the fuel cell output of at least 300 kW.

Due to the hydrocarbon and alcohol (preferably ethanol) reforming systems included in the disclosed burners, a high H ₂ concentration and a carbon monoxide (CO) concentration of less than 20 ppm, preferably less than 10 ppm, more preferably less than 5 ppm And all the procedures associated with the system as well as the hydrocarbon and alcohol reforming systems are performed by a marine vehicle propulsion system, preferably an air-independent propulsion system (AIP Lt; _{RTI ID} = 0.0 > H2 < / RTI >

This can be used, for example, to supply a fuel cell in the form of a proton exchange membrane (PEM), the fuel cell having up to 945 kg / h reformed gas with a high hydrogen content of up to 50 kg / Has a power requirement of more than 300 kW in a stream of up to 465 kg / h of reformed gas stream with a high hydrogen content of at least 600 kW, preferably at most 25 kg / h. The system can be integrated into an anaerobic propulsion system, a marine vehicle, or even a hydrogen production facility.

Another application is to integrate this into an offshore propulsion system, preferably an anaerobic propulsion system for a submarine, and reduce the CO concentration to 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less, Is not more than 14 m ³ , preferably not more than 10 m ³ , more preferably not more than 8 m ³ . Flow of CO and H ₂ is not necessarily in proportion to the dimensions directly, which makes it particularly suitable for the propulsion system having a very reduced space requirements.

In addition to the burners described above, the carbon-hydrogen and alcohol (preferably ethanol)

i) a reactant treatment device for effecting evaporation of hydrocarbons and / or alcohols, preferably ethanol, and H ₂ O, and preheating to reaction temperature;

ii) a hydrocarbon and / or alcohol (preferably ethanol) reforming reactor to produce a reformed gas stream having a high H ₂ concentration, preferably 75% v (dry base) A reformer comprising;

iii) the reformed gas stream in a concentration of 20 ppm CO or less has a high H ₂ concentration, and preferably comprises a purification unit to reduce to 10 ppm or less, more preferably the level of 5 ppm or less, and the apparatus comprising:

a. At least one water gas shift reactor for cooling at the inlet,

b. And at least one CO selective oxidation reactor cooling at the inlet.

Further, the reactive agent-

a. A first heat exchanger for the evaporation and preheating of hydrocarbons and / or alcohols (preferably ethanol) by heat of the reforming gas at the outlet of the reactor of one of the refiner or reformer reactors, and

b. Optionally, a second heat exchanger is provided for partial evaporation of H ₂ O by the heat of the evaporated hydrocarbons and / or the alcohol (preferably ethanol).

Alternatively, the purification apparatus may include a heat exchanger for cooling the reformed gas stream entering each CO selective oxidation reactor of the purification apparatus, wherein evaporation of a portion of the H ₂ O required in the process is performed, and each CO selective oxidation reactor The reforming gas stream is cooled. Preferably, the purification apparatus comprises third, fourth and fifth heat exchangers associated with three selective oxidation reactors.

Optionally, the reactant treatment apparatus comprises a vapor generator comprising a sixth and seventh heat exchanger for converting liquid water to steam and for effecting evaporation of water by the heat of the post-combustion gas. It also includes a cyclone or drop separator for performing the separation of the water droplets present in the eighth heat exchanger and / or the steam to selectively perform superheating of the steam to ensure dry steam flow .

Also optionally, the reformer may include a heat exchanger of claim 9 disposed in the inlet of the reformer to heat the hydrocarbon reaction agent and / or alcohol and water mixture by a reformed gas stream having a high H ₂ concentration before the reforming reactor.

In one embodiment, the system comprises an additional heat exchanger configured to heat the mixture of reactants by the post-combustion gas before the mixture enters the reaction zone of the reformer.

Optionally, the reformer also includes a tenth heat exchanger that provides the necessary heat to the reaction bed to support the resulting endothermic reaction, wherein the hot fluid to provide the needed heat of reaction is generated in the combustion device It corresponds to the gas after combustion.

Optionally, intermediate cooling in the water gas shift reactor is also performed by an eleventh heat exchanger capable of lowering the temperature of the reformed gas having a high H ₂ concentration by heating the cathode exhaust gas flow from the fuel cell.

In one embodiment of a submerged reforming system, the release gas must be water-soluble to such an extent that it does not deteriorate the acoustic characteristics of the submarine. Also, in the case of a submarine, the amount of available oxygen is limited, and thus not all of the oxygen that may be needed to ensure that the resulting post combustion gas does not contain unburned products that adversely affect the solubility of the gas in seawater .

To ensure that the gas obtained from the combustion is completely dissolved in the seawater, the system may further comprise a catalytic post-combustor disposed at the outlet of this gas from the reformer. It is a post-catalyst combustor for carrying out the combustion of unburned products such as H ₂ , CO and methane. To burn methane, the post-combustion gas must have a high level of heat (> 450 ° C).

In an embodiment where there is no methane present in the post-combustion gas, it is not necessary to reach a high level of heat (> 450 DEG C) and thus the system includes a post-catalyst combustor at the outlet of the sixth heat exchanger for evaporation of water can do. At this point, the heat level of the post-combustion gas is below 200 占 폚.

Function after the catalytic combustor is, to reduce the unburned products _{(H 2, CO, CH 4} ) , and the concentration of oxygen within that does not affect the acoustic characteristics of the submarine, to the CO ₂ exhaust system is an acceptable level of AIP system smoke stream will be. By ensuring complete dissolution of the smoke in the seawater, the size of the number of bubbles formed can be minimized.

The hydrocarbon reforming system comprising the above burner is effective in an Explosive Atmosphere (ATEX) environment.

The present invention also relates to a hydrocarbon and / or alcohol (preferably ethanol) reforming process,

i) a reactant treatment step for effecting evaporation of hydrocarbon and / or alcohol (preferably ethanol) and H ₂ O and preheating to reaction temperature,

ii) to produce the gas stream after the water-soluble combustion, hydrocarbon used reaction agent and / or alcohol using the cathode exhaust gas from the fuel cell, which may be supplemented with a fuel and the cathode exhaust gas of the fuel cell that is supplemented with O ₂ streams A combustion step of producing a post-combustion gas which provides heat necessary for the reforming and water evaporation steps,

iii) hydrocarbons and / or alcohols (preferably ethanol) and steam reforming to produce a reformed gas stream having a high H ₂ concentration, preferably a concentration of 75% v (dry basis)

iv) the higher the CO concentration of a reformed gas stream having a H ₂ concentration of 20 ppm or less, preferably 10 ppm or less, and more preferably comprises a purification step for reducing to less than 5 ppm, and wherein the tablet comprises:

a. One or several sub-steps in which a reaction in the form of a water-gas shift, in which cooling is effected at the beginning of each step,

b. And one or several sub-steps of CO purification in which cooling takes place at the beginning of each step.

The reactant treatment step may comprise a first heat exchange for evaporation of hydrocarbons and / or alcohols, preferably ethanol, by heat of the reforming gas stream having a high H ₂ concentration obtained after the reforming step or after any sub-steps of the purification step Includes sub-steps.

Optionally, the first heat exchange step occurs after the CO selective oxidation sub-step using oxygen.

The reactant treatment step may comprise a second heat exchange sub-step for partial evaporation of H ₂ O by heat of hydrocarbons and / or an alcohol (preferably a vaporized ethanol) stream and, optionally, a third vapor superheating sub-step and / Or a fourth drop separation sub-step.

In addition, the process includes the step of burning an unburned product _{(CH 4, H 2, CO} ) , which may be of the gas after combustion.

In order to supplement the present disclosure and to better understand the features of the present invention, it should be understood that a series of drawings, such as the components of the present invention, set forth below in an illustrative, non-limiting manner in accordance with a preferred embodiment of the present invention do:
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a cross-sectional view of a burner illustrating the direction of flow of fuel and oxidant through the various burner inlets.
Figure 2 shows a reformer in which a burner and a reformer incorporating a burner can be seen.
Figure 3 shows an internal tube.
Figure 4 shows an atomizer nozzle.
Figure 5 shows a hydrocarbon and alcohol reforming system in which the burner is incorporated.

The present invention proposes a burner for a hydrocarbon and alcohol reforming system that produces an H ₂ rich stream for feeding to a fuel cell that produces a cathode exhaust gas and a cathode exhaust gas. The developed burner can treat all fuel cell exhaust gases and also treat the residues of the entire hydrocarbon and alcohol reforming system where the burner is installed.

A very important advantage of the present invention is that the product obtained using the burner is a water-soluble substance. This allows the proposed hydrocarbon and alcohol reforming system to be used in undersea marine applications such as, for example, submarines. Due to the water solubility of the product, the product is not detected and can be released to the sea at various depths.

During the burner start-up phase, the fuel used is liquid bio-ethanol supplied by the bio-ethanol storage system. This liquid bio-ethanol is atomized in the atomizer of the burner using an atomizer gas, which may be a mixture of pure O ₂ from an oxygen storage system, mixed with a recirculating combustion gas.

During normal burner operation phase, the fuel used is the fuel cell cathode exhaust gas. If the use of the cathode exhaust gas as the fuel is not sufficient, liquid bio-ethanol mixed with the cathode exhaust gas is added before it is introduced into the burner.

Some of the fuel cell cathode exhaust gases are used in other hydrocarbon and alcohol reforming systems, such as, for example, in the reforming gas step of increasing temperature. In one embodiment in which the burner comprises two inlets for gaseous fuel, one for fuel arriving at high temperature and the other for fuel arriving at low temperature, a portion of the exhaust gas has a temperature of about 300 DEG C . This is called a gaseous fuel at a high temperature. The remainder of the fuel cell cathode exhaust passes directly to the burner and reaches a temperature of approximately 60 ° C. This is called low temperature gaseous fuel.

In another embodiment, the hot gaseous fuel and the cold gaseous fuel are mixed together outside the burner and enter the burner through one fuel inlet.

When liquid bioethanol is used as fuel for additional energy supply mixed with the cathode exhaust gas, it is vaporized (in contact with hot cathode exhaust gas). Thus, the fuel enters the burner in a gaseous state.

The oxidant used in the burner of the present invention is a mixture of fuel cell anode exhaust mixed with recirculated combustion gas.

The burner of the present invention can be seen in Fig. The burner comprises a fuel and oxidant inlet duct (1). The inlet duct is divided into a first section and a second section. In the first section, the inlet duct 1 comprises an inner tube 2 and an outer tube 3 which is arranged concentrically to the inner tube 2 and which has the largest diameter. The liquid fuel A used during the start-up phase flows into the interior of the burner through the inner tube 2.

In a preferred embodiment of the present invention, the inner tube 2 is connected to the bioethanol storage system via one end thereof and the other end is connected to the sprayer 6, which is configured to atomize liquid bio-ethanol, do.

Figure 4 shows a first tube (2.1) disposed in the center of the inner tube (2) through which the liquid fuel (A) circulates to the atomizer nozzle (20) and a second tube (2) into a second tube (2.2) through which the atomizer gas (C) circulates to the atomizer nozzle (20). The atomizer gas (C) is required for accurate atomization of the liquid fuel. In a preferred embodiment, the liquid fuel is liquid bio-ethanol.

In a preferred embodiment for burner start-up, the atomizer gas is CO ₂ present on the line of the hydrocarbon and alcohol reforming system. Thereafter, the atomizer gas used is a post-combustion gas. The post-combustion gas may also be mixed with pure O ₂ . The post-combustion gas is the gas that is obtained when the fuel and oxidizer mixture are burned.

In a preferred embodiment, as can be seen in Figure 4, the gaseous fuel (B) is introduced into the outer tube (3) of the first section of the burner. Which is connected to the fuel cell and is configured for passage of the cathode exhaust gas of the fuel cell. The outer tube 3 is also configured to allow passage of the bio-ethanol to the outer tube 3 when additional energy supply is required during the normal operating phase of the burner, since the fuel cell cathode exhaust gas can not be burned to obtain sufficient energy It is connected to the auxiliary bioethanol inlet.

The second section of the burner arranged in the inlet duct 1 comprises a fuel distribution plate 7 in which a sprayer 6 is arranged and to which the inner tube 2 of the first section is connected. The gas distribution plate 7 comprises a plurality of fuel delivery orifices 10 for the passage of gaseous fuel circulating from the first section to the second section through the outer tube 3 of the inlet duct 1. The primary orifices 12 forming the primary oxidant inlet are arranged along the second section of the inlet duct 1. The primary orifice 12 is inclined with respect to the outer tube 3 in the axial and tangential directions.

The primary orifice 12 is configured for passage of the oxidant D, as can be seen in FIG. The oxidizing gas (D) flowing into the burner through the primary orifice (12) and through the secondary orifice (11) is the same mixture. Most of the oxidant (D) enters through the secondary orifice (11). Only a portion of the oxidant (D) enters the primary orifice (12) to perform the first mixing with the fuel (A, B).

A third section is arranged after the second section of the burner, which comprises an oxidant distribution plate 8 having a secondary orifice 11 which is configured for passage of the oxidant into the third section of the burner. The secondary orifices 11 are inclined in the axial direction and in the tangential direction. The inclination angle is included in the range of 20 to 40 degrees in one embodiment.

The third section also includes a sleeve in which mixing of the fuel and the oxidizer takes place, the end of which is inserted into the conical section of the combustion chamber 15, where the burner of the present invention is engaged. In one embodiment, a tertiary orifice forming a tertiary oxidant inlet is disposed at the end of the sleeve 13 closest to the combustion chamber 15. In a more preferred embodiment, the oxidant flows directly into the combustion chamber through the ring shaped section between the burner sleeve and the conical section end of the combustion chamber. The oxidizer distribution plate 8 may also be referred to as an oxidizer distribution plate.

2 shows the details of the burner and shows the oxidant distribution plate 8 with the fuel distribution plate 7 and the secondary orifice 11 with the atomizer 6 and the fuel delivery orifice 10 .

The sprayer 6 is disposed in the center of the fuel distribution plate 7 and the fuel orifice 10 is distributed around the sprayer 6 to distribute the outer tube 3 in the first section of the inlet duct 1 (B) through the first section to the second section. An igniter (flame igniter) and at least one infrared or ultraviolet sensor for flame detection are also arranged in the first distribution plate (7). In one embodiment, this includes at least two sensors to ensure proper functioning of the burner and to ensure that operation is not interrupted by a false flame extinguishing signal.

The atomizer 6 includes an atomizer nozzle 20 having a first orifice 21 of atomizer 21 which is connected to the central axis of the inner tube 2 so as to impart a clockwise rotation to the flow of liquid fuel A. [ As shown in Fig. The atomizer gas is fed through the second orifice of the atomizer, which is also inclined with respect to the central axis of the outer tube 3, but at an angle different from the angle of the first orifice 21 of the atomizer, In the counterclockwise direction.

In one embodiment of the invention, the first orifice (21) of the atomizer is smaller than the second orifice (22) of the atomizer and has a greater inclination in the tangential direction. In this embodiment, the inclination of the first orifice 21 of the atomizer is in the range of 10 to 30 degrees, and the inclination of the second orifice 22 is in the range of 30 to 60 degrees.

The distribution plate 8 has a secondary orifice 11 which is configured for the passage of an anode exhaust gas which is inclined with respect to the gas distribution plate 8 and which is mixed with an oxidant D, i.e. a gas after recirculation combustion. Due to the inclination of the second orifice 11, the influx of oxidant D through it is turbulent.

The burner comprises a third section formed by a sleeve 13 which is connected to the second section by means of an oxidant distribution plate 8 via one end thereof and to a tube which forms part of the combustion chamber 15 through the other end . The oxidant D is introduced into the third section through the secondary orifice 11 in the oxidizer distribution plate 8 where it receives a mixture of oxidant and fuel produced in the second section of the inlet duct 1. In one embodiment, as can be seen in Figures 1 and 2, it comprises a tertiary orifice on the sleeve 13 which is configured for the passage of gas after recirculation for cooling (E). Preferably, the gas flows directly into the combustion chamber 15 to which the burner is connected.

The combustion chamber 15 is surrounded by a double shell, through which gas after combustion is circulated to allow cooling of the outside thereof. In addition, the heat of the post-combustion gas is used at other stages of the bio-ethanol production system, such as, for example, to evaporate water and heat the reforming reaction. The combustion chamber 15 supports a temperature of up to 1,100 ° C, and due to the recirculation of the combustion gas through the dual shell, the outside is at a temperature of 200 ° C or less, which is effective in the atmosphere according to the ATEX 2 requirement.

In a preferred embodiment, the burner further comprises an insulating case to prevent hotspots on the surface that may correspond to an ignition source. This also contributes to making the burner available in the atmosphere according to ATEX2 requirements.

Preferably, the burner of the present invention can operate with gas fuel alone, liquid fuel alone, or both. The present invention is capable of handling gas fuel flow rates up to 300 kg / h. Which can handle liquid fuel flow rates of up to 100 kg / h (these liquid fuel flow rates reach the atomizer 6 through which they flow through the inner tube 2).

The post-combustion gas is composed of a water-soluble material such as CO ₂ and contains a minimum amount of unburned product and oxygen, that is, a uniform post-combustion gas tip is obtained.

The atomizer 6 preferably operates with a low pressure gas, i.e. a gas having a pressure of 100 millibars. Preferably, the pressure may be 60 to 70 millibar, more preferably 65 millibar.

In a preferred embodiment, the burner is integrated with a catalytic reformer operating under near-isothermal conditions. This embodiment is shown in Fig. In this embodiment, a reformer is used to produce an H ₂ rich stream as the bioethanol in a hydrocarbon and alcohol reforming system. The resulting H ₂ is used to feed the fuel cell of the system, for example, to provide energy for a mobile off-axis system such as a submarine.

The disclosed burner, when integrated with the reformer, enables a uniform distribution of temperature within the reforming tube 23 to be achieved.

In a preferred embodiment in which the burner and the reformer are integrated, the reformer is multi-tubular and integration with the burner allows a uniform temperature distribution in all the tubes.

In a preferred embodiment in which the burner is integrated with a reformer, a reduced size modifying device having a small diameter of 790 mm and a small length of 2,100 mm is achieved.

Still another object of the present invention is a hydrocarbon and alcohol reforming system comprising the disclosed burner.

According to a preferred embodiment, the system comprises a treatment device for a reactant comprising ethanol 28 and H ₂ O 29, which is a fuel in this preferred embodiment, 29) and preheating to reaction temperature.

The reactive agent-

i) a first heat exchanger 35 for the evaporation and preheating of the ethanol 28, which is preferably heated at a temperature of 350 ° C to 450 ° C by the heat of the H ₂ -rich reforming gas 31 at the outlet of the reforming reactor .

In addition, a hydrocarbon and an alcohol (preferably ethanol) reforming system comprises a purification unit to reduce the CO concentration of a reformed gas stream having a high concentration of H ₂ at a level of 5 ppm or less, and the apparatus comprising:

i) three CO selective oxidation reactors for cooling the reformed gas at the inlet by the third heat exchanger 36, the fourth heat exchanger 37 and the fifth heat exchanger 38, that is, the first CO selective oxidation reactor 32), a second CO selective oxidation reactor (33), and a third CO selective oxidation reactor (34), wherein evaporation of a portion of the H ₂ O required by the system is performed in the heat exchanger, The stream is cooled at the outlet of each CO selective oxidation reactor.

The third heat exchanger 36 cools the gas stream 31 having a high H ₂ concentration by the water stream 29 while the purification of the gas stream 31 having a high H ₂ concentration is performed by the third heat exchanger 36 in the first catalyst bed CO selective oxidation reactor 32 by the O ₂ stream 46 injected at the inlet of the first catalyst bed CO selective oxidation reactor 32.

The fourth heat exchanger 37 is disposed at the outlet of the first CO selective oxidation reactor 32 to continuously and partially cool the gas stream 31 having a high H ₂ concentration by the water stream 29, The second catalyst bed CO selective oxidation reactor 33 is arranged to perform a partial purification of the gas stream 31 having a high H ₂ concentration by the O ₂ stream 46 injected at the inlet of the fourth heat exchanger 37 do.

A fifth heat exchanger (38) of claim 2 CO selective, and are disposed at the outlet of the oxidation reactor, 33, continues to a gas stream (31) having a high H ₂ concentration by the water stream 29 to partially cool to, since the A third catalytic layer CO selective oxidation reactor 34 is arranged to perform partial refining of the gas stream 31 having a high H ₂ concentration by the O ₂ stream 46 injected at the inlet of the fifth heat exchanger 38 do.

The reactive agent processing apparatus may further comprise:

ii) a sixth heat exchanger 39 for converting the liquid water to steam and for heating the water 29 to a temperature of approximately 80 DEG C, a temperature of 100 DEG C to 150 DEG C, preferably a temperature of 115 DEG C to 125 DEG C (E) at a temperature of about < RTI ID = 0.0 > 350 C < / RTI > to < RTI ID = 0.0 > 450 C, < / RTI & And an eighth heat exchanger (42) for superheating the water (29).

The steam generator also includes a cyclone or drop separator disposed after the seventh heat exchanger 40, which is capable of performing the separation of water drops present in the steam stream, and a high water content of the post- E, the water being condensed is discharged.

The reforming device 27 may comprise the above-described integrated burner 51 forming a single assembly. The reforming device 27 may also be configured to introduce a mixture of ethanol 28 and water 29 into the reforming gas stream 31 having a high H ₂ concentration to cool the effluent gas of the reformer 30, A ninth heat exchanger 43 for heating the mixture of ethanol 28 and water 29 at the inlet of the reformer 27 and a heat exchanger 43 for heating the mixture of ethanol 28 and water 29 in the burner And a tenth heat exchanger (44) for heating the reformed gas by the obtained post-combustion gas flow (E).

In one embodiment, the reforming system further comprises an additional heat exchange (not shown) for heating the mixture of hydrocarbons and alcohol 28 and water 29 as post-combustion gas before the mixture reaches the reaction zone of reformer 30 of reformer 27 . Which is disposed at the inlet of the reformer 30.

The hydrocarbon and alcohol (preferably ethanol) reforming system also preferably comprises a purification apparatus comprising two water gas shift reactors 26 and a selective oxidation reactor. The water gas shift reaction reactor 26 is provided with an intermediate cooling step by the eleventh heat exchanger 45 which can lower the temperature of the reformed gas 31 having a high H ₂ concentration by the cathode exhaust gas 47 of the fuel cell 50 (45).

In addition, the reforming apparatus may include an integrated reformer configured to contain post combustion gas E containing methane and a post-catalyst combustor disposed at the outlet of the burner. In another embodiment, the system includes a post-catalyst combustor disposed at the outlet of the sixth heat exchanger 39 for evaporation of the water stream 29.

A further object of the invention is the use of the burners described above in a hydrocarbon and alcohol reforming system to produce a hydrocarbon stream in a submarine. As described above, the burner of the present invention can obtain a homogeneous flame that generates a uniform gas end point after combustion, and all products obtained are water-soluble. In the case of use in a submarine hydrocarbon and alcohol reforming apparatus, less oxygen than is needed may be used for overall performance operation, and therefore the post-combustion gas may contain unburned products. In this case, the present invention includes the addition of a post-catalyst combustor to the system to ensure the availability of all post-combustion gases.

Claims (34)

A burner for a hydrocarbon and alcohol reforming system integrated with a fuel cell that produces a cathode exhaust gas and an anode exhaust gas, the burner comprising basically an oxidant and fuel inlet duct (1), a sleeve (13) , And is connected to the combustion chamber (15)
An inner tube 2 into which the liquid fuel A is introduced and an outer tube 3 concentrically disposed in the inner tube 2 and having a large diameter and into which the gaseous fuel B flows, (1);
- a fuel distribution plate (7) having a first orifice (10) adjacent to the first section and connected to the outer tube (3) around the atomizer (6) and the atomizer (6) ); And a primary section in the inlet duct (1) comprising a primary orifice (12) arranged radially in the inlet duct (1), constituted for passage of the oxidant (D);
- an oxidizer distribution plate (8) adjacent to the second section and having a plurality of secondary orifices (11) having a larger diameter than the first distribution plate (7) and configured for passage of the oxidant (D); And a sleeve (13) and is divided into a third section connected to the second section via an oxidant distribution plate (8), and
The combustion chamber 15 to which the burner is connected is surrounded by a double shell for recirculation of the gas after the recirculating combustion which is configured to cool the outside of the combustion chamber 15, And an inlet for the hydrocarbon and alcohol reforming system.
The method according to claim 1,
The inner tube 2 is centrally disposed with a first tube 2.1 in which the liquid fuel A is circulated to the atomizer 6 and a second tube which is concentric with the first tube and through which the atomizer gas C And a second pipe (2.2) circulating to the sprayer (6).
The method according to claim 1,
The atomizer 6 is adapted to inject air into the first orifice 21 and the atomizer gas B of the atomizer which are inclined with respect to the central axis of the inner tube 2 to impart a clockwise rotation to the flow of the liquid fuel A. And an atomizer nozzle (20) having a second orifice (22) of the atomizer inclined with respect to a central axis of the inner tube (2) to impart a clockwise rotation.
The method according to claim 1,
Characterized in that the burner further comprises an auxiliary inlet connected to the outer tube (3), which is configured for passage of the liquid fuel.
The method according to claim 1,
The burner includes a low temperature cathode exhaust gas inlet configured for passage of cathode exhaust gas from the fuel cell, a cathode for passing the cathode exhaust gas after being recycled to cool the components of the hydrocarbon and alcohol reforming system into which the burner is incorporated Further comprising an insulating case of a burner including a hot cathode exhaust gas inlet, a high temperature cathode exhaust gas inlet, and an oxidant inlet which is configured for passage of the oxidizing agent.
The method according to claim 1,
Characterized in that the burner further comprises an insulating case of a burner comprising an inlet for the passage of a mixture of the cold cathode exhaust gas and the hot exhaust gas and an inlet for the passage of the oxidizing agent.
The method according to claim 5 or 6,
Wherein said case further comprises an auxiliary inlet configured for passage of liquid fuel. ≪ RTI ID = 0.0 >< / RTI >
8. The method according to any one of claims 1 to 7,
Wherein the liquid fuel is bioethanol. ≪ RTI ID = 0.0 > 11. < / RTI >
9. The method according to any one of claims 1 to 8,
Wherein the gaseous fuel is selected from a mixture of a cathode exhaust gas of the fuel cell and a cathode exhaust gas and liquid bio-ethanol.
10. The method according to any one of claims 1 to 9,
Characterized in that the oxidant is selected from the group consisting of a mixture of the anode exhaust gas of the fuel cell and the gas (E) after the recirculation combustion, pure O ₂ mixed with the gas after the recirculating combustion, or pure O ₂ mixed with CO _2. Burners for reforming systems.
The method according to claim 1,
Characterized in that the burner comprises at least one infrared or ultraviolet sensor disposed in the first distribution plate (7).
In the hydrocarbon and alcohol reforming system, the system of claims 1 to 11 as disclosed in any one of items burner and the hydrocarbon and alcohol to the steam (29) to produce a reformed gas stream 31 has a high H ₂ concentration And a reforming device (27) comprising a reformer (30) for reforming the reforming gas (28).
13. The method of claim 12,
Characterized in that the burner is incorporated in a reforming device (27).
The method according to claim 12 or 13,
The system comprises:
i) a reactant treatment device for effecting evaporation of the hydrocarbons and / or the alcohol (28) and H ₂ O (29) and preheating to the reaction temperature;
ii) it comprises a purification unit to reduce the CO concentration of a reformed gas stream having a high H ₂ concentration to a level below 20 ppm, and the apparatus comprising:
A water gas shift reactor (26) cooled at at least one inlet,
- a CO selective oxidation reactor (32, 33, 34) cooled at at least one inlet,
The reactive agent processing apparatus may further comprise:
- hydrocarbons and the alcohol (28) are evaporated by the heat of the reforming gas stream having a high H ₂ concentration at the outlet of the reactor of one of the reactors (32, 33, 34, 26) of the purifier or reformer And a first heat exchanger (35) for superheating the hydrocarbons and the alcohol (28).
15. The method of claim 14,
Characterized in that the reactant treatment system is also a second heat exchanger for partial evaporation of H ₂ O (29) by heat of the evaporated hydrocarbon and alcohol stream (28).
16. The method according to any one of claims 14 to 15,
The purifier cools the reformate gas stream at the inlet of each of the CO selective oxidation reactors (32, 33, 34) to perform evaporation of a portion of the H ₂ O (28) required in the process, while the CO selective oxidation reactor (32, 33, 34), the reformed gas stream 31. heat exchanger (36, 37, 38), a hydrocarbon and an alcohol-modified system comprising the for cooling has a high H ₂ concentration in each of the inlet.
17. The method of claim 16,
Characterized in that the purification apparatus comprises a third heat exchanger (36), a fourth heat exchanger (37) and a fifth heat exchanger (38) associated with the three selective oxidation reactors (32, 33, 34) Alcohol reforming system.
15. The method of claim 14,
The reactant treatment device comprises a sixth heat exchanger 39 and a seventh heat exchanger 40 for converting liquid water to steam and for performing water evaporation in two stages by the heat of the water-fired gas (E) stream, And a steam generator comprising the steam generator.
19. The method of claim 18,
The reactant treatment system may further comprise an eighth heat exchanger (42) for superheating the steam and / or a cyclone or drop separator for separating water drops present in the steam stream Hydrocarbon and alcohol reforming systems.
15. The method of claim 14,
The reformer heats the mixture of hydrocarbon and alcohol 28 and water 29 with a reformed gas stream 31 having a high H ₂ concentration prior to the catalyst bed stage of the reformer 30 and a reformer flue gas And a ninth heat exchanger (43) disposed at an inlet of the reforming device (27) for cooling.
13. The method of claim 12,
The system comprises an additional heat exchanger arranged at the inlet of the reformer 30 of the reforming device 27 for heating the mixture of hydrocarbon and alcohol 28 and water 29 by post combustion gas E Characterized by a hydrocarbon and alcohol reforming system.
21. The method of claim 20,
Characterized in that the reformer also comprises a tenth heat exchanger (44) for supplying the required heat to the reforming reactor layer (30) by means of a water-soluble combustion gas (E).
15. The method of claim 14,
Characterized in that the purification apparatus comprises an eleventh heat exchanger (45) for performing cooling at the inlet of the water gas shift reactor (26).
18. The method of claim 17,
The third heat exchanger 36 cools the gas stream 31 having a high H ₂ concentration by the water stream 29 while the purification of the gas stream 31 having a high H ₂ concentration is carried out by a third heat exchanger Is carried out in the first catalyst bed CO selective oxidation reactor (32) by an O ₂ stream (46) injected at the inlet of the first catalyst bed (36).
25. The method of claim 24,
The fourth heat exchanger 37 and continues to partly cool the gas stream 31 has a high H ₂ concentration by claim 1 CO stream (29) is arranged at the outlet of the selective oxidation reactor 32, the The second catalyst bed CO selective oxidation reactor 33 (hereinafter referred to as " second oxidation catalyst ") is used to perform partial purification of the gas stream 31 having a high H ₂ concentration by the O ₂ stream 46 injected at the inlet of the fourth heat exchanger 37 ) Is arranged on the downstream side.
26. The method of claim 25,
The fifth heat exchanger 38 and continue partially cooling a gas stream 31 has a high H ₂ concentration by the water stream (29) is arranged at the outlet of claim 2 CO selective oxidation reactor 33, the A third catalyst bed CO selective oxidation reactor 34 (hereinafter referred to as " CO ") is used to perform partial purification of the gas stream 31 having a high H ₂ concentration by the O ₂ stream 46 injected at the inlet of the fifth heat exchanger 38 ) Is arranged on the downstream side.
13. The method of claim 12,
Said system configured to perform the combustion in the reformer 27, unburned product (methane, H ₂ and CO) of the gas (E) after combustion by using the excess oxygen from the combustion occurring in the integrated burner 51 in the And a catalytic post-combustor disposed at an outlet of the burner and the reformer.
19. The method of claim 18,
Wherein the system further comprises a post-catalyst combustor disposed at an outlet of the sixth heat exchanger (39).
In the hydrocarbon and alcohol reforming process,
i) a reactant treatment step for carrying out the evaporation of the hydrocarbons and / or the alcohol (28) and H ₂ O (29) and the preheating to the reaction temperature,
ii) the cathode exhaust gas 47 of the fuel cell, which is a fuel that can be supplemented with hydrocarbons and / or alcohols used as reactant 28, and O ₂ stream 46 A combustion step for producing post combustion gas (E) for providing the necessary heat for the reforming and water evaporation steps, using the anode exhaust gas (48) of the fuel cell,
iii) hydrocarbon / alcohol to produce a reformed gas stream 31 has a high H ₂ concentration and the steam reforming step,
iv) comprises a purification step for reducing CO concentration of a reformed gas stream having a high H ₂ concentration to below 20 ppm, and wherein the tablet comprises:
a. One or several sub-steps in which a reaction in the form of a water-gas shift, in which cooling is effected at the beginning of each step,
b. Comprising one or several sub-steps of a CO purification in which cooling occurs at the beginning of each step,
The reactant treatment step may comprise a first heat exchange for evaporation of hydrocarbons and alcohol (28) by heat of the reforming gas stream (31) having a high H ₂ concentration obtained after the reforming step or after any sub- Wherein the hydrocarbon and alcohol reforming process comprises a sub-step.
30. The method of claim 29,
Characterized in that the treatment step comprises a second heat exchange sub-step for partial evaporation of H ₂ O (29) by heat of the hydrocarbon and alcohol streams.
30. The method of claim 29,
Wherein the reactant treatment step comprises a third vapor superheating sub-step and / or a fourth drop separation sub-step.
30. The method of claim 29,
Wherein the first heat exchange sub-step for evaporating the hydrocarbons and the alcohol (28) is a step wherein ethanol is overheated at a temperature of 350 ° C to 450 ° C.
30. The method of claim 29,
The process is a hydrocarbon and an alcohol reforming process comprising a methane combustion step of the H ₂ and CO in the gas after combustion.
Use of a burner for hydrocarbon and alcohol reforming systems as set forth in claims 1 to 11 for use in a hydrocarbon and alcohol reforming system of a submarine.

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