• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    For the purification of a gaseous effluent containing carbon compounds and nitrogen oxides by means of a regenerative afterburner system, at least two regenerators (A, B, C) filled with heat accumulator bodies are provided ( 7a, 7b, 7c) and connected by a combustion chamber (10), in which the gaseous effluent is alternately heated in a regenerator (A, B, C), the carbon compounds are oxidized in the combustion chamber (10) and, with the addition of a compound containing nitrogen and hydrogen, the nitrogen oxides are reduced in the combustion chamber (10) thermally and therefore non-catalytically. The remaining oxides of nitrogen are removed by means of a catalytically active heat accumulator layer (6a, 6b, 6c) and the addition of a nitrogen-containing compound and additional hydrogen in the regenerator (A, B, C) from which clean gas comes out.
    公开号:FR3062071A1
    申请号:FR1850601
    申请日:2018-01-25
    公开日:2018-07-27
    发明作者:Thomas Binninger；Kai Schulze
    申请人:Chemisch Thermische Prozesstechnik GmbH；
    IPC主号:
    专利说明:

    © Agent (s): JACOBACCI CORALIS HARLE.
    © PROCESS AND DEVICE FOR THE PURIFICATION OF GASEOUS EFFLUENTS.
    FR 3 062 071 - A1
    ©) For the purification of a gaseous effluent containing carbon compounds and nitrogen oxides by means of a regenerative afterburner system, at least two regenerators (A, B, C) are provided, filled with accumulators of heat (7a, 7b, 7c) and connected by a combustion chamber (10), according to which the gaseous effluent is alternately heated in a regenerator (A, B, C), the carbon compounds are oxidized in the combustion chamber ( 10) and, with the addition of a compound containing nitrogen and hydrogen, the nitrogen oxides are reduced in the combustion chamber (10) thermally and therefore, non-catalytic. The remaining nitrogen oxides are removed by means of a catalytically active heat accumulator layer (6a, 6b, 6c) and the addition of a compound containing additional nitrogen and hydrogen to the regenerator (A, B, C) from which the clean gas leaves.
    Xi closed open
    Technical field to which the invention relates
    The invention relates to a method for the purification of a gaseous effluent containing carbon compounds and nitrogen oxides in a regenerative afterburner system which has at least two regenerators filled with heat accumulators and connected by a combustion chamber. , in which the gaseous effluent is heated alternately in at least one regenerator into which it is introduced, the carbon compounds are oxidized in the combustion chamber and, with the addition of a compound containing nitrogen and hydrogen as a reducing agent, a simultaneous reduction of nitrogen oxides takes place in the combustion chamber, and the hot clean gas formed is extracted by means of at least one additional regenerator. Another object of the invention relates to a device for implementing the method.
    Technological background
    Such a process is known from document DE 10 2009 055 942 B4. In a regenerative thermal combustion system, the carbon compounds are oxidized in the multistage combustion chamber at a temperature above 800 ° C and the nitrogen oxides are thermally reduced by the addition of a compound containing nitrogen and hydrogen.
    In cement production, but also in other industrial processes where fuels are burned to generate high temperatures, environmental protection aspects as well as the costs of raw materials and fuels play an increasingly important role. important. In particular, emissions of nitrogen oxides (NOX), ammonia (NH3) and carbon monoxide (CO) must be reduced, while the cost of raw materials and fuels must be lowered by reducing the quantity of fuels, as well as low cost fuels and raw materials called secondary fuels or secondary raw materials. In addition to organic carbon compounds, such gases also contain carbon monoxide and ammonia. When ammonia (NH3) or urea, used as a reducing agent, is introduced in a metered amount into the combustion chamber, there is a risk of ammonia leakage as a by-product, and therefore of the harmful ammonia will escape into the atmosphere.
    Object of the invention
    The object of the invention is to make it possible to obtain a purification of gaseous effluents, in particular for the cement industry, which reduces the emissions of organic pollutants as well as carbon monoxide, nitrogen oxides and ammonia by reducing the cost of fuels / raw materials.
    According to the invention, this object is achieved by the process described in the introduction, in which a layer of catalytically active heat accumulator reducing the remaining nitrogen oxides to nitrogen using a compound comprising nitrogen and hydrogen is respectively provided as the lower part of the regenerator. Preferred embodiments of the method according to the invention have the following characteristics:
    - the catalytically active heat accumulator layer is configured as a honeycomb structure having prismatic channels;
    - the catalytically active heat accumulator layer is used simultaneously as a heat exchanger in which part of the heat of the outgoing gas is accumulated and is available for the raw gas entering after the changeover;
    - the compound containing nitrogen and hydrogen introduced into the combustion chamber is introduced therein hyperstoichiometrically, and the layer of catalytically active heat accumulator uses the compound containing nitrogen and available hydrogen in addition to reduce nitrogen oxides;
    - at least part of the compound containing nitrogen and hydrogen to reduce nitrogen oxides is already provided with the gaseous effluent;
    - aqueous solutions of ammonia, carbamic acid or urea are used as a compound containing nitrogen and hydrogen to reduce nitrogen oxides in order to decrease the required reaction temperature;
    - the catalytically active heat accumulator layer also reduces dioxins and furans in the gaseous effluent;
    - during a partial cycle, as the temperature of the combustion chamber decreases, the quantity of compound containing nitrogen and hydrogen supplied is continuously increased in the third zone of the combustion chamber of the regenerator to from which clean gas is extracted;
    - the temperature required for selective catalytic reduction in the area of the catalytically active heat accumulator layer is a temperature between 150 and 300 ° C, which is achieved by dissipating the heat of the gases extracted from the combustion chamber to the layer of heat accumulator passed through;
    - the compound containing nitrogen and hydrogen from the third zone of the regenerator combustion chamber from which the clean gas is extracted is supplied in a hyperstoichiometric ratio;
    - the process is used for the purification of gaseous effluents generated during the production of cement clinker;
    - secondary fuels / raw materials are used for the production of cement clinker so that the gaseous effluent has a carbon monoxide content sufficient for the autothermal functioning of the regenerative thermal afterburner system;
    - the nitrogen oxides present in the gaseous effluent, formed mainly by the primary combustion of the rotary kiln, are gases partially degraded by the addition of a compound containing nitrogen and hydrogen through d a selective non-catalytic reduction before the gaseous effluent is supplied to a heat exchanger for the preheating of the raw flour.
    The preferred devices for implementing the method according to the invention have the following advantageous characteristics:
    - the catalytically active heat accumulator layer contains titanium oxide, tungsten oxide and vanadium oxide as catalyst;
    - the catalytically active layer consists of elements which have a height of 100 to 1000 mm, preferably 300 to 600 mm, in the direction of flow;
    - instead of three regenerators into which the gaseous effluent penetrates and from which the clean gas leaves while the third is purged, there is a plurality of parallel inlet and outlet regenerators;
    - a separate regenerator is provided to purge the raw gas.
    According to the invention, the gaseous effluent is freed from nitrogen oxides (NOX), ammonia (NH3) and combustible carbon compounds. The carbon compound can be, for example, carbon monoxide or an organic carbon compound, for example, benzene, dioxins or furans.
    The gaseous effluent is introduced into at least two regenerators filled with heat accumulating bodies and connected by a combustion chamber. Preferably, heat storage bodies made of ceramic, in the form of a prism, having a multitude of channels parallel to the main axis of the prism, are used as heat storage bodies, in particular like those described in document EP 0472605 B2.
    The gaseous effluent is alternately introduced in cycles into at least one regenerator whose heat accumulating bodies have been preheated. The gaseous effluent preheated in this way is introduced into the combustion chamber which has an elevated temperature of more than 800 ° C, in particular between 850 and 1000 ° C. At this high temperature, the carbon compounds present in the combustion chamber undergo combustion thanks to the atmospheric oxygen present in the gaseous effluent, while the nitrogen oxides are reduced by means of a nitrogen and hydrogen compound. in the combustion chamber at this high temperature.
    The clean gas formed is then extracted by at least one additional regenerator whose heat accumulating bodies are heated, while at the same time, the gaseous effluent is cooled again.
    Preferably, at least one additional regenerator is provided which, after the raw gas cycle, is purged with the clean gas extracted from the combustion chamber. Instead of two or three regenerators, for example, a plurality of regenerators can also be provided, with the same number of gaseous effluent regenerators and clean gas regenerators, and a regenerator for purging being provided in each case.
    In accordance with the invention, the oxidation of carbonaceous compounds and the reduction of nitrogen oxides in the gaseous effluent are firstly carried out thermally, that is to say without using a catalyst, by reaction of nitrogen oxides with organic components as well as CO in a first zone of the combustion chamber, which extends from the heat accumulator bodies of the regenerator into which the gaseous effluent is introduced, up to the connection zone to which the regenerators are connected. The remaining nitrogen oxide, as well as a compound containing nitrogen and hydrogen, for example, ammonia in the form of an evaporated aqueous solution, will not be thermally reacted, with the formation of nitrogen, only in a second zone of the combustion chamber, which extends essentially from one end to the other of the space of the combustion chamber above the connection zone of the regenerators. Thus, a regenerative thermal afterburner system is used with which, in addition to the oxidation of organic pollutants, NOX is also reduced to nitrogen (N2) in two stages.
    Although carbon monoxide is largely oxidized to carbon dioxide in the combustion chamber, according to the invention, part of the nitrogen oxides is already reduced to nitrogen by carbon monoxide. In addition, nitrogen is formed due to the reduction of nitrogen oxides using the nitrogen and hydrogen-containing compound. Preferably, ammonia, urea or carbamic acid is used as the nitrogen and hydrogen containing compound.
    The nitrogen and hydrogen-containing compound used to reduce nitrogen oxides can be introduced into the combustion chamber of the regenerative thermal afterburner or may already be partially transported with the off-gas.
    The nitrogen and hydrogen containing compound is preferably introduced into the combustion chamber as an aqueous solution. Here, the solution may contain additives to reduce the required reaction temperature, for example, organic compounds such as alcohols. For optimal distribution of the aqueous solution of the nitrogen and hydrogen containing compound in the combustion chamber, it is possible to use nozzles with two fluids, i.e. a nozzle having an opening central for the aqueous solution, and an opening concentric to the previous one for the compressed gas, or ultrasonic atomizers each having a constant pressure or, preferably, a pulsed pump pressure.
    The zone which extends from the zone of connection to the heat accumulators of the regenerator from which the clean gas is extracted is known as the third zone.
    The compound containing nitrogen and hydrogen is introduced into the combustion chamber by means of injection devices, preferably, injection lances, which are distributed over the cross section of the combustion chamber, preferably between the first and second zones or between the second and third zones.
    When the gaseous effluent already contains part of the nitrogen and hydrogen-containing compound, part of the nitrogen oxides is reduced to nitrogen in the first zone. Furthermore, the nitrogen oxides are reduced to nitrogen in the second zone by means of the compound containing nitrogen and hydrogen introduced at the start of the second zone.
    The remaining nitrogen oxides, which are always present in the gaseous effluent when it enters the third zone, are reduced to nitrogen by means of the compound containing nitrogen and hydrogen which is injected into the using the injection device at the start of the third zone.
    The residence time of the gaseous effluent in the first zone and the third zone of the combustion chamber is preferably from 0.3 to 1 second, in particular from 0.4 to 0.6 seconds in each case , while the residence time of the gaseous effluent in the second zone of the combustion chamber is preferably from 0.5 to 2 seconds, in particular from 0.8 to 1.5 seconds. A cycle preferably lasts 1 to 4, in particular, 2 to 3 minutes.
    Since at the end of each cycle, the temperature of the heat accumulator bodies through which the gaseous effluent passes, and therefore the temperature in the first and second zones of the combustion chamber, which means that the performance of purification are reduced, the amount of nitrogen compound injected by means of the injection device at the start of the third zone is preferably increased during a cycle.
    According to the invention, the nitrogen oxides present in the gaseous effluent can thus be reduced by an amount of compound containing nitrogen and hydrogen such that not only the emission of oxides is prevented. nitrogen, but also the release of the nitrogen and hydrogen containing compound into the atmosphere, and thus the strict limit values for nitrogen oxides as well as for nitrogen and hydrogen compounds , especially ammonia, can be reliably met.
    The process according to the invention is particularly suitable for gaseous effluents containing nitrogen oxides having a high content of organic and / or inorganic carbon compounds, for example, a carbon monoxide content of more than 0.1 percent by volume, in particular, more than 0.4 percent by volume. The enthalpy of combustion of carbonaceous compounds can ensure the autothermal functioning of the afterburner system. This means that no additional fuel is required to operate the afterburner. If provided, the burner in the combustion chamber is therefore only used to start the afterburner.
    The purification of gaseous effluents according to the invention can thus be used in industrial processes in which fuels and / or raw materials are used which could not be used previously due to the formation of odor, of compounds volatile organic (VOC) and carbon monoxide.
    Consequently, the purification of the gaseous effluents according to the invention is particularly suitable for the gaseous effluents from industrial processes in which nitrogen oxides are formed due to a high process temperature in the presence of air and, in particular. in addition, carbon compounds such as carbon monoxide and organic compounds are produced. This is also the case, for example, when burning lime, and also in the steel industry, for example.
    According to the invention, at least one layer of catalytically active heat accumulator is respectively used as the lower part of the regenerators. This means that each regenerator has at least one layer of catalytically active heat accumulator at its lower part opposite the combustion chamber, and at least one layer of catalytically active heat accumulator on the side facing the chamber. combustion.
    At the same time, the catalytically active heat accumulator layer preferably forms a heat exchanger, which means that there is no functional separation between the heat accumulator bodies.
    Preferably, the compound containing nitrogen and hydrogen introduced into the combustion chamber is introduced therein in a hyperstoichiometric manner, the layer of catalytically active heat accumulator using the ammonia formed in excess in order to improve the reduction. nitrogen oxides.
    A hyperstoichiometric determination of the nitrogen and hydrogen containing compound may be advantageous since the catalytically active heat accumulator layer can accumulate the excess nitrogen and hydrogen containing compound, which already reduces a part of the nitrogen oxides in the raw gas during the next raw gas cycle when the raw gas flows through the regenerator.
    As a nitrogen and hydrogen containing compound to reduce nitrogen oxides, an aqueous solution of ammonia, carbamic acid or urea with or without additives is preferably used to decrease the required reaction temperature. Thanks to the catalytically active heat accumulator layer, dioxins and furans can also be eliminated from the gaseous effluent by the regenerative thermal afterburner system according to the invention.
    The temperature of the catalytically active heat accumulator layer from which the clean gas is extracted, which is required for the catalytic reduction, is preferably between 150 and 300 ° C.
    The process according to the invention is particularly suitable for purifying the gaseous effluents generated during the production of cement clinker.
    Secondary fuels and secondary raw materials are used in most cases for the production of cement clinker. In particular, profitable waste such as used tires, used oil, plastic waste, or biogenic fuels such as paper fiber residues or animal meal, are used as such. The gaseous effluent thus has a sufficient carbon monoxide content for the autothermal operation of the regenerative thermal afterburner system.
    During the production of cement clinker, the hot gaseous effluent formed by the primary combustion of the rotary kiln is introduced into a heat exchanger to preheat the raw flour. Preferably, the nitrogen oxides formed mainly by the primary combustion of the rotary kiln are therefore partially degraded in the gaseous effluent by providing a compound containing nitrogen and hydrogen by means of selective non-catalytic reduction. , before the gaseous effluent is supplied to the heat exchanger for preheating raw flour. The gaseous effluent leaving this heat exchanger can then be purified by the process according to the invention.
    In the process, the nitrogen and hydrogen containing compound can be provided in a hyperstoichiometric ratio.
    The catalytically active heat accumulator layer of the regenerative afterburner system according to the invention may contain or may be formed from titanium oxide, tungsten oxide and / or vanadium oxide. substances.
    The catalytically active layer may consist of catalyst elements which have a height of 100 to 1000 mm, preferably 300 to 600 mm, in the direction of flow of the gas.
    Instead of three regenerators for the supply of gaseous effluent, the evacuation of clean gas or for purging, the regenerative thermal afterburner system according to the invention can also have a plurality of parallel regenerators for the supply of gaseous effluent, l evacuation of clean gas or to purge.
    In addition, a separate regenerator can be provided to purge the raw gas out of the regenerator into which the latter was introduced during the previous cycle.
    Apart from the gaseous effluents generated during the production of cement clinker, the device according to the invention is also suitable for the purification of gaseous effluents from the production of nitric acid, adipic acid, fertilizers or uranium trioxide.
    Detailed description of an exemplary embodiment
    The invention will be explained in more detail below by way of example with reference to the accompanying drawings, in which:
    Figure 1 schematically shows an enlarged view of the operating position AB of the regenerative thermal afterburner system, in which the gaseous effluent is introduced into the regenerator A, the clean gas is extracted from the regenerator B and the regenerator C is purged, and Figure 2 also schematically shows the two other operating positions BC and CA, in which the gaseous effluent is introduced into the regenerator B, the clean gas is extracted from the regenerator C and the regenerator A is purged, or the gaseous effluent is introduced into regenerator C, the clean gas is extracted from regenerator A and regenerator B is purged, respectively.
    Each of the regenerators A, B, C, the end of which is opposite to the combustion chamber 10 of the regenerative thermal afterburner systems, is connected via an inlet locking device 1a, 1b, 1c to the gaseous effluent duct 1 , through which the gaseous effluent to be purified is introduced into the regenerator A, B, C via an outlet locking device 2a, 2b, 2c up to the clean gas conduit 2, through which the clean gas is released into the atmosphere through a chimney, for example, and via a purge gas interlock 3a, 3b, 3c, to a purge gas conduit 3a, 3b, 3c. The locking devices can be configured in the form of valves or flaps.
    The main fan 4 for generating negative pressure in the regenerators A, B, C is provided in the clean gas pipe 2 downstream of the regenerative thermal afterburner system. The purge gas pipe is connected to the gaseous effluent pipe 1 by means of a locking device and an auxiliary fan 5.
    In the operating position AB according to Figures 1 and 2, the gaseous effluent is introduced into the regenerator A, the clean gas is extracted from the regenerator B and the regenerator C is purged, while in the following cycle in the operating position BC, the gaseous effluent is introduced into the regenerator B, the clean gas is extracted from the regenerator C and the regenerator A is purged; in the following cycle according to the operating position CA, the gaseous effluent is introduced into the regenerator C, the clean gas is extracted from the regenerator A and the regenerator B is purged, after which, the operating position AB is resumed in the cycle following.
    The gaseous effluent which is supplied through the gaseous effluent conduit 1 has a carbon monoxide content, for example, from 0.2 to 1 percent by volume, a nitrogen oxide content, for example, from 100 to 1000 mg / Nm3 and an oxygen content, for example, of 8 to 13 volume percent, the remainder being substantially nitrogen, water and carbon dioxide.
    Each of the regenerators A, B, C has a layer of catalytically active heat accumulator 6a, 6b, 6c at its lower part opposite the combustion chamber 10, as well as heat accumulator bodies 7a, 7b, 7c to a certain distance above the layer of catalytically active heat accumulator 6a, 6b, 6c on the side facing the combustion chamber 10.
    The catalytically active heat accumulator layer 6a, 6b, 6c is separated from the heat accumulator bodies 7a, 7b, 7c arranged above a space 10a, 10b, 10c.
    This means that the catalytically active heat accumulator layer 6a, 6b, 6c can be purified separately or removed from the regenerator A, B, C, for example.
    In addition, each of the regenerators A, B, C optionally has a narrowing 8a, 8b, 8c above the heat storage bodies 7a, 7b, 7c and below the connection zone V1, V2 at the level of which two regenerators Adjacent A, B, C are connected to each other.
    The combustion chamber 10 of the regenerative thermal afterburner system is made up of several zones, namely zones 11a, 11b, 11c between the heat accumulator bodies 7a, 7b, 7c and the connection zone V1, V2 of regenerator A, B , C respectively, and zone 12 above the connection zones V1, V2.
    The first zone is zone 11a, 11b, 11c between the heat accumulators 7a, 7b, 7c and the connection zone V1, V2 of regenerator A, B, C in which the gaseous effluent from the gaseous effluent conduit 1 is introduced, therefore the area 11a of Figures 1 and 2 in the operating position AB.
    In the first zone 11a, 11b, 11c, carbon monoxide and / or organic compounds are burnt in the gaseous effluent.
    At the connection areas V1, V2, an injection device 14a, 14b, 14c is respectively provided on each regenerator A, B, C.
    In the second zone 12, which is formed by the zone above the connection zones V1, V2, the nitrogen oxides present in the gaseous effluent leaving the first zone 11a, 11b, 11c are largely reduced to nitrogen at means of a compound containing nitrogen and hydrogen injected using the injection device 14a, 14b, 14c disposed above in each case, in this case, thermally, it is ie non-catalytic.
    The third zone 11a, 11b, 11c is formed by the zone between the connection zone V1, V2 and the heat accumulators of the regenerator A, B, C from which the gaseous effluent is brought to the clean gas conduit 2, therefore zone 11b in the operating position AB according to FIGS. 1 and 2.
    In the third zone 11a, 11b, 11c, a compound containing additional nitrogen and hydrogen is injected into the gaseous effluent leaving the second zone 12 by means of the injection device 14a, 14b, 14c at the level of the connection zone V1, V2, therefore zone 11b in the operating position AB according to FIGS. 1 and 2, in order to catalytically reduce the remaining nitrogen oxides to nitrogen by means of the heat accumulator layer catalytically active 6a, 6b, 6c.
    The fourth zone of the combustion chamber 10, which is formed by the zone between the connection zones V1, V2 and the heat storage bodies 7a, 7b, 7c, therefore the zone 11c in the operating position AB according to the Figures 1 and 2, is supplied with purified gas from the second zone 12 in order to rid the heat accumulator bodies 7a, 7b, 7c and the catalytically active heat accumulator layer 6a, 6b, 6c, therefore the heat accumulator bodies 7c and the layer of catalytically active heat accumulator 6c in the operating position AB according to FIGS. 1 and 2, residues of raw gas, by sucking this gas in the purge gas pipe 3.
    According to the invention, the reduction of nitrogen oxides by carbon compounds, such as carbon monoxide, in the gaseous effluent in the operating position AB of the first zone 11a, for example, and the reduction of oxides d nitrogen by means of the compound containing nitrogen and hydrogen injected using the injection device 14a into the second zone 12, are thus produced purely thermally, whereas after the injection of the compound containing nitrogen and hydrogen using the injection device 14b and after passing through the regenerator 7b, a catalytic reduction of the nitrogen oxide remaining on the heat accumulator layer catalytically active 6b takes place in the third zone 11b.
    After this first cycle, the cycle switches to the next cycle according to the operating position B-C, then to the cycle according to the operating position C-A and then returns to the cycle according to the operating position A-B in Figure 2.
    The gaseous effluent from the gaseous effluent pipe 1 is thus introduced alternately into the regenerators A, B and C where, as can be seen in Figures 1 and 2, the gaseous effluent to be purified is introduced into the regenerator A preheated, and the clean gas is extracted through the regenerator B so that the gas flow takes place along the arrow 15 in the combustion chamber 10.
    If a gaseous effluent containing a compound containing nitrogen and hydrogen and / or carbon monoxide is introduced into the preheated heat accumulator bodies of regenerator A, B, C, part of the nitrogen oxides of l 'gaseous effluent in the first zone 11a, 11b, 11c will be reduced.
    The compound containing nitrogen and hydrogen introduced at the start of the second zone 12 via the injection device 14a, 14b, 14c makes it possible to obtain a thermal reduction of the nitrogen oxides in the second zone 12.
    On the other hand, by injecting the compound containing nitrogen and hydrogen at the end of the second zone 12 or at the beginning of the third zone 11a, llb, 11c via the injection device, quantities additional nitrogen oxide is reduced catalytically in the catalytically active heat accumulator layer 6a, 6b, 6c.
    Thanks to the locking devices 16a, 16b, 16c in the supply pipe 16 of compound containing nitrogen and hydrogen from the injection devices 14a, 14b and 14c, the supply of compound containing nitrogen and hydrogen can be regulated in each case so as to have a continuous increase in the nitrogen-containing compound and hydrogen added during an operating cycle.
    Since the heat accumulator layer 6a, 6b, 6c and the heat accumulator bodies 7a, 7b, 7c cool during an operating cycle due to the gaseous effluent introduced, thus lowering the temperature in the zone 12 of the combustion chamber 10, the non-catalytic thermal reduction rate is reduced to reduce the nitrogen oxides in the combustion chamber 10.
    We can thus compensate for the reduction in the reduction rate due to non-catalytic thermal reduction in zone 12 by increasing the supply of a compound containing nitrogen and hydrogen in the third zone 11a, 11b, llc, therefore by means of the injection device 14b in the operating position AB according to FIGS. 1 and 2, which is supplied to the layer of catalytically active heat accumulator 6b, that is to say by increasing the reduction rate due to catalytic reduction.
    In particular, in the case of an autothermal operation of the afterburner system, the burner 18 is used to start the system.
    The example below, which was implemented using a system for the production of cement clinker and a system for the purification of gaseous effluent according to Figures 1 and 2, aims to explain further l 'invention.
    Example
    A gaseous effluent from a rotary kiln for the production of clinker has the following composition:
    percent by volume of carbon dioxide
    0.5 volume percent carbon monoxide volume percent oxygen
    500 mg / Nm3 of nitrogen oxides mg / Nm3 of ammonia
    100 mg / Nm3 of organic carbon.
    The gaseous effluent whose volume is 300,000 Nm3 / h reaches the regenerative thermal afterburner system via the conduit
    I with the fan 4. The heat accumulators, for example, of regenerator A, heat the gaseous effluent to a temperature of 900 ° C., temperature at which, in the first zone 11a of the combustion chamber 10, the oxides nitrogen are reduced by the excess ammonia always present, introduced into the gaseous effluent in the system during the previous cycle, and by part of the carbon monoxide with the formation of nitrogen. The excess amount of carbon monoxide is oxidized to carbon dioxide by the oxygen present in the gaseous effluent and contributes to the autothermal mode of operation of the afterburner system. Volatile organic pollutants and olfactory active substances present in the gaseous effluent also burn, forming carbon dioxide and water vapor in the first zone
    It has combustion chamber 10.
    After leaving the first zone 11a of the combustion chamber 10, the gaseous effluent has the following composition:
    percent by volume of carbon dioxide
    0.1 volume percent carbon monoxide
    9.6 percent by volume of oxygen
    400 mg / Nm3 of nitrogen oxides mg / Nm3 of ammonia mg / Nm3 of organic carbon.
    At the start of the second zone 12 of the combustion chamber 10, 150 kg / h of a 25 percent ammonia solution are injected into the water in the direction of flow according to arrow 15 in order to reduce additional quantities of nitrogen oxides still present. Clean gas is extracted through regenerator B, for example. At the end of the second zone 12 of the combustion chamber 10, that is to say at the start of the third zone 11b, 80 kg / h of an ammonia solution at 25 percent by additional weight are injected in the water in the direction of flow in order to further reduce the additional quantities of nitrogen oxides still present and to produce an excess of ammonia.
    At the end of the third 11b of the combustion chamber 10, the purified gaseous effluent has the following composition:
    volume percent of carbon dioxide volume percent of carbon monoxide
    9.5 volume percent oxygen
    250 mg / Nm3 of nitrogen oxides mg / Nm3 of ammonia mg / Nm3 of organic carbon.
    After passing through the catalytically active layer 6b of the clean gas regenerator B, the gaseous effluent has the following composition:
    volume percent of carbon dioxide volume percent of carbon monoxide
    9.5 volume percent oxygen
    150 mg / Nm3 of nitrogen oxides mg / Nm3 of ammonia mg / Nm3 of organic carbon.
    If the direction of flow is reversed according to arrow 17, the dosage of the ammonia solution injected is reversed. The direction of flow is reversed approximately every two to three minutes. Clean gas leaves the afterburner at an average temperature of 40 ° C above the inlet temperature.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    1. Process for the purification of a gaseous effluent containing carbon compounds and nitrogen oxides in a regenerative afterburner system which has at least two regenerators (A, B, C) filled with heat accumulators (7a, 7b, 7c) and connected by a combustion chamber (10), in which the gaseous effluent is heated alternately in at least one regenerator (A, B, C) into which it is introduced, the carbon compounds are oxidized in the chamber combustion (10) and, with the addition of a compound containing nitrogen and hydrogen as a reducing agent, a simultaneous reduction of nitrogen oxides takes place in the combustion chamber (10) , and the hot clean gas formed is extracted by means of at least one additional regenerator (A, B, C), characterized in that a layer of catalytically active heat accumulator (6a, 6b, 6c) reducing the oxides nitrogen remaining in nitrogen using a com installed containing nitrogen and hydrogen is respectively provided as the lower part of the regenerator (A, B, C).
    [2" id="c-fr-0002]
    2. Method according to claim 1, according to which the catalytically active heat accumulator layer (6a, 6b, 6c) is configured in the form of an alveolar structure having prismatic channels.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, wherein the catalytically active heat accumulator layer (6a, 6b, 6c) is used simultaneously as a heat exchanger in which part of the heat of the outgoing gas is accumulated and is available for the raw gas entering after the changeover.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, according to which the compound containing nitrogen and hydrogen introduced into the combustion chamber (10) is introduced therein in a hyperstoichiometric manner, and according to which the layer d he catalytically active heat accumulator (6a, 6b, 6c) uses the excess nitrogen and hydrogen-containing compound to reduce nitrogen oxides.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, according to which at least a part of the compound containing nitrogen and hydrogen for reducing nitrogen oxides is already supplied with the gaseous effluent.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which aqueous solutions of ammonia, carbamic acid or urea are used as a compound containing nitrogen and hydrogen to reduce nitrogen oxides in order to decrease the required reaction temperature.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, according to which the catalytically active heat accumulator layer (6a, 6b, 6c) also reduces the dioxins and furans in the gaseous effluent.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, according to which, during a partial cycle, as the temperature of the combustion chamber decreases, the quantity of compound containing nitrogen and hydrogen supplied is increased continuously in the third zone (11a, 11b, 11c) of the combustion chamber (10) of the regenerator (A, B, C) from which the clean gas is extracted.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, in which the temperature required for the selective catalytic reduction in the region of the catalytically active heat accumulator layer (6a, 6b, 6c) is a temperature between 150 and 300 ° C, which is reached by dissipating the heat of the gases extracted from the combustion chamber (10) towards the heat accumulator layer (6a, 6b, 6c) passed through.
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, in which the compound containing nitrogen and hydrogen from the third zone (11a, 11b, 11 c) of the combustion chamber (10) of the regenerator (A , B, C) from which the clean gas is extracted is supplied in a hyperstoichiometric ratio.
    [11" id="c-fr-0011]
    11. Method according to any one of the preceding claims for the purification of gaseous effluents generated during the production of cement clinker.
    [12" id="c-fr-0012]
    12. The method of claim 11, wherein secondary fuels / raw materials are used for the production of cement clinker so that the gaseous effluent has a carbon monoxide content sufficient for the autothermal operation of the regenerative thermal afterburner system. .
    [13" id="c-fr-0013]
    13. The method of claim 11 or 12, wherein the nitrogen oxides present in the gaseous effluent, formed mainly by the primary combustion of the rotary kiln, are gases partially degraded by the addition of a compound containing l nitrogen and hydrogen through selective non-catalytic reduction before the off-gas is supplied to a heat exchanger for preheating raw flour.
    [14" id="c-fr-0014]
    14. Device for implementing the method according to any one of the preceding claims, characterized in that the catalytically active heat accumulator layer (6a, 6b, 6c) contains titanium oxide, tungsten oxide and vanadium oxide as catalyst.
    [15" id="c-fr-0015]
    15. Device for implementing the method according to claim 14, wherein the catalytically active layer (6a, 6b, 6c) consists of elements which have a height of 100 to 1000 mm, preferably 300 to 600 mm , in the direction of flow.
    [16" id="c-fr-0016]
    16. Device according to claim 14 or 15, wherein, instead of three regenerators (A, B, C) where the gaseous effluent enters and from which the clean gas leaves while the third is purged, there are a plurality of parallel input and output regenerators.
    [17" id="c-fr-0017]
    17. Device according to any one of claims 14 to 16, in which a separate regenerator is provided for purging the raw gas.
    [18" id="c-fr-0018]
    18. Use of the device according to any one of claims 14 to 17 for the purification of gaseous effluents generated during the production of cement clinker, nitric acid, adipic acid, fertilizer or trioxide uranium.
    1/2
    类似技术:
    公开号 | 公开日 | 专利标题
    US9272240B2|2016-03-01|Method and device for purifying exhaust gases
    FR3062071A1|2018-07-27|METHOD AND DEVICE FOR THE PURIFICATION OF GASEOUS EFFLUENTS
    FR2931204A1|2009-11-20|DRY TRIFUNCTIONAL CATALYTIC REDUCTION OF NOX FROM GAS TURBINE
    FR2967360A1|2012-05-18|METHOD AND DEVICE FOR REDUCING NOX EMISSIONS DURING INCINERATION OF EXHAUST GASES
    FR2488678A1|1982-02-19|METHOD AND APPARATUS FOR COMBUSTION TO SIGNIFICANTLY REDUCE THE EMISSION OF NITROGEN COMPOUNDS FORMED DURING COMBUSTION
    FR2510423A1|1983-02-04|PROCESS FOR MELTING GLASS WITH TWO-STEP CONTROL OF NOX FORMATION
    KR20080096534A|2008-10-30|Method of reducing nitrogen oxide on the primary side in a two-stage combustion process
    EP3013740B1|2019-10-16|Direct-fired heating method and facility for implementing same
    EP1951616A2|2008-08-06|Method for producing synthetic gas using an oxygen-containing gas produced by at least one gas turbine
    KR100597695B1|2006-07-07|A Selective Catalyst And Non-Catalyst Reduction System Using Regenerative Heat Recovery
    FR2966906A1|2012-05-04|HEAT RECOVERY VAPOR GENERATOR
    US20140182492A1|2014-07-03|Method for optimizing the burnout of exhaust gases of an incinerator
    HU0102798A2|2001-12-28|Method for the heat treatment of solids
    WO2018115499A1|2018-06-28|Process and plant for denitrification of combustion gases
    KR20050020624A|2005-03-04|Process for NOx-reduction in combustion chamber and device for carrying out said process
    FR2640728A1|1990-06-22|METHOD AND APPARATUS FOR REDUCING THE FORMATION OF NITROGEN OXIDES DURING COMBUSTION
    CA2813667C|2020-10-13|Denitrification process for smoke produced by a combustion furnace and installation for the implementation of said process
    WO1992019532A1|1992-11-12|Method for producing sulphur from a combustible effluent and at least one acidic gas containing hydrogen sulphide, and thermal reactor
    FR2809638A1|2001-12-07|METHOD AND DEVICE FOR REGENERATING USED ABSORBENTS FROM THERMAL GENERATOR FUME TREATMENT
    EP3359502B1|2019-08-14|Process for calcining mineral rock in a regenerative parallel-flow vertical shaft furnace and furnace used therefor
    EP2212241A2|2010-08-04|Method and system for processing gaseous effluents for independently producing h2 and co
    US20220003412A1|2022-01-06|Method for purifying a raw gas stream and purification device
    EP3610196B1|2021-09-15|Method and facility for producing electricity from a solid recycled waste load
    EP2371444B1|2013-02-20|Process and device for the purification of fumes containing acidic pollutants
    EP2823875B1|2015-12-23|Method for purifying combustion fumes
    同族专利:
    公开号 | 公开日
    DE102017101507A1|2018-07-26|
    IL257003D0|2018-03-29|
    GB2560248A8|2018-10-10|
    GB2560248A|2018-09-05|
    US10569220B2|2020-02-25|
    CN109028108A|2018-12-18|
    US20180214821A1|2018-08-02|
    GB2560248B|2020-10-14|
    GB201800937D0|2018-03-07|
    CA2992199A1|2018-07-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1990014560A1|1989-05-17|1990-11-29|Walter Kanzler|Installation and process for heat treatment of waste gases|
    EP0472605B2|1989-05-17|2003-01-22|Schedler, Johannes, Dipl.Ing.|Installation and process for heat treatment of waste gases|
    WO1999047245A1|1998-03-17|1999-09-23|Heed Bjoern|Pollution control|
    CN2757903Y|2004-11-09|2006-02-15|赖正昕|Heat storage type SCR denitrating and dioxime removing equipment|
    DE102009055942B4|2009-11-26|2012-02-02|Chemisch-Thermische Prozesstechnik Gmbh|Process and apparatus for purifying exhaust gases|
    EP2759329A1|2013-01-29|2014-07-30|Chemisch Thermische Prozesstechnik GmbH|Method and device for purifying exhaust gases|
    DE102013109977A1|2013-09-11|2015-03-12|Thyssenkrupp Industrial Solutions Ag|Process and plant for purifying exhaust gases with a regenerative post-combustion plant|
    DE3348099C2|1983-10-03|1994-10-20|Wahlco Power Products Inc|Device for preheating a stream of combustion air|
    DE3536958C1|1985-10-17|1986-12-11|Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe|Method and device for preheating combustion air and for the catalytic reduction of pollutants in flue gas|
    GB8607810D0|1986-03-27|1986-04-30|Stordy Combustion Eng Ltd|Operating burners|
    DE4018786A1|1990-06-12|1991-12-19|Krupp Polysius Ag|METHOD FOR PURIFYING THE EXHAUST GASES FROM PLANTS FOR PRODUCING CEMENT CLINKER|
    US5233934A|1992-08-20|1993-08-10|Wahlco Environmental Systems, Inc.|Control of NOx reduction in flue gas flows|
    DE4313861A1|1993-04-28|1994-11-03|Rothemuehle Brandt Kritzler|Unit for nitrogen oxide decrease in furnace exhaust gases|
    US5547650A|1994-03-24|1996-08-20|The Regents Of The University Of California|Process for removal of oxides of nitrogen|
    US5589142A|1994-07-27|1996-12-31|Salem Englehard|Integrated regenerative catalytic oxidation/selective catalytic reduction abatement system|
    US6264905B1|1999-10-12|2001-07-24|Hera, Llc|Method and apparatus for reducing “ammonia slip” in SCR and/or SNCR NOX removal applications|
    US7758831B2|2004-09-30|2010-07-20|Babcock Power Environmental Inc.|Systems and methods for removing materials from flue gas via regenerative selective catalytic reduction|
    AT507773B1|2009-07-15|2010-08-15|Scheuch Gmbh|METHOD AND APPARATUS FOR RELIEVING SMOKE GASES|
    WO2014010262A1|2012-07-12|2014-01-16|新東工業株式会社|Regenerative exhaust gas purification device|
    JP6476115B2|2012-08-17|2019-02-27|ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ|V / TiW catalyst activated by zeolite|
    CN104930525A|2014-03-20|2015-09-23|化学热处理技术有限责任公司|Method and for purifying exhaust gas|
    DE102015203244A1|2015-02-24|2016-08-25|Steinmüller Babcock Environment Gmbh|Mehrzugkessel|
    DE102015108014B3|2015-05-20|2016-11-24|Chemisch Thermische Prozesstechnik Gmbh|Process and installation for cleaning exhaust gases laden with nitrogen oxides|
    JP6520420B2|2015-06-04|2019-05-29|株式会社豊田自動織機|Chemical heat storage device|
    KR101763661B1|2015-06-30|2017-08-02|기련이엔씨|Selective Catalytic Reduction Device Using Regenerative Heat Recovery System|
    CN105536521A|2016-01-12|2016-05-04|哈尔滨工业大学（威海）|Heat accumulating type oxidation device for catalysis denitration|
    CN106051792A|2016-05-30|2016-10-26|江苏三井环保股份有限公司|RTO regenerative thermal oxidation system|JP6616737B2|2016-05-31|2019-12-04|日立造船株式会社|Exhaust gas denitration device, incinerator and exhaust gas denitration method|
    EP3750618A1|2019-06-12|2020-12-16|CTP Chemisch Thermische Prozesstechnik GmbH|Method and waste gas purification system for purifying waste gases|
    法律状态:
    2020-01-31| PLFP| Fee payment|Year of fee payment: 3 |
    2020-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2021-12-31| PLSC| Publication of the preliminary search report|Effective date: 20211231 |
    2022-01-27| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102017101507.8|2017-01-26|
    DE102017101507.8A|DE102017101507A1|2017-01-26|2017-01-26|Method and device for exhaust gas purification|
    [返回顶部]