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    • 专利摘要:
    Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste. The invention falls within the technical sector of the treatment of organic waste and in the energy sector for the valorization of waste with a high concentration of organic matter, through the processes of supercritical water oxidation and supercritical water gasification. It allows to purify an aqueous residue with high organic matter concentration by means of an oxidation reactor, and part of the heat due to the strongly exothermic reactions, it is transmitted through its wall towards an external casing through which another high pressure organic waste stream circulates. and they are heated until they carry out endothermic gasification reactions that generate combustible gases (mainly hydrogen). The reactor and the casing form a device similar to a concentric tube heat exchanger, in which the heating fluid is independent of the cooling fluid. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2660713A1
    申请号:ES201600787
    申请日:2016-09-23
    公开日:2018-03-23
    发明作者:Juan Ramón PORTELA MIGUÉLEZ；Jezabel SÁNCHEZ ONETO；Enrique José MARTÍNEZ DE LA OSSA FERNÁNDEZ；Belén GARCIA JARANA；Pau CASADEMUNT LANZAT
    申请人:Universidad de Cadiz；
    IPC主号:
    专利说明:

    APPARATUS FOR INTEGRATED TREATMENT OF OXIDATION AND GASIFICATION IN SUPERCRITICAL WATER OF ORGANIC WATER WASTE.  
    5   Technical Sector
    The present invention falls within the technical sector of the treatment of organic waste and in the energy sector of waste recovery, in both cases by the processes of oxidation in supercritical water and gasification in supercritical water.
    the
    Background of the invention
    15 20 25 Industrial wastes often have a high concentration of organic compounds and / or contain toxic contaminants that hinder or prevent their proper treatment through biological processes, so thermal treatments may be the most appropriate and effective alternative. Among the heat treatments, the incineration, pyrolysis or conventional gasification of many wastes is not feasible if they have a high moisture content (aqueous waste, wet biomass, etc.), as large amounts of energy are required for drying prior to heat treatment. , resulting in an inefficient process to produce thermal energy. However, for aqueous organic waste and for wet biomass, processes in supercritical water, whose reaction medium is precisely water, can be very adequate and efficient. The special properties of water in a supercritical state have increased interest in its study as a reaction medium, mainly for the oxidation and gasification of organic compounds. These processes are called supercritical water oxidation (OASC) and supercritical water gasification (GASC), as they are carried out
    under conditions of pressure and temperature above the critical point of pure water (221 bar and 374 OC), where conventional oxidation and gasification reactions can be carried out extremely quickly and completely. Thanks to the solubility of organic compounds and gases in supercritical water, it is possible to obtain a single homogeneous reaction phase, so that oxidation or gasification processes take place without interfacial limitations of matter transfer, which increases considerably the effective reaction speed and allows to dispense with mechanical agitation means, greatly simplifying the design of the reactor.
    In the supercritical water oxidation process (OASC), any organic compound can be completely oxidized and if the residue has a high concentration of organic matter, the process releases a lot of heat since the oxidation reactions that take place during the OASC process are strongly exothermic. In this way, the process can be started at a temperature of 375 oC, and as the reactions take place and give off heat, they increase the temperature of the reaction medium by increasing the speed and efficiency of the process. The process effluent has enough energy to allow preheating of the reactor feed streams, making possible a process that operates autothermally, and may even be surplus of energy. In fact, if the concentration of the waste that is fed to the process is very high (> 10% by weight) and heat is not removed externally, the temperature in the reactor could even exceed 800 ° C, which would exceed the safety limits which guarantee the structural integrity of the construction material of the reactor itself. However, this excess energy in the reactor can be used to heat any process stream, generate steam, etc. In the present invention it is proposed to use a fraction of the heat generated in the OASC process to heat another aqueous stream of waste that needs to reach high temperature to apply another heat treatment.
    On the other hand, the supercritical water gasification (GASe) process is also a promising technology for the gasification of aqueous organic waste, mainly biomass with a high moisture content, which is not suitable to be treated by conventional thermal methods. In the GASe process, water not only provides its special properties as a reaction medium, but also acts as a reagent. GASe technology has great advantages over conventional gasification processes for the production of hydrogen from hydrocarbons. It needs lower temperatures and polymerization reactions that generate tars are inhibited. Supercritical water has great solvent power for organic compounds and biopolymers, achieving the production of a gas of energy interest, rich in hydrogen and methane, with low carbon monoxide content. However, the GASe process also has significant drawbacks from the energy point of view, since it is necessary to preheat the current to be treated at temperatures that, when catalysts are not used, can exceed 600 oC for the proper gasification of the organic compounds In addition, the GASe process is endothermic, that is, it absorbs heat during the development of the reactions that take place, so if no heat is supplied to the reactor, the effluent will have a lower temperature than the inlet feed. This prevents the thermal self-maintenance of the process, since although the effluent yields part of its heat to the feed to preheat it, an external supply of energy will always be necessary to raise the feed temperature to the temperature necessary for the GASe process.
    In order to take advantage of the OASe and GASe processes, reducing their respective limitations described above, the present invention proposes the integration of the OASe and GASe processes, resulting in a very advantageous combination, in which both processes complement each other. from the energy point of view. In the present invention, the treatment can be carried out by means of the OASe process of aqueous streams with a high concentration of organic compounds avoiding excessive temperatures for reactor safety due to the exothermic nature of the reactions, since a large part of the Heat that is released in the supercritical oxidation reactor will be removed by the aqueous stream of waste to be gasified. In turn, the GASe process will be greatly favored from an energy point of view, since preheating of the current to be treated (up to temperatures> 500 oC) is made possible by the heat that said current withdraws from the OASe reactor.
    The following describes all those patents related to the OASe and GASe processes that may be related to the control of the release of energy in the OASe process or to the improvement of the thermal efficiency of the GASe process, there being no invention to date propose an integrated combination of both processes to cover both objectives in the same device.
    Several publications (W02006052207 A 1, W00230836A1) and patents (KR249496BB1, US6030587, ES2108627A1) have proposed configurations of OASe reaction units in which the heat generated in the reactor is used, causing it to exchange part of its heat with the current power supply, thus reducing the maximum temperature reached in the reactor and at the same time preheating the input current, so that the process's energy self-sufficiency is favored. Patent application P201500670 proposes a system for producing supercritical deionized water that can be used directly in a turbine for the production of electrical energy. Deionized water circulates through a housing that surrounds the entire length of an OASe tubular reactor, from which excess heat is removed to increase its temperature to reach conditions of 500-550 ° e and supercritical pressure.
    Several patents propose devices and / or procedures to reduce the external supply of energy necessary to carry out the GASC process, using catalysts that make the GASC process efficient at lower temperatures (JP2012050924 (A), CN104129757 (A), JP2014189589 (A) , JP2014189590 (A », proposing combined systems of subcritical and supercritical gasification to reduce the energy expenditure of the process (CN102443443) or finally a small number of patents propose combined systems of combustion and GASC process. The patents of the latter group are more related to the present invention and are briefly described below:
    Patent CN103771549 (B) provides an experimental system in which it integrates a porous wall reactor, cold wall reactor, a tubular reactor and a hydrothermal combustion reactor to study oxidation, gasification or partial oxidation in supercritical water.
    Patent CN102874916 (B) describes a system and method of treatment of wastewater in two stages (gasification and oxidation) in supercritical water condition. The gasification reaction stage comprises a sludge preheating stage, where high temperature sludge feeds the gasification reactor. The gasified material is separated by a separator in the oxidation stage obtaining a material in the gas phase and another in the solid-liquid phase. The solid-liquid phase material is used as feed in the oxidation reactor. Furthermore, in the CN103833190 (A) patent it allows the oxidized material to pass through the gasification stage exchanger, so that the heat released by the oxidation reaction supplies the gasification reaction.
    Patent KR20130047472 refers to a coal combustion equipment using supercritical water to carry out a reaction with a low grade carbon. Coal and water mix in
    a specific ratio (8-10% by weight of water per part by weight of coal) and pumped into a tubular reactor to perform a combustion reaction, without additional heat input. CN103131478 (A) provides a gasification method in which pulverized carbon, oxygen and water vapor are contacted to obtain a crude gas. Subsequently, said gas is cooled with water to obtain purified gas and liquid products. A next step to separate the oil-water product phase generates carbon gasification wastewater. The carbon gasification wastewater obtained is completely oxidized by an oxidizing agent.
    In the CN102373097 patent a combined method is proposed where a coal gasification process, a residual carbon oxidation process and a power generation process in a steam turbine are coupled.
    None of the inventions described above allow the integration of
    15 OASC and GASC processes are coupled and complementary, so that the exothermic nature of the OASC process is used to raise the temperature of the current to be treated by the GASC process, achieving a balance between the heat generation of the OASC process (avoiding that the reactor temperature is excessive) and the consumption of
    20 energy required by the GASC process (managing to increase the inlet temperature thanks to the heat given off by the OASC reactions and counteract the endothermic character of the gasification reactions).
    In the present invention, the streams of waste to be oxidized and of waste to be gasified circulate through independent circuits, so that it is possible to establish a different working pressure for each of the two processes, and the feed rate of the OASC process does not It is affected by the flow imposed for the GASC process. In this way, the flow of the GASC process can be less than, equal to or greater than the feed flow to the OASC reactor, so that the amount of heat removed from the OASC reactor is not limited and it is possible to control its temperature in the
    suitable ranges. In the event that the temperature of the OASC reactor decreases excessively (for example by reducing the concentration of the feed), it is possible to decrease or even stop the flow of waste to be gasified, allowing a rapid restoration of the operation of the OASC reactor 5 to the desired temperature In addition, most of the heat generated in the OASC process will be transmitted to the stream of waste to be gasified, which will be heated to temperatures> 450 oC for its transformation into combustible gases. Said stream of waste to be gasified will be fed with a preheating, and at a pressure higher than the critical pressure of 10 water (220 bar), so that when heat is removed from the OASC reactor its temperature rises to temperatures greater than 450 oC. In this way, the aqueous stream of waste to be gasified only changes from a liquid state to a supercritical state, without changing at any time to a gaseous state, and crosses the temperature range before and after
    15 the critical temperature (374 oC) where its heat capacity has very high values, offering optimum performance as a cooling fluid, since it allows the removal of large amounts of heat without unduly modifying its temperature. Description of the invention
    The invention is based on a system of combined treatment of supercritical water oxidation (OASC) and gasification in supercritical water (GASC) of industrial, urban or wet biomass aqueous waste whose content is mainly organic in the form of residual water. , emulsion or mud. The OASC process will be carried out using an oxidizer stream, preferably oxygen, others can be used as oxygen enriched air, atmospheric air, hydrogen peroxide, etc. In the present invention the OASC reaction and GASC reaction units are separated by a metal wall through which
    exchange heat energy, so that the exothermic character of the OASC process is used to raise the temperature of the current to be treated by the GASC process, achieving a balance between the heat generation of the OASC process, preventing the reactor temperature from being excessive, and the energy consumption required by the GASC process, increasing the inlet temperature thanks to the heat given off by the OASC reactions and counteracting the endothermic nature of gasification reactions.
    The apparatus consists of a continuous tubular reactor of length between 10 and 500 meters provided with an external casing, preferably of cylindrical geometry and of somewhat smaller length than the OASC reactor, so that a first section of length between 1 and 200 m of the reactor OASC tubular can only be found surrounded by thermal insulation, without being surrounded by the housing, so that in that area it is not refrigerated and the generation of heat due to exothermic reactions causes an increase in the temperature of the reaction medium, which at its Once you accelerate the oxidation process in this initial phase. Subsequently, the second section of the OASC reactor enters the housing / cooling zone where its temperature is controlled so that it never exceeds the values that are considered optimal for each construction material (generally temperature <600 ° C, although if the construction materials of the reactor allow it said temperature could be higher). However, if the residue to be oxidized gives off a lot of heat (because it is very concentrated, because it oxidizes easily or because it has a high heat of reaction), the housing can be constructed covering the OASC reactor in its entire length. The volume of the tubular reactor and the housing will be sufficient so that the residence time inside the oxidation reactor is between 30 seconds and 5 minutes, and the volume of the gasification reactor will be sufficient so that the residence time respectively is between 60 seconds and 30 minutes, so that in both reactors the reactions take place with an extension greater than 90%, preferably with oxidation and gasification efficiency greater than 99%. The internal diameter of the OASC tubular reactor and the effective diameter of the housing They are designed based on the volumetric flow of waste streams to be treated under the operating conditions to meet the residence times specified above. In addition, in each circuit the fluids circulate at a linear speed> 2 mIs, to generate a turbulence and a drag speed that prevents sedimentation of the possible solid matter that contains the residues or that can be formed in the reactions of each process, thus reducing the possible problems of filling the pipes.
    To favor the performance of the gasification process, the outer wall of the tubular reactor and the inner wall of the housing may contain a suitable catalyst (impregnation of the surface with metals of Ni, Ru, Au, Pd, etc. or its coating with a metal sheet containing any of said elements) to increase the speed of the process, increase its performance at a lower temperature or increase the selectivity towards hydrogen production.
    The reactor and the housing together form a device similar to a concentric tube heat exchanger, in which the internal tube is the OASC reactor itself, where oxidation of the waste occurs with its consequent heat generation due to strongly exothermic reactions , thus acting as a heating fluid, while a stream of waste to be gasified at a lower temperature circulates through the annular space between the inner and outer tube, thus acting as a cooling fluid. The waste streams to be oxidized and the waste to be gasified are independent, so that it is possible to establish different operating conditions (inlet temperature, working pressure or a feed rate) for each of the two processes. Being a system of concentric bodies separated by a wall, and high pressure processes taking place on both sides, the thickness of said wall can be reduced between 20 and 50% compared to conventional OASC reactors in which greater need is required mechanical resistance in the reactor wall, since inside the reactor there are pressures greater than 220 bar and outside there is atmospheric pressure. This reduction in wall thickness of the OASC reactor reduces the material costs of the process and reduces the resistance to heat transmission between the fluids circulating on both sides of said wall.
    Thanks to the external circulation of the fluid to be gasified at a lower temperature, the fluid that circulates through the oxidation reactor yields a large part of the heat that is generated by reaction, preventing its temperature from increasing excessively even if the oxidation of waste is being carried out very concentrates, whose treatment in conventional OASC reactors without refrigeration would result in temperatures above 900 oC, which would be unfeasible because they are dangerous to the integrity of building materials. In the proposed invention, although a large amount of energy can be released in the reactor, the desired operating temperature can be controlled and adjusted on its walls, at any temperature between 400 and 700 oC, while the circuit of The gasification flow rate can be adjusted so that the temperature of the waste stream can rise to the desired value, between 400 and 700 oC. To optimize the heat exchange in the system, the heating fluid and the cooling fluid will preferably circulate in countercurrent, but it is also possible to circulate them in direct current. Since both fluids are independent, it is possible to modify their flow rates over a wide range to improve the control, stability and energy efficiency of both processes, OASC and GASC. In order to avoid heat losses to the outside, the oxidation tubular reactor and the external housing of the system are heat-insulated on its external surface by means of a thermal insulation layer.
    The outlet effluent from the oxidation reactor will still have a temperature between 400 and 500 oC, so it can be used in a first economizer to start preheating the current to be gasified and in a second economizer to use the remaining heat to preheat the current of residue to oxidize. In the case where the use of two economizers is not sufficient to maintain the processes in an energy-efficient way, that is, if the heat given up by the reactor effluent in the economizer is not sufficient to increase the temperature of the waste stream to be oxidized to the desired temperature for the start of the OASe process (generally close to 400oe, but being possible between 350 and 450 ° C), the system will have an additional external pre-heating system to raise the temperature from said feed to the desired value of input to the OASe reactor. To improve the sustainability of the process, the external pre-heating systems will consist of solar energy concentrators or another renewable energy system so that the process is sustainable and does not require the use of fuel or electrical resistors. However, other devices such as electric heaters, boilers, etc. could be used.
    The effluents from the OASe process and the GASe process can still have a temperature greater than 150 ° e after giving up some of their heat to preheat the feed streams. This temperature is reduced to values below 40 ° e by a final cooler of the oxidized stream and a final cooler of the gasified stream. To increase the energy use of the invention, these chillers can be devices for using the heat removed to produce low pressure steam or domestic hot water, increasing the energy efficiency of the invention and reducing the overall operating costs.
    A simplified scheme of the invention is shown in Figure 1. This description is not limited to particular systems, devices and methods described, as these may vary. The terminology used in the description is only intended to describe the particular versions or embodiments, and is not intended to limit the scope. Brief description of the drawings
    Figure 1.- Represents a scheme of a combined supercritical oxidation system of high concentration aqueous waste. with a housing
    5 external for the gasification of another aqueous stream of organic aqueous waste. according to the present invention. Each of the elements that make up the system are listed below:
    one. Aqueous residue to oxidize
    2. High pressure pump for aqueous residue to oxidize
    10 3. Economizer 1 for waste to be oxidized (heat exchanger)
    Four. Economizer 2 for waste to be oxidized (heat exchanger)
    5. External pre-heating system
    6. Oxidizer
    7. High pressure oxidant drive system
    15 8. Mixer
    9. OASC tubular reactor
    10. Oxidized effluent
    11 aqueous waste to gasify
    12. High pressure pump for aqueous waste to gasify 20 13. Economizer for waste to gasify (heat exchanger)
    14. Gasification housing
    fifteen. Thermal isolation
    16. Gasified effluent
    17. Oxidized stream cooler device
    18. Rusty effluent depressurizer device
    19. OASC process gas-liquid separator
    twenty. OASC gas stream
    twenty-one. OASC purified liquid stream
    22. Gas stream cooler device
    2. 3. Gasified effluent depressurizer device
    24. GASC process gas-liquid separator
    25.GASC gas stream
    26.GASC purified liquid stream Description of an embodiment of the invention
    Below is a description of an example of the mode of operation of the invention, referring to the numbering adopted in Figure 1. The mode of operation is not limited to what is described below, and can be adjusted to the needs of control, stability and process efficiency
    Initially, the stream of aqueous residue to be oxidized (1) is circulated by means of a high pressure pump (2) capable of exceeding the critical water pressure. The current (1) is preheated by a first economizer
    (3) and a second economizer (4) and later with an external preheating system (5) until a suitable temperature is reached to carry out the OASC process properly (generally at temperatures of 400 oC, although it can be valid between 350 -450 OC). The economizers (3) and (4) will begin to provide heat to the current (1) when the process is running at high temperature, at which time it may become feasible to dispense with the heat supply supplied by (5). Next, the high pressure impulse of the oxidant stream (6) is started by means of its corresponding high pressure drive system (7), at the same pressure as the waste stream to be oxidized (1). The streams (1 and 6) must be fed in the proper proportion so that, when contacted in the mixer (8), there is sufficient amount of oxidant to oxidize all the organic matter that is fed to the tubular reactor (9). Progressively close the pressure regulating valve (18) until a pressure around 240 bar is reached, being possible between 220 and 1000 bar, to keep the water at the desired pressure for the process, always above its critical pressure .
    When the organic matter and the oxidant come into contact, they form a homogeneous medium under supercritical conditions, the exothermic oxidation reactions will begin to take place at high speed, generating heat and increasing the temperature throughout the reactor (9), to temperatures of 400 -700 oC (depending on the optimum value for the process and the maximum operating temperatures allowed by the reactor materials) in the effluent (10) at the exit of the same. At this time, the waste stream to be gasified (11) is circulated by activating the high pressure pump
    (12) at small flow rates and progressively closing the pressure regulating valve (23) until a pressure around 240 bar is reached, being possible between 220 and 1000 bar, to keep the water always above its critical pressure. Said stream of waste to be gasified first passes through an economizer (13) and then through the housing (14) so that it begins to remove heat from the OASC reactor (9), lowering its temperature between 10 and 100 ° C at its output, preferably around 50 oC. Then, the concentration of the residue to be oxidized fed can be increased (1), so that as its oxidation occurs and the reactor effluent temperature rises again (between 10 and 100 oC), the flow rate of the pump (12) of the waste to be gasified (11) so that the cooling it causes is increased and the temperature at the outlet of the OASC reactor decreases again. The flow rate and concentration of the waste stream (1) are adjusted until the temperature of the waste stream to be gasified (11) is maintained in the proper range for gasification (generally between 450-750 OC).
    The effluent from the oxidation circuit (10) will have a high temperature (400-5000 C) and its energy is used first in the economizer (13) to preheat the waste stream to be gasified (11) and then to preheat the current of residue to be oxidized (1) by means of the economizer (3).
    The entire OASC tubular reactor (9) and the housing (14) are thermally insulated from the surroundings by a thermal insulation system (15) of a material suitable for temperatures up to 1000 ° C and with a thickness sufficient to minimize losses of heat to the outside. The effluent from the gasification circuit (16) will have a high temperature (> 500 ° C) and its energy is used in the economizer (4) to preheat the waste stream to be oxidized (1).
    The economizers (3), (4) and (13) are heat exchangers, preferably concentric tubes in which the effluent from the hot reactor circulates through the inner tube and through the annular space between the inner and outer tube circulates in countercurrent The fluid to be heated.
    Once a part of the heat of the effluent from the OASC process has been used, the cooler (17) reduces the temperature of the oxidized stream from 350 150 ° C to room temperature. This cooler (17) can be a device that takes advantage of the heat removed to produce low pressure steam or domestic hot water. After leaving the cooler (17), the effluent is depressurized to near ambient pressure through the valve (18) and then introduced into the gas-liquid separator (19), separating the gas stream at low pressure and temperature (20) and a liquid stream purified at low pressure and temperature (21).
    Similarly, once part of the heat from the GASC process effluent has been used in its corresponding economizer (4), the cooler (22) reduces the temperature of the gas stream from 374-200 oC to room temperature. This cooler (22) can be a device that takes advantage of the heat removed to produce low pressure steam or domestic hot water. After leaving the cooler (22), the effluent is depressurized to near ambient pressure through the valve (23) and then introduced into the gas-liquid separator (24), separating the gas stream rich in combustible gases (25) and a purified liquid stream (26).
    The plant has all the necessary safety elements, temperature, pressure, liquid and oxidant flow sensors and different level sensors for water and waste tanks. Finally, by means of the necessary control elements and an automaton, all the signals are registered and monitored to a PC, allowing the proper control of the operation through the process interface. In this way, the necessary operating conditions are established to treat the maximum concentration of waste with the desired oxidation efficiency and the flow rate and the combustible gas content of the gassed stream (15) are maximum and allow the degree of cooling necessary for operate safely, without exceeding in any case the safety temperature of the OASC reactor material (9) or the housing that forms the GASC reactor (14).
    权利要求:
    Claims (17)
    [1]
    1. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, comprising:
    a) An integrated OASC tubular reactor system (9) through which a stream of waste to be oxidized (1) circulates, surrounded by an external housing that acts as a GASC reactor (14) through which a stream of waste to be gasified circulates ( 11), which in turn acts as a refrigerant for the OASC reactor (9)
    b) A waste feed line to be oxidized, consisting of a stream of aqueous waste (1) and a high pressure pump (2) for said waste.
    c) An oxidant feed line, consisting of an oxidant current (6) and a high pressure delivery system (7) for the oxidant.
    d) An economizer (3) to preheat the current to be oxidized by transferring energy from the effluent (10) of the OASC tubular reactor (9).
    e) An economizer (4) to preheat the current to be oxidized by transferring energy from the effluent (16) of the GASC reactor (14).
    f) An economizer (13) to preheat the stream to be gasified
    (11) through the transfer of energy from the effluent (10) from the OASC reactor (9).
    g) A mixer (8) of the feed stream of aqueous residue to be oxidized (1) with the oxidant stream (6).
    h) OASC reactor (9), externally and concentrically surrounded in part or all of its length, of the cooling housing which in turn functions as a GASC reactor (14), the entire OASe reactor system (9) being and the GAS e housing
    (14) surrounded by thermal insulation (15) to minimize heat losses with the outside.
    i) A system for conditioning the final effluent of the OASe process for its discharge, equipped with a cooler (17) and depressurizing device (18) and gas and liquid phase separator (19), and two outlet lines that will contain the gas stream at low pressure and temperature (20) and the purified residue at low pressure and temperature (21).
    j) A system for conditioning the final effluent of the GASe process to discharge the liquid stream and use the gas phase rich in combustible gases, equipped with a cooler (22), depressurizing device (23), gas and liquid phase separator (24 ), and two outlet lines that will contain the gaseous stream at low pressure and temperature (25) and the purified residue at low pressure and temperature (26).
    [2]
    2. Apparatus for integrated supercritical oxidation and gasification treatment of organic aqueous wastes according to claim 1, wherein the OASe reactor and GASe reactor together form a device similar to a concentric tube heat exchanger, wherein the inner tube is the OASe reactor, where oxidation of the residues occurs using an oxidant stream, (preferably oxygen, others can be used as oxygen enriched air, atmospheric air, hydrogen peroxide, etc.) with the consequent heat generation due to the reactions strongly exothermic, thus acting as a heating fluid, while a waste stream circulates through the housing (that is, through the annular space between the inner tube and the outer outer tube)
    to gasify at a lower temperature, so it acts as a fluid
    refrigerant and its gasification takes place when it reaches the
    suitable temperature for said process.
    [3]
    3. Apparatus for integrated supercritical oxidation and gasification treatment of organic aqueous wastes, according to claim 2, characterized in that in order to optimize the heat exchange between the OASe reactor and the GASe casing, the heating fluid and the cooling fluid will preferably circulate countercurrently, but it is also possible to circulate them in direct current.
    [4]
    Four. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste according to claim 3, wherein the OASe reactor and the GASe reactor form a system of concentric bodies separated by a wall, through which heat transmission takes place between the internal fluid (heating fluid) and external fluid (cooling fluid) of the device, in which the wall between them, being subjected to high pressure on both sides, requires a thickness between 20 and 50% less to achieve the necessary mechanical resistance to withstand the operating conditions of the process.
    [5]
    5. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste according to claim 3, characterized in that it simultaneously produces the purification of a stream of aqueous residue by oxidation in supercritical water (generating energy due to exothermic oxidation reactions) and purification and recovery energy from another aqueous stream of waste by gasification in supercritical water (removing energy
    due to the preheating of said current and the endothermic gasification reactions) producing a hydrogen-rich combustible gas.
    [6]
    6. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the outer shell can be constructed to concentrically wrap a fraction or the entire length of a tubular oxidation reactor in supercritical water, so that depending on the residue to be oxidized (according to its concentration, reactivity and / or heat of reaction), it may be convenient to have several meters of reactor (between 1 and 200 m) in which the start of the OASe process without external cooling, so that the desired temperature is reached before coming into contact with the cooling / gasification housing.
    [7]
    7. Apparatus for integrated oxidation treatment and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the total volume of the tubular reactor will be sufficient so that the residence time inside the oxidation reactor is between 30 seconds and 5 minutes, and the volume of the gasification reactor will be sufficient so that the residence time is between 60 seconds and 30 minutes, so that in both reactors the reactions take place with the extension greater than 90%, preferably with oxidation and gasification efficiency greater than 99 %.
    ,
    [8]
    8. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the internal diameter of the OASe tubular reactor and the effective diameter of the housing are designed according to the volumetric flow of the waste streams to be treated in the operating conditions, so that in each circuit the fluids circulate at a linear speed> 2 ml causing the possible solid particles that contain the residues or that can be formed in the reactions of each process are kept in suspension, reducing or avoiding their sedimentation and possible problems with filling the pipes.
    [9]
    9. Apparatus for integrated oxidation and supercritical gasification treatment of organic aqueous wastes, according to claim 3, in which to favor the performance of the gasification process, the outer wall of the tubular reactor and the inner wall of the housing may contain a suitable catalyst (with Ni, Ru, Au, Pd, etc. metals or combinations thereof, by impregnating the surface or its coating with a metallic sheet containing any of said elements) to increase the speed of the process, increase its performance at a lower temperature or increase the selectivity towards hydrogen production.
    [10]
    10. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the pre-heating of the stream to be gasified is carried out in an economizer, and subsequently, both its final heating up to the reaction conditions and its
    The gasification process is carried out in an external housing that concentrically wraps part or all of a tubular oxidation reactor in supercritical water, in which the treatment of an organic aqueous residue is carried out.
    [11]
    11. Device for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the current to be oxidized and the current to be gasified are independent, so that each can circulate in
    10 different operating conditions (flow, concentration, pressure, initial temperature, etc.).
    [12]
    12. Device for integrated treatment of oxidation and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the stream of waste to be gasified (GASC process) circulating through the housing is not the feed of the process that generates heat ( OASC process), which allows adjusting and optimizing pressure, temperature and flow conditions for the stability of the OASC process and the GASC process and generation
    20 energy
    [13]
    13. Device for integrated oxidation treatment and supercritical gasification of organic aqueous waste, according to claim 3, wherein the stream to be gasified can be fed at high flow and reach temperatures between 400 and 700 oC, using the heat generated in the tubular reactor of Oxidation in supercritical water, in which the treatment of a high concentration organic waste is carried out, allowing the OASC process to be applied to waste with a concentration much higher than that which could be treated in conventional OASC systems where there is no refrigeration of the reactor or in the OASC systems in which the cooling of the reactor is carried out with the OASC process's own feed current.
    [14]
    14. Device for integrated treatment of supercritical oxidation and gasification of organic aqueous waste, according to claim 3, characterized in that it consists of three economizers of concentric tube heat exchanger type, in which the hot effluent circulates through the inner tube, and through the annular space between the inner and outer tube circulates countercurrent fluid to be heated.
    [15]
    15. Apparatus for integrated oxidation treatment and supercritical gasification of organic aqueous waste, according to claim 3, characterized in that the final cooler of the oxidized stream and the final cooler of the gasified stream can be devices for using heat removed to produce low steam pressure or domestic hot water, increasing the energy efficiency of the invention and reducing the overall operating costs.
    [16]
    16. Apparatus for integrated oxidation and supercritical gasification treatment of organic aqueous waste, according to claim 3, characterized in that in addition to generating a gas stream
    5 fuel through the GASe process, the OASe process can work in a self-sufficient way thanks to the economizer that uses the energy of the oxidized effluent (with temperatures between 400 and 500 ° C) to preheat the feed of waste to be oxidized to the temperature necessary for its treatment (350-450 ° C).
    [17]
    17. Apparatus for integrated treatment of oxidation and supercritical gasification of organic aqueous waste "according to claim 3, in the event that an extra energy input is necessary, a heating system based on a solar concentrator or other system is used
    15 renewable energy.
    ...
    ...
    ...
    ...
    N
    Fig. L
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    同族专利:
    公开号 | 公开日
    WO2018065641A1|2018-04-12|
    ES2660713B2|2018-06-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US6051145A|1997-04-24|2000-04-18|Hydroprocessing, Llc|Method for handling an effluent in a hydrothermal process|
    CN102874916A|2012-09-25|2013-01-16|西安交通大学|Supercritical water gasification-oxidation method for treating organic wastewater and recycling synthesis gas|
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