DEVICE FOR THE REDUCTION OF NOX AND N2O CONTENT IN GASES AND PROCESS FOR THE REDUCTION OF NOX AND N2

专利摘要:
device and process for the elimination of nox and n2o. the present invention relates to a device and a process for decreasing the content of nox and n2o in gases. the device comprises: a) a container (1) and arranged in this b) two subsequent reaction steps for the elimination of nox (step deno x) by reducing nox with a reducing agent containing nitrogen, and subsequently for the elimination of n2o by catalytic decomposition of n2o in n2 and in o2 (step den2o), which are constituted by one or several catalyst beds (7, 8) respectively and which are crossed by the gas to be purified, where c) by at least one catalyst bed from the denox step (7) contains a catalyst for the reduction of nox with nitrogen-containing reducing agents, which contains zeolites doped with transition metals, including lanthanides, d) at least one catalyst bed from the step den2o (8) contains a catalyst for the decomposition of n2o into n2 and into o2, which contains one or more active catalytic compounds of elements selected from groups 5 to 11 of the periodic table of elements, except for zeolites doped with iron and e) an Before the denox step (7), a device is provided for introducing the nitrogen-containing reducing agent into the gas flow containing nox and n2o. the combination of catalysts used in accordance with the present invention allows for a very simple structure and very economical operation of the reactor.
公开号:BR112014014516B1
申请号:R112014014516-4
申请日:2012-12-08
公开日:2020-09-08
发明作者:Meinhard Schwefer；Rolf Siefert；Stefan Pinnow
申请人:Thyssenkrupp Industrial Solutions Ag；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a device as well as a process for the catalytic elimination of NOx and N2O.
[0002] [002] In the case of many processes, as for example. in the case of combustion processes or in the case of industrial production of nitric acid or caprolactam, a residual gas charged with nitrogen monoxide NO, nitrogen dioxide NO2 (together known as NOX) as well as with hilarious N2O gas results. While NO and NO2 have long been known as compounds of ecotoxic relevance (acid rain, smog formation) and in relation to the respective maximum permitted emissions, limit values have been stipulated worldwide, in the last decade the hilarious gas has gradually also become center of attention for environmental protection, considering that it contributes significantly to the degradation of the stratospheric ozone layer and the greenhouse effect. Consequently, for reasons of environmental protection, there is an urgent need for technical solutions, which will make it possible to eliminate hilarious gas emissions together with NOX emissions.
[0003] [003] For the elimination of N2O on the one hand and NOx on the other hand, numerous possibilities are known.
[0004] [004] In the case of NOx reduction, it is worth mentioning the selective catalytic reduction (SCR) of NOX by means of ammonia in the presence of TiO2 catalysts containing vanadium (compare eg G. Ertl, H. Knotzinger, J. Weitkamp: Handbook of Heterogeneous Catalysis, Vol. 4, Pages 1633-1668, VCH Weinheim (1997)). This depending on the catalyst can be carried out at temperatures of approx. 150 ° C to 450 ° C and according to the technical specifications it is preferably carried out between 200 ° C and 400 ° C, particularly between 250 ° C and 350 ° C. It is the most used variant for the reduction of NOX of waste gases from industrial processes and in the case of a corresponding dimensioning of the catalyst beds, it allows a NOX decomposition greater than 90%.
[0005] [005] There are also processes for the reduction of NOX based on zeolite catalysts, which are carried out with the use of different reducing agents. In addition to the zeolites exchanged with Cu (compare eg EP-A-914,866) particularly zeolites containing iron appear to be of interest for practical applications.
[0006] [006] Thus US-A-5,451,387 and EP-A-756,891 describe processes for the selective catalytic reduction of NOX with NH3 through zeolites exchanged with iron, which preferably operate at temperatures between 200 ° C and 550 ° C, particularly approximately 400 ° C.
[0007] [007] Unlike the reduction of NOX in waste gases, which has been established in the art for many years, for the elimination of N2O there are comparatively few technical processes, which in most cases are based on a thermal or catalytic decomposition of N2O . An overview regarding catalysts, whose adequacy of principle is proven for decomposition and for the reduction of hilarious gas, is given by Kapteijn et al. (Kapteijn F. et al., Appl. Cat. B: Environmental 9 (1996) 2564). The catalytic decomposition of hilarious gas in N2 and O2 in this case compared to catalytic reduction with selected reducing agents, such as NH3 or hydrocarbons, offers the advantage that there are no costs for the consumption of reducing agents. However, a decrease in effective N2O based on a catalytic decomposition, unlike the reduction of N2O or also NOX, with conventional decomposition catalysts can only be effectively achieved at temperatures above 400 ° C, preferably above 450 ° C.
[0008] [008] As particularly suitable for the catalytic decomposition of N2O in N2 and in O2 in turn arise the catalysts of zeolites loaded with transition metals (US-A-5,171,553).
[0009] [009] The iron-charged zeolite catalysts (eg EP-A-955,080 or WO-A-99 / 34,901) are described as particularly advantageous. The activity of zeolite catalysts loaded with iron for the decomposition of N2O in this case by simultaneous presence of NOX is significantly increased, as scientifically disclosed for example by Kӧgel et al. in Catalysis Communications 2 (2001), 273-276 or by Perez-ramirez et al. in the Journal of Catalysis 208 (2003), 211-223. This property seems to coincide only with iron doped zeolites. Zeolites doped with other transition metals such as copper or cobalt do not exhibit this behavior.
[0010] [010] In many cases the decomposition of N2O is even inhibited by the presence of NOX, as is known eg. Applied Catalysis B: Environmental 9 (1996), 25-64 [Chap. 5.1], by Applied Catalysis B: Environmental 12 (1997), 277286, as well as by Catalysis Today 35 (1997), 113-120. This applies for example to catalysts containing Cu, Co and Rh, which in the absence of NOX have a very high activity for the decomposition of N2O, however in the presence of NOX they have a significantly reduced activity. Catalysts of this nature will hereinafter be referred to as "sensitive to NOX".
[0011] [011] In addition to the catalysts and processes for reducing NOX and decomposing N2O mentioned above, combined processes for the elimination of NOX and N2O are also described in the patent literature. In this case, for example, processes based on a catalytic reduction of NOX with NH3 (in a DeNOX step) and in a catalytic decomposition of N2O in N2 and in O2 through zeolite catalysts containing iron (in a DeN2O step).
[0012] [012] Thus WO-A-01 / 51,182 for example describes a process for the elimination of NOX and N2O from the residual gas of nitric acid production, in which the residual gas to be purified is first conducted through a DeNOX step and subsequently through a DeN2O step with zeolite catalysts loaded with iron. In the suggested DeNOX step, the NOX content is reduced in order to regulate an optimal NOX / N2O ratio from 0.001 to 0.5, which leads to an accelerated N2O decomposition in the subsequent DeN2O step. Details for the development of this process are not disclosed.
[0013] [013] The sequence of process steps described in WO-A-01 / 51,182 from the point of view of the process technique is very advantageous, considering that the process is located in the residual gas of nitric acid production, between the absorption tower and the waste gas turbine in an ascending temperature profile; that is, the residual gas before entering the DeNOX stage has a reduced inlet temperature, which is <400 ° C, preferably <350 ° C, so that classic DeNOX catalysts based on V2O5-TiO2 can also be used . Subsequently, after the DeNOX stage before entering the DeN2O stage, a (single) heating of the residual gas is carried out in order to reach a temperature between 350 ° C and 500 ° C, so that an efficient catalytic decomposition of N2O is possible . Subsequently, the waste gas is sent to a waste gas turbine, in which, with the relaxation and cooling of the waste gas, a recovery of the thermal content of the waste gas is carried out.
[0014] [014] It is also possible to reverse the two process steps, that is, in a sequence, in which the decomposition of N2O is first envisaged and subsequently the decomposition of NOX, as disclosed in WO-A-97 / 10,042, in WO-A-01 / 51,181, WO-A-03 / 105,998 and WO-A-2006 / 119,870. WO-A-01 / 51,181, in addition to the process, also describes a device for carrying it out. This is characterized by a sequence of two subsequent catalyst beds, of which at least one is traversed radially by the gas and in which, if necessary, between the catalyst beds there is a device for introducing a gas reducing agent into the gas stream that leaves the first catalyst bed. In the case of these processes, the residual gas usually at a temperature <500 ° C is conducted through two reaction zones containing zeolite catalysts loaded with iron, which can be spatially separated in relation to each other or connected in relation to each other. In this case, N2O decomposition is carried out in the first DeN2O step with a non-reduced NOX content, that is, with the full use of the NOX co-catalytic effect on N2O decomposition and, subsequently, after the intermediate addition of ammonia, catalytic reduction of NOX. Considering that the reduction of NOX should preferably be carried out at the same temperature as the decomposition of N2O, in the DeNOX stage, Fe zeolite catalysts are also used, which unlike the classic SCR catalysts, such as for example. catalysts based on V2O5-TiO2, can also be operated at temperatures above> 400 ° C. In this case, intermediate cooling of the process gas is not necessary.
[0015] [015] Finally from JP-A-06 / 126,177, the combined elimination of NOX and N2O is known based on a catalytic reduction of NOX with NH3 (in a DeNOX step) and a catalytic decomposition of N2O into N2 and O2 (in a DeN2O step). According to that document, the sequence of steps can be arbitrary. For the decomposition of N2O, a carrier catalyst is suggested, which contains 0.001% by weight to 2% by weight of metallic platinum or rhodium or metallic rhodium and copper. In addition to these metals, iridium, ruthenium, iron, cobalt and nickel are also suggested. As substrates are mentioned aluminum oxide, silicon dioxide and zirconium dioxide as well as zeolites. Details for the selection of NOX reduction catalysts are not disclosed.
[0016] [016] Chemical reduction of NOX and parallel N2O has also been described. In this case it is known that the reduction of NOX occurs significantly more quickly than the reduction of N2O. In the case of these reduction processes for the reduction of NOX, a reduction gas containing nitrogen, for example ammonia, is usually used, while for the reduction of N2O, the same reduction gas is usually used, such as ammonia, but also hydrogen, a hydrocarbon. or carbon monoxide. Examples of processes of said nature can be found in WO-A-03 / 84,646 and US-A-4,571,326. The process according to USA-4,571,326 can also be carried out on one or a sequence of several catalysts. Due to the more accelerated reduction of NOX in the case of the use of a catalyst bed, two zones are formed, in which in the first zone NOx is essentially reduced and in the subsequent zone and directly connected to it, essentially N2O is reduced. This variant is represented by eg. in Figure 4 of US-A-4,571,329. In Figure 5 of US-A-4,571,329, a sequence of two catalyst beds is shown; these border directly with each other and form a zone, in which essentially NOx is reduced, followed by a zone, in which essentially N2O is reduced. As catalysts for the reduction of N2O, zeolites doped with selected iron or hydrogen are used.
[0017] [017] US-A-2002/0127163 describes a process for the selective catalytic reduction of N2O with ammonia. As catalysts, zeolites are used, which are preferably doped with metals. This reduction process can be combined with a NOX reduction. In Figure 10 of said document it is disclosed, that the processes of said nature can be carried out in one or in a sequence of catalyst beds. Subsequently, a simultaneous reduction of NOX and N2O can be carried out, as well as a first reduction of N2O followed by a reduction of NOX. For the catalytic reduction of N2O, a minimum amount of 0.5 mol of ammonia per mol of N2O is required. According to the description, the sequence of the reduction steps is controlled by the selection of the catalysts. A catalytic decomposition of N2O into nitrogen and oxygen is expressly not the subject of the disclosed invention.
[0018] [018] Reactors are known from the patent literature for different gas phase reactions, which comprise a sequence of at least two catalyst beds.
[0019] [019] US-A-2,475,855 describes a reactor for endothermic or exothermic catalytic reactions, within which are several radial catalyst beds. These are arranged separately from each other and axially present a tube, in which the reagents are fed into the catalyst through it radially. Reverse flow direction is also possible. The reactor is used for example during the catalytic cracking of hydrogen.
[0020] [020] US-A-4,372,920 describes a reactor for homogeneous catalytic gas phase reactions, within which there are also several radial catalyst beds. These are arranged separately from each other and axially also have a tube. The reactants pass through axially parts of the individual catalyst beds and radially through other parts of said catalysts. The reactor can be used for example for the synthesis of ammonia or methanol.
[0021] [021] EP-A-1,022,056 describes a reactor for the treatment of fluids, which comprises two beds that directly border each other with adsorption agents or catalysts in a container. The beds are made up of granulates of different granulometries, in which the lower bed has the largest granulometry. Among these is a perforated metal plate, whose perforations have a diameter, which is larger than the diameter of the grains of the upper bed and smaller than the diameter of the lower bed. The reactor can be used for filtration, purification, separation and catalytic conversion of fluids.
[0022] [022] US-A-3,733,181 describes a reactor for the catalytic reduction of nitric oxides and for the catalytic oxidation of hydrogen and carbon monoxide in waste gases. The reactor comprises a combination of two concentric beds of catalysts for the two reactions, through which the residual gas is conducted. Air is added between the two beds to the residual gas to be treated.
[0023] [023] EP-A-967,006 has a device for performing catalytic reactions of a fluid in a gas phase. This in a reactor comprises an arrangement of two catalyst beds, which directly border each other, respectively are essentially developed in a cylindrical shape and of which one is radially traversed and the other is axially traversed. This device can be used for example for the dephosphorization of natural gas.
[0024] [024] So far in commercial processes for NOX reduction and N2O decomposition combined in gases in the low to medium temperature range of approximately 200 ° C to 600 ° C, essentially doped zeolites with iron are used. As described above, catalysts of said nature are particularly characterized by a very high activity for the reduction of NOX by means of ammonia and by a high activity for the decomposition of N2O, which in the presence of NOX is significantly increased.
[0025] [025] Other catalysts for the decomposition of N2O, which are deactivated due to the simultaneous presence of NOX, in industrial practice, that is to say in gases containing NOX as well as containing N2O, can only be used under specific conditions. It would be desirable that the spectrum of application of catalysts of the said nature could be broadened, so that these catalysts could also be used in the elimination of nitric oxides from waste gases.
[0026] [026] Based on the information available so far regarding catalysts other than iron doped zeolites, which could be used for the catalytic decomposition of N2O, in the case of these other catalysts a combined process for the elimination of oxides would have to be envisaged. nitric oxides, in which in a first step a reduction of NOX would be carried out as far as possible comprehensive eg with ammonia and in a subsequent step the remaining N2O would be decomposed or reduced. A more or less complete elimination of NOX of said nature in a first step could be carried out by adding relatively large amounts of ammonia. However in this case, in the case of the use of classic SCR catalysts, e.g. those based on V2O5-TiO2, there is a danger that in the case of limited amounts of catalyst it will not react the total amount of ammonia added with NOX and therefore result in an undesired leakage of ammonia. This in the case of combined NOX reduction and N2O decomposition is problematic, considering that ammonia in this case enters the subsequent DeN2O stage and in the case of the use of zeolites not doped with transition metals it is at least partially oxidized to form NOX , it means NO and NO2. This in turn leads to partial inhibition or deactivation of the DeN2O catalyst.
[0027] [027] Furthermore, it is known that classic SCR catalysts can generally only be used at temperatures up to 400 ° C. In order to avoid a staggered heating of the gas flow to be treated and to allow a simple development at the equipment level, the two nitric oxide decomposition steps, that is, the DeNOX step and the DeN2O step, must be operated at approximately equal temperatures.
[0028] [028] Therefore, the present invention aims to disclose a device and a process for the broadest possible elimination of N2O and NOX in gases, in which a combination of selected DeNOX catalysts with catalysts hitherto unused or used is used. only used to a limited extent for catalytic decomposition of N2O. In this case, catalysts should be used in particular to reduce NOX or to decompose N2O, which are characterized by very high catalytic efficiency.
[0029] [029] In addition, the present invention aims to disclose a device and a process which can be operated in a simple and economical way.
[0030] [030] Surprisingly it was found that the combination of zeolites selected in the DeNOX stage with catalysts selected in the DeN2O stage allows a simple and very economical elimination of nitric oxides in gases.
[0031] [031] The zeolite catalysts selected for the DeNOX step due to their high activity in the temperature range of approximately 350 ° C to 600 ° C can be used without problems and are combined with the DeN2O catalysts, which are active in the same range of temperatures.
[0032] [032] The use of transition metal doped zeolites according to the present invention as DeNOX catalysts compared to conventional SCR catalysts, such as e.g. based on V2O5-WO3 / TiO2 or Pt / Al2O3, it presents several advantages.
[0033] [033] On the one hand, said zeolites in the medium temperature range are highly active and selective, whereas conventional V2O5-WO3 / TiO2 catalysts can only be used at temperatures up to 400 ° C. Therefore, said zeolites allow the combination with DeN2O catalysts, which are highly active in the average temperature range.
[0034] [034] Another decisive advantage of zeolites doped with transition metals as DeNOX catalysts compared to conventional SCR catalysts is their behavior in case of reducing agent overdose.
[0035] [035] As mentioned above, an overdose of the reducing agent of the said nature, that is to say, an over-stoichiometric addition of NH3 in comparison with the reduction stoichiometry - e.g. the reaction of NOX with NH3, which in a known way occurs with a molar ratio of 1: 1 - is very advantageous, to achieve a comprehensive reduction of NOX as much as possible. While in the case of conventional SCR catalysts the excess dosed ammonia glides comprehensively through the catalyst bed and penetrates the subsequent DeN2O catalyst, where it is at least partially oxidized to form NOX, in the case of the use of a zeolite catalyst doped with transition metals according to the present invention there is no leakage of NH3 of said nature. The excess NH3 dosed, which neutralizes with NOX, in these catalysts is oxidized by O2 and / or N2O selectively N2 and H2O also present in the residual gas. Thus, in the case of a relatively small volume of catalyst in the DeNOX step, a complete reduction of NOX can be achieved, so that in the subsequent DeN2O step, NOX-sensitive catalysts can be used for the decomposition of N2O.
[0036] [036] A complete reduction of NOX without leakage of NH3 in the case of conventional SCR catalysts, if it were even possible, could only be achieved in the case of an enormous dimensioning of the catalyst bed. However, this principle in comparison with the process according to the present invention is not economical.
[0037] [037] Another advantage in the case of the use of transition metal doped zeolite catalysts in the DeNOX stage is that, in addition to the NOX reduction, they simultaneously catalyze the decomposition of N2O, so that in the DeNOX stage, a certain portion of N2O. Surprisingly and positively this effect, particularly in the case of the use of iron doped zeolite catalysts in combination with NOX-sensitive catalysts in the DeN2O stage, acts in such a way that the decomposition of N2O above the two reaction steps only shows a reduced dependence on the content NOX at the exit or entrance of the DeN2O stage (compare Figure 11).
[0038] [038] DeN2O catalysts sensitive to NOX in the context of this application should be understood as DeN2O catalysts, in which case the catalytic decomposition of N2O is significantly impaired by the simultaneous presence of NOX in the gas stream to be treated, that is, it is significantly reduced by equal rest conditions. In this case, within the scope of the present application, these are NOX-sensitive DeN2O catalysts, when the temperature, at which in the conditions of Experiment 5 described below (NOX content = 1000 ppm) a 50% N2O decomposition is achieved, is at least minus 10 K higher than the temperature for 50% N2O decomposition under the conditions of Experiment 4 described below (NOX content = 0 ppm).
[0039] [039] In general terms, the problems mentioned above are solved through the device described below and the process described below.
[0040] A) um recipiente (1) e, dispostas neste; B) duas etapas de reação subsequentes para a eliminação de NOX (etapa DeNOX) por redução de NOX com um agente de redução contendo nitrogênio, e, subsequentemente, para a eliminação de N2O por decomposição catalítica de N2O em N2 e em O2 (etapa DeN2O) , as quais apresentam um ou vários leitos de catalisador (7, 8) respectivamente e as quais são atravessadas pelo gás a purificar, em que; C) pelo menos um leito de catalisador da etapa DeNOX (7) contém um catalisador para a redução de NOX com agentes de redução contendo nitrogênio, o qual contém zeólitos dopados com metais de transição, incluindo lantanídeos; D) pelo menos um leito de catalisador da etapa DeN2O (8) contém um catalisador para a decomposição de N2O em N2 e em O2, o qual contém um ou vários compostos catalíticos ativos de elementos selecionados dos grupos de 5 a 11 da Tabela Periódica dos Elementos, excetuando os zeólitos dopados com ferro, e; E) antes da etapa DeNOX (7) estar previsto um dispositivo para a introdução do agente de redução contendo nitrogênio no fluxo de gás contendo o NOX e o N2O. [040] The present invention relates to a device for reducing the content of NOX and N2O in gases, particularly process gases and waste gases, characterized by comprising: A) a container (1) and, arranged therein; B) two subsequent reaction steps for the elimination of NOX (DeNOX step) by NOX reduction with a nitrogen-containing reducing agent, and subsequently for the elimination of N2O by catalytic decomposition of N2O into N2 and O2 (DeN2O step ), which have one or more catalyst beds (7, 8) respectively and which are crossed by the gas to be purified, in which; C) at least one catalyst bed from the DeNOX step (7) contains a catalyst for the reduction of NOX with nitrogen-containing reducing agents, which contains zeolites doped with transition metals, including lanthanides; D) at least one catalyst bed from the DeN2O step (8) contains a catalyst for the decomposition of N2O into N2 and O2, which contains one or more active catalytic compounds from elements selected from groups 5 to 11 of the Periodic Table of Elements, except for iron doped zeolites, and; E) before the DeNOX step (7) a device is provided for the introduction of the nitrogen-containing reducing agent in the gas stream containing NOX and N2O.
[0041] [041] The device according to the present invention comprises a container A), in which the two reaction steps with the catalyst beds are arranged. In this case, it can be a conventional pressure vessel, which can be produced, for example, in steel. The container is provided with inlet and outlet holes for the gas to be purified, for the purified gas and possibly for auxiliary agents to be introduced into the container, such as the NOX reducing agent. In addition, the container may be provided with conventional auxiliary devices, such as inspection holes, flanges, necks or removable covers.
[0042] [042] The device according to the present invention is characterized by having at least two reaction steps, which contain selected catalysts. The catalyst beds of these reaction steps can directly border each other or be arranged at a distance from each other, for example through a free spatial section, which may eventually have flow-conducting elements or auxiliary construction elements. This means that the gas passing through these beds passes from one bed to the other, without requiring any devices for modifying the composition of the gas, such as mixing devices or heating devices, between these catalyst beds. Optionally, between the catalyst beds, flow-conducting or support elements of the catalyst beds or stabilizing elements, such as perforated metal sheets or metal mesh bottoms, may be provided.
[0043] [043] Before the DeNOX stage, a device E) is provided for the introduction of a NOX reducing agent in the gas flow containing NOX and N2O. These prior to the introduction of the gas flow to be purified can end up in the reactor in the gas flow duct or also in the reactor before the introduction of the gas flow in the first catalyst bed. In the case of device E) for the introduction of a NOX reducing agent in the gas stream containing NOX and N2O, it can be a simple tube, which at the end on the side of the reactor preferably has one or more valves. The tube can flow directly into the supply tube for the gas containing NOX and N2O.
[0044] [044] According to a preferred embodiment the device according to the present invention contains at least one measurement point F) for the flow or quantity of gas and / or at least one measurement point G) for the determination of the concentration of NOX (or the respective individual components) in the gas. The measuring point F) is usually arranged before the DeNOX stage. The measuring point G) for the NOX concentration contained in the gas is found before the DeNOX stage, after the DeNOX stage and before the DeN2O stage or after the DeN2O stage.
[0045] [045] According to a more preferred embodiment of the device according to the present invention, measuring point G) is arranged after the DeN2O step or more preferably before the DeNOX step in the gas supply tube for nitric oxide gas and purifying.
[0046] [046] From the value of the measuring point F) and the value of the measuring point G), the required amount of reducing agent for the DeNOX step can be determined and measured.
[0047] [047] According to a preferred embodiment of the device according to the present invention, the measuring points F) and G) for determining the quantity of reducing agent fed through a control or regulation unit H) are coupled with a regulating device I) for example with a control or adjustable valve, with which the flow or quantity of the reducing agent that passes through the device E) can be regulated. The control or control unit H) for this purpose provides a reference value, with which the control device I) can be actuated properly. Alternatively to the gas containing nitric oxide, a mixture of inert gas, for example nitrogen, and gas reducing agent can also be added; in this case the regulation of the quantity of reducing agent fed can be carried out by varying the portion of inert gas. Dosages of said nature are known to the person skilled in the art.
[0048] [048] The layout, design and passage through the catalyst beds can be carried out in different ways.
[0049] [049] Catalyst beds often have a geometric shape, which in one dimension is smaller than in the other two dimensions. In this case, the two largest dimensions define a surface, with which it is possible to describe the arrangement of the catalyst bed in the reactor. In the device according to the present invention, the catalyst beds in relation to these surfaces can be positioned in parallel or perpendicular to the main axis of the container; combinations of catalyst beds positioned and parallel and perpendicular or perpendicular and parallel are also possible. The gas passes through the catalyst beds along the smallest dimension, that is to say transversal to the surface, which is defined by the two largest dimensions. A flow of said nature is hereinafter referred to as "lateral flow".
[0050] [050] According to the simplest embodiment of the device according to the present invention, the catalyst beds of the two reaction steps have the form of two or more overlapping horizontal layers, possibly separated by a hollow space. The gas can, for example, be introduced from above into the first catalyst arrangement for the reduction of NOX, passing through it in the downward direction and subsequently eventually first into an empty intermediate space and subsequently into additional catalyst arrangements for the decomposition of the N2O. The purified gas leaves the last catalyst array on the underside to the reactor outlet zone and leaves the reactor. An embodiment of said nature of the device according to the present invention is shown in Figures 3 and 4.
[0051] [051] According to a preferred embodiment of the device according to the present invention, at least one catalyst bed of one reaction step, preferably at least one catalyst bed of the two reaction steps, is developed or is disposed of. shape that is laterally, particularly radially crossed by the gas to be purified. Beds that are traversed laterally or radially compared to beds that are axially traversed, result in a significantly lower pressure loss, considering that due to a larger surface of affluence for the gas at the same spatial speed, they allow the regulation of reduced linear velocities. In the case of the use of radially traversed catalyst beds, it must be taken into account that through properly arranged flow-conducting elements, for example metal plates arranged on the front sides of the radial beds, the gas path is predetermined, which is also radially traversed by the volume filled by the catalyst and cannot escape on the front sides.
[0052] [052] According to a preferred embodiment, the radial beds of one or more preferably of the two reaction steps have the shape of a hollow cylinder. In the latter case, the hollow cylinders are preferably concentrated concentrically within each other, in which the hollow cylinders come into contact with the outer or inner cladding surface or between these there is an empty space. In the case of this embodiment, the inner hollow cylinder in the center has a hollow space, through which gas can be introduced into the catalyst or evacuated from the catalyst. According to a variant, the gas can be introduced axially and flows radially outwards; first through the inner hollow cylinder with the NOX reduction catalyst and subsequently through the outer hollow cylinder with the catalyst for the decomposition of N2O or subsequently through a hollow space and subsequently through the outer hollow cylinder with the catalyst for the decomposition of N2O . The residual gas subsequently purified through the outer casing of the outer hollow cylinder flows into the reactor outlet zone and subsequently out of the reactor. An embodiment of said nature of the device according to the present invention is shown in Figure 1.
[0053] [053] According to another operational method, a device of the said nature can also be traversed in the reverse direction, in which the outer hollow cylinder is formed by the NOX reduction catalyst and the inner cylinder is formed by the catalyst for the decomposition of NOX. N2O. An embodiment of said nature of the device according to the present invention is shown in Figure 2.
[0054] [054] Other embodiments of the reactor according to the present invention are shown in Figures 5 and 6.
[0055] [055] Before entering the gas in the first catalyst bed to the gas containing NOX and N2O, at least one nitrogen-containing reducing agent is added for NOX reduction. The type of introduction of the gas flow reduction means (s) to be treated within the scope of the present invention can be freely chosen. The reducing agent can be introduced in the form of a gas or also a liquid or an aqueous solution, which evaporates in the gas stream to be treated. The supply of the gas stream to be treated is carried out using a suitable insertion device, such as eg. through a corresponding pressure valve or correspondingly developed valves. In the case of the use of different reducing agents, feeding and introduction into the gas to be purified can be carried out separately or jointly.
[0056] [056] To promote the mixing of the gas stream to be purified with the fed reducing agent and to achieve a homogeneous distribution of the reducing agent in the gas flow before entering the DeNOX step, before entering the DeNOX step, a mixer is provided, which is preferably arranged in the tube for the gas flow to be treated.
[0057] [057] The mixer within the scope of the present invention can be freely chosen, for example as a static mixer with corresponding inserts or as a dynamic mixer. It is also considered to be the simplest form of a pipe preferably turbulently traversed as a mixer within the scope of the present invention.
[0058] a) uma atividade catalítica elevada e uma selectividade para a conversão química de NOX com agentes de redução contendo nitrogêneo em N2 e H2O; b) uma atividade catalítica significativa para a oxidação seletiva de agente de redução doseado sobreestequiometricamente com O2 e/ou N2O em N2 e H2O; c) e tanto quanto possível uma atividade significativa para a decomposição de N2O em N2 e O2. [058] In the DeNOX stage, selected DeNOX catalysts are used, which in the temperature range between 350 ° C and 600 ° C, particularly between 400 ° C and 600 ° C, have the following properties: a) a high catalytic activity and a selectivity for the chemical conversion of NOX with reducing agents containing nitrogen into N2 and H2O; b) a significant catalytic activity for the selective oxidation of reducing agent dosed over stoichiometrically with O2 and / or N2O in N2 and H2O; c) and as much as possible a significant activity for the decomposition of N2O into N2 and O2.
[0059] [059] In the case of DeNOX catalysts these are catalysts, which contain zeolites doped with transition metals, including lanthanides, preferably with cobalt, particularly with copper and more preferably zeolites doped with iron. Other possible transition metals, which preferably arise together with cobalt, copper and / or iron in zeolites, are manganese, vanadium, chromium or nickel.
[0060] [060] In the case of zeolites it is preferable to deal with "high silica" zeolites, which have a high hydrothermal resistance.
[0061] [061] Preferably the zeolites are selected from the group of types MFI, BEA, FER, MOR and MEL or respective mixtures, preferably of the type BEA or MFI, more preferably it is a ZSM-5 zeolite.
[0062] [062] The exact indications regarding the construction or structure of the types of zeolites used in accordance with the present invention are given in the Atlas of Zeolite Stucture Types, Elsevier, 4th revised edition, 1996, to which reference is explicitly made.
[0063] [063] Furthermore, zeolites called "vaporized" are preferably used, that is to say zeolites in which after a hydrothermal treatment a part of the aluminum atoms has been moved to intermediate spaces. Zeolites of said nature and their production are known to the person skilled in the art.
[0064] [064] The content of transition metals in zeolites, in relation to the mass of zeolites, may fluctuate in additional zones, for example being up to 25%, however preferably from 0.1% to 10% and particularly from 2% to 7 %.
[0065] [065] The doping of zeolites with transition metals can be carried out, for example, from the H form or preferably from the NH4 form of the zeolites by ion exchange (in aqueous phase or by reaction in solid state) with corresponding salts of the transition metals . The catalyst powders usually obtained are calcined in an air chamber oven at temperatures between 400 ° C and 650 ° C. After calcination, the zeolites containing transition metals are intensively washed in distilled water and dried after zeolite filtration. This and other corresponding methods for loading or doping transition metals are known to the person skilled in the art. Finally, the zeolites containing transition metals obtained in this way are displaced and mixed with adjuvant agents suitable for plasticization and with binding agents, such as for example aluminosilicate or boemite, and extruded for example to form cylindrical catalyst bodies.
[0066] [066] The DeNOX catalyst can be presented as a molded body of any size and geometry, preferably with geometries, which have a large surface to volume ratio and during which a reduced pressure loss is generated as much as possible. Typical are all geometries known in catalysis, such as e.g. cylinders, hollow cylinders, multiple orifice cylinders, rings, granulate fractionation devices, trifoliate or honeycomb structures. The size of the particles or molded catalyst bodies used can vary widely. These typically have an equivalent diameter in the range of 1 mm to 10 mm. Equivalent diameters from 2 mm to 5 mm are preferred. In this case, the equivalent diameter is the diameter of a sphere of equal volume.
[0067] [067] After the NOX reduction, the gas to be treated is directed directly to the DeN2O stage, which contains one or more catalyst beds with catalyst for the decomposition of N2O into nitrogen and oxygen.
[0068] [068] In accordance with the present invention in the DeN2O step (s) catalysts are used, which in the temperature range between 350 ° C and 600 ° C have a high catalytic activity for the decomposition of N2O into N2 and in O2. Particularly, catalysts are used, whose activity for the decomposition of N2O is significantly limited by the presence of NOX (NOX-sensitive DeN2O catalysts).
[0069] [069] These catalysts contain one or more active catalytic compounds from elements selected from groups 5 to 11 of the Periodic Table of the Elements. Particularly preferred are compounds of elements from groups 9 to 11 of the Periodic Table of Elements. Among these, the compounds of the elements Co, Pt, Pd, Ir, Rh, Ni and / or Cu, preferably Co, Rh, Ni and / or Cu and, in this case, particularly Co or Rh, are preferred. Iron-doped zeolites are excluded from the catalysts used in the DeN2O stage. In the case of this group of catalysts, these are not "NOX sensitive" DeN2O catalysts.
[0070] [070] In the case of the active catalytic compounds themselves, it can be metallic and / or oxidic compounds, in which the latter can be present both as single oxides and also as mixed binary, ternary or polar oxides with different types of structure, such as like e.g. perovskites or spinel. These are described e.g. in Catalysis Letters 35 (1995), 372-382, Applied Catalysis 73 (1991), 165-171, Catal. Rev.-Sci. Eng .; 34 (4), 409-425 (1992) or in Actes du 2ième Congrès International sur la Catalyse 97 (1961), 1937-1953. Mixtures of different active catalytic compounds can also be used.
[0071] [071] Examples of more preferred active catalytic compounds include metal rhodium, rhodium oxides, such as RhO2 or RhO3, CoO, Co2O3, Co-containing spinels, such as Co3O4, CuxCo3-xO4, or Co-containing perovskites, such as LaCoO3, or perovskites containing Co substituted at sites A and B.
[0072] [072] The active catalytic compounds can be contained in the catalysts in pure form or be applied on suitable substrates or mixed with them.
[0073] [073] In the first case, these are called complete catalysts, which, in addition to the active compounds, may also contain additives known to the person skilled in the art, such as binding agents or other production-related additives such as plasticizers, pore-forming agents , fiber reinforcing agents or auxiliary compaction agents. Methods for producing catalysts of this nature are known to the person skilled in the art. In the case of "carrier catalysts" the active catalytic compounds are applied on the substrate. Therefore, the active catalytic compound is subject to dispersion and stabilization both against mechanical loads and also against thermal loads. Methods for producing such catalysts are also known to the person skilled in the art.
[0074] [074] In the case of substrates it is preferably refractory oxides, such as SiO2, TiO2 or Al2O3 or mixtures of two or more of these or materials, which in themselves have a certain catalytic activity for the decomposition of N2O, such as for example. MgO, zeolites, hydrotalcites or mixtures of two or more of these.
[0075] [075] Preferably DeN2O catalysts are used, which contain no or almost no zeolites, preferably less than 15% by weight in zeolites, particularly less than 5% by weight in zeolites.
[0076] [076] Preferred substrates for compounds containing Rh are SiO2, TiO2, Al2O3, hydrotalcites or zeolites, e.g. of the MFI type. These are described e.g. in Chemical Engineering and Technology 24 (2001), 281-285, or in Catalysis Today 35 (1997), 113-120.
[0077] [077] The most preferred substrates for compounds containing Rh are SiO2, TiO2 and hydrotalcites. The Rh content of these catalysts is preferably 0.1% by weight to 10% by weight, preferably 0.5% by weight to 5% by weight. More preferably, Rh-containing catalysts also contain CeO2. The CeO2 portion is preferably 5 wt% to 50 wt%, particularly 10 wt% to 30 wt%.
[0078] [078] Preferred carriers for compounds containing Co are zeolites or carriers containing magnesium oxide. In the case of zeolites, Si structure groups such as MFI, BEA, FER, MEL or MOR are more preferred. The production of co-doped zeolites of said nature is known to the person skilled in the art. In the case of decesium magnesium carriers it may be pure MgO or compounds containing MgO such as e.g. hydrotalcites. These catalysts are described e.g. in Appl. Catal. B: Environmental 7 (1996), 397-406 or in Appl. Catal. B: Environmental 13 (1997), 69-79.
[0079] [079] Catalysts are more preferred, which essentially consist of at least one oxide magnesium compound and at least one oxide cobalt compound, in which the content of oxide cobalt compounds is between 0.1% by weight and 50% by weight and the content of oxide magnesium compounds is between 50% by weight and 99.9% by weight, respectively with respect to the total mass of catalyst and in which at least 30% by weight of the Co atoms contained in the catalyst are present in the trivalent state. Catalysts of said nature and their production are described in EP 1 257 347 B1.
[0080] [080] In addition, catalysts with a carrier, which consists of at least 50% by weight of MgO or a mixed oxide, which consists of at least 50% by weight of MgO, and a functional waxy oxide layer is applied to the carrier. Such catalysts and their production are described in DE 10 2007 038 711 A1.
[0081] [081] The DeN2O catalyst can be presented as a molded body of any size and geometry, preferably with geometries, which have a large surface to volume ratio and during which a reduced pressure loss is generated as much as possible. Typical are all geometries known in catalysis, such as e.g. cylinders, hollow cylinders, multiple orifice cylinders, rings, granulate fractionation devices, trifoliate or honeycomb structures. The size of the particles or molded catalyst bodies used can vary widely. These typically have an equivalent diameter in the range of 1 mm to 10 mm. Equivalent diameters from 1 mm to 4 mm are preferred. In this case, the equivalent diameter is the diameter of a sphere of equal volume.
[0082] a) adição de agente de redução contendo nitrogênio a um fluxo de gás contendo N2O e NOX para a redução do NOX; b) condução do fluxo de gás contendo N2O, NOX e agente de redução através de pelo menos um leito de catalisador de uma etapa DeNOX (7), o qual contém um catalisador para a redução do NOX através do agente de redução, o qual contém zeólitos dopados com metais de transição, incluindo lantanídeos, e; c) condução do fluxo de gás que sai da etapa DeNOX através de pelo menos um leito de catalisador de uma etapa DeN2O (8), o qual contém um catalisador para a decomposição do N2O em N2 e em O2, o qual é selecionado do grupo dos catalisadores contendo um ou vários compostos catalíticos ativos de elementos selecionados dos grupos de 5 a 11 da Tabela Periódica dos Elementos com exceção dos zeólitos dopados com ferro. [082] The present invention also relates to a process for reducing the content of NOX and N2O in gases, particularly in process gases or waste gases, characterized by comprising the following measures: a) adding nitrogen-containing reducing agent to a gas stream containing N2O and NOX to reduce NOX; b) conducting the gas flow containing N2O, NOX and reducing agent through at least one catalyst bed of a DeNOX step (7), which contains a catalyst for the reduction of NOX through the reducing agent, which contains zeolites doped with transition metals, including lanthanides, and; c) conduction of the gas flow leaving the DeNOX stage through at least one catalyst bed of a DeN2O stage (8), which contains a catalyst for the decomposition of N2O into N2 and O2, which is selected from the group of catalysts containing one or more active catalytic compounds of elements selected from groups 5 to 11 of the Periodic Table of the Elements with the exception of zeolites doped with iron.
[0083] [083] In the zone before the gas enters the reactor until directly before the catalyst bed of the (first) DeNOX stage the gas containing NOX and N2O is mixed with a NOX reducing agent containing nitrogen. In this case, it can be any nitrogen-containing reducing agent, which is known to the person skilled in the art and has a high activity for NOX reduction.
[0084] [084] Examples include azanes, hydroxyl derivatives of azanes such as amines, oximes, carbamates, urea or urea derivatives. Examples of azanes include hydrazine and more particularly ammonia. An example of a hydrophilic derivative of azanes is hydroxylamine. Examples of amines include primary aliphatic amines, such as methylamine. An example of carbamate is ammonium carbamate. Examples of urea derivatives are N, N'-substituted ureas, such as N, N'-dimethylurea. Ureas and urea derivatives are preferably used in the form of aqueous solutions.
[0085] [085] Most preferably ammonia is used as a reducing agent for NOX.
[0086] [086] The reducing agent is added in quantities, as required for the reduction of at least a part of NOX in the DeNOX step. In this case the degree of NOX decomposition in the process according to the present invention in relation to the NOX input concentration is usually greater than 70%, preferably greater than 80%, more preferably greater than 90%, particularly greater than 95%.
[0087] [087] When selecting the amount of reducing agent, it should be taken into account that it is completely or approximately completely converted in the DeNOX step, so that as much as possible, no leakage of the reducing agent from the DeNOX step to the step will result. DeN2O or a leak less than 25 ppmv, preferably less than 10 ppmv and particularly a leak less than 5 ppmv. The amounts of reducing agent required for this purpose vary depending on the type of reducing agent as well as the quantity and type of catalyst and the other operational parameters such as pressure and temperature.
[0088] [088] In the case of the use of ammonia as a reducing agent for NOx, an amount of NH3 is usually used, which in relation to the NH3 and NOX components at the entrance of the DeNOX step results in an NH3 / NOX molar ratio of 0.8 to 3, preferably from 1 to 2.5, more preferably from 1.2 to 2 and particularly from 1.3 to 1.8.
[0089] [089] The amount of NOX reducing agent can be determined and measured in different ways. For example, through the measuring point G) at the exit of the DeN2O step, the NOX content can be measured and through simple regulation, that is, through regulation unit H), controlling device I) for the dosing of the agent reduction, so that the desired NOX content (reference value) is set at the exit of the DeN2O step.
[0090] [090] Limitations are imposed on this regulation strategy in the process according to the present invention, namely whenever the NOX content in the DeNOX stage must be completely reduced, so that the measurement point G) at the exit of the DeN2O stage does not it provides any significant measured value and therefore any regulation value.
[0091] [091] Therefore, according to a preferred embodiment, the NOX content and the residual gas flow, that is, the quantity of which is measured before entering the DeNOX stage and in which from the values via a control unit H) with the indication of a suitable ratio of the amounts of reducing agent and NOX, the required amount of reducing agent is determined and the regulating device I) is adjusted accordingly.
[0092] [092] The appropriate ratio of the amounts of reducing agent and NOX can be determined by calibrating the device according to the present invention. The corresponding values for the molar ratio in the case of NH3 as a reducing agent are mentioned above. In the DeNOX stage, the temperature in the case of the process according to the present invention is usually between 300 ° C and 600 ° C, preferably between 350 ° C and 550 ° C and more preferably between 400 ° C and 550 ° C.
[0093] [093] The DeNOX step according to the present invention can be operated at normal pressure or preferably at overpressure. Typically the pressure in this stage is comprised between 1 absolute bars and 50 absolute bars, preferably between 1 absolute bars and 25 absolute bars, more preferably between 4 absolute bars and 15 absolute bars. In this case, a higher operating pressure in the DeNOX step reduces the amount of catalyst required for the NOX reduction. Higher pressure with the same operating parameters generally leads to a higher degree of NOX decomposition at the exit of the DeNOX step.
[0094] [094] The amount of catalyst in the DeNOx step has to be measured, so that with the corresponding addition of reducing agent, as mentioned above, the desired degree of NOX decomposition can be achieved and as much as possible without the occurrence of a leakage of reducing agent.
[0095] [095] In this case, the amount of catalyst varies depending on the operational parameters of the DeNOX step, such as the volumetric flow of the gas, the service pressure and the operating temperature. Typical spatial speeds in the DeNOX stage are between 5,000 h-1 and 200,000 h-1, preferably between 10,000 h-1 and 100,000 h-1 and, more preferably, between 20,000 h-1 and 60,000 h-1. In this case, within the scope of the present description for space velocity, the quotient of parts by volume of gas mixture (measured at 273.15 K and 1.01325 absolute bars) per hour in relation to a part by volume of catalyst must be understood. Therefore, the spatial speed can be regulated through the volumetric flow of the gas and / or through the amount of catalyst.
[0096] [096] In accordance with the present invention, the process parameters in the DeNOX stage, that is to say the spatial speed, temperature and pressure, within the above-mentioned zones are selected, so that in the case of a gas with a certain content NOX with a corresponding addition of NOX reducing agent at the exit of the DeN2O step results in a residual NOX content of less than 150 ppmv, preferably less than 100 ppmv, more preferably less than 50 ppmv, even more preferably less than 20 ppmv, particularly less than 10 ppmv and even more preferably less than 1 ppmv.
[0097] [097] In the DeN2O step, the temperature during the process according to the present invention is usually between 300 ° C and 600 ° C, preferably between 350 ° C and 550 ° C and more preferably between 400 ° C and 550 ° C. The temperature in the DeN2O step is generally selected, so that it does not differ by more than 50 ° C, preferably not more than 20 ° C, from the temperature in the DeNOX step. As temperature of each stage, the temperature of the gas flow directly at the entrance of the stage in question is considered.
[0098] [098] Also the DeN2O step according to the present invention can be operated at normal pressure or preferably at overpressure. Typically the pressure in this stage is comprised between 1 absolute bars and 50 absolute bars, preferably between 1 absolute bars and 25 absolute bars, more preferably between 4 absolute bars and 15 absolute bars. In this case, a higher operating pressure in the DeN2O step reduces the amount of catalyst required for the decomposition of N2O.
[0099] [099] The amount of catalyst in the DeN2O step has to be measured, so that the desired degree of N2O decomposition can be achieved.
[0100] [100] The reactor bed of the DeN2O stage is preferably filled with catalyst, so that - in relation to the incoming gas flow - a spatial speed between 2,000 h-1 and 50,000 h-1 results, preferably a space speed between 2,500 h-1 and 25,000 h-1 and, more preferably, a space speed between 3,000 h-1 and 20,000 h-1. The spatial velocity, as in the case of the described NOX reduction, can be regulated through the volumetric flow of the gas and / or through the amount of catalyst.
[0101] [101] In the process according to the present invention the degree of NOX reduction in the DeNOX step as well as the process parameters in the DeN2O step, that is to say the spatial speed, temperature and pressure, within the zones for these parameters of above mentioned processes are selected, so that for a gas with a certain N2O content at the entry of the DeN2O step, a reduction in the N2O content results to values below 100 ppmv, preferably below 50 ppmv, more preferably below 30 ppmv and , even more preferably, less than 15 ppmv. In total a comprehensive N2O decomposition should be performed.
[0102] [102] Figures 1 to 6 describe preferred embodiments of the device according to the present invention and the process according to the present invention.
[0103] [103] Figure 1 represents a device according to the present invention in longitudinal section, in which the two catalyst beds are developed in the form of two hollow cylinders placed inside each other. The reactor consists of a container (1), provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor through a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX gas reducing agent are homogeneously mixed with each other, abandons the latter. The inlet flow (5) is conducted from the mixer (4) to the inlet space (6) of the reactor and from there it passes through a bed of DeNOX catalyst (7) and subsequently a bed of DeN2O catalyst (8). These catalyst beds are arranged in a radial basket in the form of two beds placed within each other and form a hollow cylinder respectively. The inner lining surface of the outer hollow cylinder in this case directly borders the outer lining surface of the inner hollow cylinder. The inner hollow cylinder inside forms a hollow space, which forms the outlet space (9) for the purified gas (10). After passing through the outlet space (9), it leaves the reactor through the outlet (12). To guide the flow, the two catalyst beds (7, 8) on the respective upper side are provided with a gas-impermeable cover (13). The remaining walls (15) of the radial basket are permeable to gas and e.g. developed as a metallic mesh. The bottom side (14) of the radial basket supports the catalyst beds and is developed in a gas-impermeable manner, for example as a closed plate.
[0104] [104] Figure 2 represents a device according to the present invention in longitudinal section, in which the two catalyst beds are developed in the form of two hollow cylinders placed inside each other. The structure of this device is similar to the structure of the reactor according to Figure 1. However, in this case, the gas to be purified flows in the opposite direction from the inside out through the catalyst beds. The reactor in this case also consists of a container (1), which is provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor in a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX gas reducing agent are homogeneously mixed with each other, abandons the latter. The inlet flow (5) is conducted from the mixer (4) to the inlet space (6) of the reactor. This according to this embodiment ends in the inner hollow space of the hollow cylinder formed by the bed of internal catalyst. From the inlet space (6) the gas stream to be purified (5) passes through a bed of DeNOX catalyst (7) and subsequently a bed of DeN2O catalyst (8). These catalyst beds according to this embodiment are also arranged in a radial basket in the form of two beds placed within each other and form a hollow cylinder respectively. In this case the inner lining surface of the outer hollow cylinder in this case also directly borders the outer lining surface of the inner hollow cylinder. According to this embodiment, the gas to be purified passes through the two catalyst beds radially from the inside out. The outlet space (9) for the purified gas (10) in this case starts at the outer coating surface of the DeN2O catalyst bed (8). After passing through the outlet space (9) the purified gas (10) leaves the reactor through the outlet (12). To guide the flow, the two catalyst beds (7, 8) on the respective upper side in this case are also provided with a gas-impermeable cover (13); however, it must be provided with a hole in the center for the passage of the inlet flow (5). The remaining walls (15) of the radial basket are permeable to gas and e.g. developed as a metal mesh. The bottom side (14) of the radial basket must be developed in a gas-impermeable manner to ensure the desired passage of the catalyst beds.
[0105] [105] Figure 3 represents a device according to the present invention in longitudinal section, in which the two catalyst beds are first axially and subsequently radially traversed by the gas to be purified. The reactor consists of a container (1), provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor in a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX reducing agent are homogeneously mixed with one another, abandons the latter. The inlet flow (5) is conducted from the mixer (4) to the inlet space (6) of the reactor and from there it passes through a bed of DeNOX catalyst (7) in the axial direction, which is applied as a horizontal bed between two gas-permeable bottoms (15). After passing through the NOX catalyst bed (7), the purified NOX gas flows into the intermediate space (16), which flows into an internal hollow space (17), which is surrounded by a DeN2O catalyst bed (8) in cylindrical form. To guide the flow, the catalyst bed (8) on the respective upper side is provided with a gas-impermeable cover (13), which connects to the container wall (1). The gas to be purified flows from the hollow space (17) radially outwards through the DeN2O catalyst bed (8) and on the outer coating surface of the cylinder it exits to the outlet space (9) for the purified gas (10). After passing through the outlet space (9) the purified gas (10) leaves the reactor through the outlet (12). To ensure the desired passage through the catalyst bed (8), the bottom side (14) of the radial basket is developed in a gas-impermeable manner.
[0106] [106] Figure 4 represents a device according to the present invention in longitudinal section, in which the two catalyst beds are developed in the form of two horizontally arranged beds. The structure of this device is similar to the structure according to Figure 2. However, in this case, the gas to be purified flows axially through two subsequent catalyst beds (7, 8). The reactor in this case also consists of a container (1), provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor through a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX reducing agent are homogeneously mixed with one another, abandons the latter. The inlet flow (5) is directed from the mixer (4) to the inlet space (6) of the reactor and from there it passes through a bed of DeNOX catalyst (7) in the axial direction as well as a bed of DeN2O catalyst (8) directly subsequent, which are applied as horizontal beds between gas-permeable bottoms (15) respectively. The purified gas (10) exits from the bottom side of the DeN2O catalyst bed (8) to the outlet space (9). After passing through the outlet space (9) the purified gas (10) leaves the reactor through the outlet (12).
[0107] [107] Figure 5a represents a device according to the present invention in longitudinal section, in which the DeNOX catalyst bed (7) is present as a horizontal bed and several DeN2O catalyst beds (8) are present in the form of beds vertically arranged. The reactor consists of a container (1), provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor in a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX reducing agent are homogeneously mixed with one another, abandons the latter. The inlet flow (5) is directed from the mixer (4) to the inlet space (6) of the reactor and from there it passes through a bed of DeNOX catalyst (7) in the axial direction, which is supported or bounded by permeable bottoms to gas (15). After passing through the DeNOX catalyst bed (7), the purified NOX gas flows into an intermediate space (16) and from there through an arrangement (18) of several vertical DeN2O catalyst beds (8) not further detailed in the Figure 5a. The arrangement (18) has a rectangular cross section and is connected to the container lining (1) by means of fixing elements (19) on the upper side and on the lower side. The purified NOX gas flows from top to bottom through the arrangement (18), in which the N2O contained in the gas is decomposed into nitrogen and oxygen. The purified gas (10) exits the lower front side of the arrangement (18) to the outlet space (9) and exits the reactor through the outlet (12).
[0108] [108] In the upper part of Figure 5b, a section of the arrangement (18) is shown along line A. The arrangement (18) is inside the container (1) and forms a parallelepiped, which is surrounded by metal plates (20). The internal space of the parallelepiped is formed by a sequence of spatial sections (8, 9, 17) vertically arranged and which directly border each other. These spatial sections are bounded by gas-permeable walls (15) respectively, for example of metal mesh. In the case of spatial sections (8), in this case, there are several beds of DeN2O catalyst, which extend vertically inside the arrangement (18). In the case of space sections (9) these are outlet spaces for the purified gas (10). In the case of space sections (17) these are entry spaces for purified NOX gas.
[0109] [109] The bottom part of Figure 5b shows the arrangement (18) in longitudinal section, together with a flow profile for the gas. The purified NOX gas flows from the upper side of the arrangement (18) through the inlet spaces (17) to the DeN2O catalyst beds (8) which extend vertically and there is purified from N2O. Then the purified gas (10) flows into the outlet spaces (9) and subsequently leaves the reactor. To guide the flow on the upper front side of the arrangement (18), gas-impermeable metal plates (22) are provided, which only allow the purified NOX gas to enter the inlet spaces (17) and not on the front sides of the beds of DeN2O catalyst (8) or in the outlet spaces (9). To guide the flow on the lower front side of the arrangement (18), metal plates (23) are arranged, which only allow the purified gas (10) to escape through the outlet spaces (9) and not through the front sides of the beds of DeN2O catalyst (8) and inlet spaces (17).
[0110] [110] Figure 6a represents a device according to the present invention in longitudinal section, in which the two catalyst beds are developed in the form of several beds arranged vertically respectively. The structure of this device is similar to the structure of the reactor according to Figure 5a. However, in this case, the gas to be purified flows axially through two subsequent catalyst beds respectively and arranged vertically respectively (not further detailed in Figure 6a). The reactor in this case also consists of a container (1), provided with an inlet (11) and an outlet (12) for the gas. The gas containing nitric oxides and to be purified (2) together with a NOX reducing agent (3), for example ammonia, is fed to the reactor through a mixer (4) arranged at the inlet (11) through tubes not shown. The gas mixture as an inlet flow (5), in which the gas containing nitric oxides as well as the NOX reducing agent are homogeneously mixed with one another, abandons the latter. The inlet flow (5) is conducted from the mixer (4) to the inlet space (6) of the reactor and from there it passes through an arrangement (18) of various combinations not further detailed in Figure 6a DeNOX and DeN2O catalyst beds (7, 8). The arrangement (18) has a rectangular cross section and is connected to the container lining (1) by means of fixing elements (19) on the upper side and on the lower side. The gas to be purified flows from top to bottom through the arrangement (18), in which the nitric oxides contained in the gas are eliminated. The purified gas (10) exits the lower front side of the arrangement (18) to the outlet space (9) and exits the reactor through the outlet (12).
[0111] [111] Figure 6b shows a connection of the arrangement (18) in longitudinal section together with a flow profile for the gas. The gas to be purified flows from the upper side of the arrangement (18) through the inlet spaces (6) to the DeNOX catalyst beds (7) and is then purified from NOX. From the DeNOX catalyst bed (7) the gas flows directly to a DeN2O catalyst bed (8), where the remaining N2O in the gas is decomposed into nitrogen and oxygen. Then the purified gas (10) flows into the outlet spaces (9) and subsequently leaves the reactor. The catalyst beds (7, 8) are brought together to form pairs that directly border each other respectively, which extend vertically inside the arrangement (18) and whose longitudinal sides - through which the exchange is carried out gas - are directly in contact. For conducting the flow on the upper front side of the arrangement (18), gas-impermeable metal plates (22) are provided, which only allow the purified NOX gas to enter the inlet spaces (6) and not on the front sides of the beds catalyst (7, 8) or in the outlet spaces (9). For conducting the flow on the lower front side of the arrangement (18), gas-impermeable metal plates (23) are provided, which only allow the purified gas (10) to escape through the outlet spaces (9) and not through the sides of the catalyst beds (7, 8) and inlet spaces (6). The catalyst beds (7, 8) are laterally bounded by gas-permeable walls (15), which are developed for example as a metal mesh.
[0112] [112] In Figure 6c, an alternative arrangement connection (18) is shown in longitudinal section together with a flow profile for the gas. The gas to be purified flows from the upper side of the arrangement (18) through the inlet spaces (6) to the DeNOX catalyst beds (7) and is then purified from NOX. From the DeNOX catalyst bed (7) the gas flows directly into an intermediate space (25) and is subsequently conveyed to a DeN2O catalyst bed (8), in which the remaining N2O in the gas is decomposed into nitrogen and oxygen. Then the purified gas (10) flows into the outlet spaces (9) and subsequently leaves the reactor. The catalyst beds (7, 8) are brought together to form pairs that directly border each other respectively, which extend vertically inside the arrangement (18) and whose front sides - through which the exchange is carried out gas - are directly in contact. For conducting the flow on the upper front side of the arrangement (18), gas-impermeable metal plates (22) are provided, which only allow the purified NOX gas to enter the inlet spaces (6) and not on the front sides of the beds catalyst (7), in the intermediate spaces (25) and in the outlet spaces (9). For conducting the flow on the lower front side of the arrangement (18), gas-impermeable metal plates (23) are provided, which only allow the purified gas (10) to escape through the outlet spaces (9) and not through the sides of the catalyst beds (8), the intermediate spaces (25) and the entry spaces (6). In addition to conducting the flow in the center of the arrangement (18) between the front sides of the catalyst beds (7, 8) as well as between the inlet spaces (6) and the outlet spaces (9), waterproof metal sheets are arranged gas (24), which only allow the gas to be purified from the DeNOX catalyst beds (7) to the intermediate spaces (25) and from there to the DeN2O catalyst beds (8) and not the direct passage from the entrance (6) to the exit spaces (9). The catalyst elements (7, 8) are laterally bounded by gas-permeable walls (15), which are developed e.g. like metal mesh.
[0113] [113] The following experiments and the following embodiment examples explain the process according to the present invention and the device according to the present invention or individual elements thereof without limiting the scope of the present invention.
[0114] [114] Experiments 1 to 3: Reduction of NOX using iron doped zeolite catalysts at different temperatures
[0115] [115] Experiments 1 to 3, the results of which are shown in Figures 7 to 9, based on the example of an iron doped zeolite catalyst demonstrate the peculiar effect of the DeNOX step according to the present invention or of the catalysts for the reduction of NOX used in this in the temperature range between 360 ° C and 500 ° C. In the case of the catalysts used in experiments 1 to 3, it was zeolite doped with iron of the type ZSM-5, which were produced by ion exchange in solid state from zeolite powder ZSM-5 in the form of ammonia. Detailed indications for the preparation can be taken from M. Rauscher, K. Kesore, R. Monnig, W. Schwieger, A. Tissler, T. Turek: "Preparation of highly active Fe-ZSM-5 catalyst through solid state ion exchange for the catalytic decomposition of N2O "in Appl. Catal. 184 (1999), 249-256. The obtained catalyst powder was calcined for 6 h at 823 K, washed and dried overnight at 383 K. After the addition of corresponding binding agents, extrusion was followed to form cylindrical catalyst bodies.
[0116] [116] The catalyst pellets were introduced into a tubular reactor of an experimental equipment, which was connected to a real residual gas from a nitric acid production unit. The operating temperature in the reaction zones was regulated by heating. The analysis of the gas flows entering and leaving the reactor was carried out with the aid of an FTIR gas analyzer (from Ansynco) or with a paramagnetic measurement for the oxygen content.
[0117] [117] The exact experimental and operational conditions are shown in Table 1 below. Table 1: Operational conditions for experiments 1 to 3
[0118] [118] The results of experiments 1 to 3 are shown in Figures 7 to 9. The legend in Figure 7 is also valid for Figures 8 and 9. The reference "out" in the legend designates the concentration at the reactor output respectively . As is evident, the NH3 reducing agent for the complete reduction of NOX without problem can also be dosed in largely over-stoichiometric amounts, without an NH3 leak.
[0119] [119] Experiments 4 and 5: NOX inhibitory effect on catalytic decomposition of N2O in the case of a NOX-sensitive DeN2O catalyst
[0120] [120] Figure 10 shows an example of a catalyst, which was produced in a similar way to the example of EP 1 257 347 B1 and after tempering it presented a mass ratio of the resulting oxides Co3O4: MgO = 3: 7, the inhibitory effect of NOX on the catalytic decomposition of N2O. Thus, under the selected conditions (compare Table 2 below) the temperature required for the decomposition of N2O in the presence of 1000 ppmv NOX was approx. 100 K higher than without NOX. Table 2: Experimental conditions for experiments 4 and 5
[0121] [121] The effect of the process according to the present invention / of the device according to the present invention is clarified by the following examples.
[0122] [122] In an experimental equipment with two subsequent tubular reactors, which were connected to a real residual gas from a nitric acid production unit, in a first step a DeNOX catalyst was introduced and in a second step a DeN2O catalyst sensitive to NOX.
[0123] [123] Before the first stage, NH3 was added as a reducing agent for NOX. The analysis of the incoming and outgoing gas flows to and from the reactor was carried out with the aid of an FTIR gas analyzer (from Ansyco) or with a paramagnetic measurement for the oxygen content. The operating temperature in the reaction steps was regulated by preliminary heating of the inlet gas flow in the tubular reactors and by heating the reaction zone.
[0124] [124] As a NOX-sensitive DeN2O catalyst in the DeN2O step, a Co3O4 / MgO-based catalyst was used in the form of a tablet, which was produced in a manner analogous to the example of the EP 1 257 347 B1 patent and had a relationship of the resulting oxides Co3O4: Mgo of 3: 7. The amount of catalyst was selected so that in relation to the apparent volume of the DeN2O catalyst, a spatial speed of 20,000 h-1 resulted. The temperature of the DeN2O step was 500 ° C.
[0125] [125] In the DeNOX step on the one hand (example 1) an extruded zeolite with iron type ZSM-5 was used, as it had already been used in experiments 1 to 3. The amount of catalyst was selected so that in relation to the apparent volume of the catalyst resulted in a space speed of 50,000 h-1. The temperature of the DeN2O step was also 500 ° C.
[0126] [126] On the other hand (example 2, comparative) in the DeNOX stage, a classic SCR catalyst based on Ceram V2O5-WO3 / TiO2 in the form of granules was used. For this purpose, the corresponding complete combs of the catalyst are crushed and after the thinning of the fine portion is introduced into the reactor. The amount of catalyst was selected so that in relation to the apparent volume of the DeNOX catalyst, a spatial speed of 48,000 h-1 resulted. The temperature of the DeNOX stage was set at 260 ° C so that the flow of outgoing gas in this case before entering the DeN2O stage had to be reheated.
[0127] [127] The exact experimental and operational conditions are shown in Table 3 below. Figure 11 illustrates the experimental results obtained. Table 3: Experimental conditions of examples 1 and 2
[0128] [128] As is evident in Figure 11, in example 1 according to the present invention a significantly higher N2O transformation is obtained than in comparative example 2. Surprisingly in this case in example 1 according to the present invention when compared to example 2, in which Co3O4 / MgO is preceded by a classic DeNOX catalyst based on V2O5-WO3 / TiO2, the decomposition of N2O achieved in addition in a wide area is more or less dependent on the NOX content at the exit of the DeN2O stage . The process according to the present invention or the device according to the present invention allows the simultaneous elimination of N2O and NOX from gases with high decomposition rates. In the case of the comparative example this is not possible considering that in the case of a high NH3 dosage, that is to say at the latest in the case of a ratio of [NH3] in: [NOX] out ≥ 1, an NH3 leak from the DeNOX step occurs , which in the DeN2O stage leads to at least partial NOX formation. This in turn not only results in an increase in NOX concentration, but also an inhibition of N2O decomposition in the DeN2O stage and therefore a dramatic setback in N2O decomposition.

权利要求:
Claims (17)
[0001]
DEVICE FOR THE REDUCTION OF NOx AND N2O CONTENT IN GASES, comprising: A) a container (1) and, arranged therein; B) two subsequent reaction steps for the elimination of NOx (DeNOX step) by NOx reduction with a nitrogen-containing reducing agent, and subsequently for the elimination of N2O by catalytic decomposition of N2O into N2 and O2 (DeN2O step ), which have one or more catalyst beds (7, 8) respectively and which are crossed by the gas to be purified, in which; C) at least one catalyst bed from the DeNOx stage (7) contains a catalyst for the reduction of NOx with nitrogen-containing reducing agents, which contains zeolites doped with transition metals, including lanthanides; D) at least one catalyst bed from the DeN2O step (8) contains a catalyst for the decomposition of N2O into N2 and O2, which does not contain zeolites or contains less than 15% by weight in zeolites and which contains one or more active catalytic compounds of elements selected from groups 5 to 11 of the Periodic Table of the Elements, except for iron doped zeolites, and; E) before the DeNOx step (7) a device is provided for introducing a nitrogen-containing reducing agent into the gas stream containing NOx and N2O; characterized by catalysts containing Rh, applied over ZrO2, TiO2 or hydrotalcites or their mixtures with these support materials, are present in the DeN2O step or in which contained catalysts, supported on hydrotalcites or magnesium oxide or their mixtures with these support materials present in the DeN2O stage.
[0002]
DEVICE, according to claim 1, characterized in that a mixer is provided, through which the gas containing NOx and N2O are conducted, as well as the reducing agent, and after mixing they are conducted to the DeNOX step, in which case preferably it is a static mixer, which is arranged before the container (1) or at the entrance to the container (1) or directly before the DeNOX stage.
[0003]
DEVICE, according to claim 1, characterized in that measurement points F) are provided for the flow or quantity of gas and / or measurement points G) for determining the NOX concentration or one of the respective individual components, wherein a measuring point F) is preferably arranged before the DeNOX stage and a measuring point G) is arranged before the DeNOX stage, after the DeNOX stage and before the DeN2O stage or after the DeN2O stage.
[0004]
DEVICE, according to claim 3, characterized in that a measuring point G) is arranged after the DeN2O step or, more preferably, before the DeNOX step in the supply pipe for the gas containing the nitric oxide and to be purified.
[0005]
DEVICE, according to claim 3, characterized by measuring points F) and G) for determining the quantity of reducing agent fed, via a control or regulation unit H), to be coupled to a regulation device I ), which allows a change in the supply of the amount of reducing agent, preferably with a control or adjustable valve, with which the flow or the amount of reducing agent that passes through device E can be regulated.
[0006]
DEVICE, according to claim 1, characterized in that at least one catalyst bed of one reaction step, preferably at least one catalyst bed of the two reaction steps is developed or is arranged to be laterally and, particularly, radially , crossed by the gas to be purified, in which the catalyst bed is preferably crossed radially by one or both reaction steps in the form of a hollow cylinder.
[0007]
DEVICE, according to claim 6, characterized by the catalyst beds radially traversed in the two reaction steps present in the form of hollow cylinders, which are concentrically placed inside one another, in which the outer hollow cylinder preferably contains catalysts for the NOX reduction, whose particles or shaped bodies have an equivalent diameter from 2 mm to 5 mm and the hollow inner cylinder contains catalysts for the decomposition of N2O, whose particles or shaped bodies have an equivalent diameter from 1 mm to 4 mm.
[0008]
DEVICE, according to claim 1, characterized in that in the DeNOX stage, catalysts are contained, which contain zeolites doped with Co, Cu and / or Fe, particularly zeolites doped with Fe.
[0009]
DEVICE, according to claim 1, characterized in that in the DeN2O step, catalysts are contained, which contain one or more active catalytic compounds of elements selected from groups 9 to 11 of the Periodic Table of the Elements, preferably composed of the elements Co, Pt, Pd, Ir, Rh, Ni and / or Cu, more preferably Co, Rh, Ni and / or Cu and particularly Co or Rh.
[0010]
DEVICE, according to claim 9, characterized in that the catalytic compounds active in the DeN2O catalysts are contained in pure form or are applied on suitable substrates or are mixed with them, being used as particularly refractory oxide substrates, preferably SiO2, TiO2, ZrO2, Al2O3 or mixtures of two or more of these or materials, which themselves have a certain catalytic activity for the decomposition of N2O, particularly MgO, zeolites, hydrotalcites or their mixtures.
[0011]
PROCESS FOR REDUCING NOx AND N2O CONTENT IN GASES, comprising the following steps: a) adding nitrogen-containing reducing agent to a gas stream containing N2O and NOX to reduce NOX; b) conducting the gas flow containing N2O, NOx and reducing agent through at least one catalyst bed of a DeNOx step (7), which contains a catalyst for the reduction of NOX through the reducing agent, which contains zeolites doped with transition metals, including lanthanides, in which NOX is transformed by reducing NOX with the reducing agent containing nitrogen, and; c) conduction of the gas flow leaving the DeNOx stage through at least one catalyst bed of a DeN2O stage (8), which contains a catalyst for the decomposition of N2O into N2 and O2, which is selected from the group catalysts containing no zeolites, or containing less than 15% by weight of zeolites, and containing one or more active catalytic compounds from elements selected from groups 5 to 11 of the Periodic Table of the Elements with the exception of iron doped zeolites, in whereas N2O is transformed by catalytic decomposition of N2O into N2 and O2, characterized by catalysts, containing Rh supported on ZrO2, TiO2 or hydrotalcites, or mixed with these support materials, are present in the DeN2O step, or in which co-containing catalysts, supported on hydrotalcites or magnesium oxide or mixed with these materials of support, in the DeN2O stage.
[0012]
PROCESS, according to claim 11, characterized in that the amount of reducing agent is selected so that it is totally or almost totally transformed in the DeNOx step, so that no transfer of the reducing agent from the DeNOx step to the DeN2O step results or only a slip of less than 25 ppmv results.
[0013]
PROCESS, according to claim 11, characterized in that the reducing agent for NOx is ammonia, which is preferably added in an amount such that, in relation to the NH3 and NOx components at the entrance of the DeNOX step, a NH3 / molar ratio results NOX from 0.8 to 3, preferably from 1 to 2.5, more preferably from 1.2 to 2 and particularly from 1.3 to 1.8.
[0014]
PROCESS, according to claim 11, characterized by the reaction agent containing nitrogen being added to the gas stream containing N2O and NOx in such an amount that the degree of NOx degradation, in relation to the NOx input concentration, is higher 70%, preferably greater than 80%, more preferably greater than 90%, particularly greater than 95% and / or where in the DeN2O step the spatial velocity, temperature and pressure are selected so that the outlet gas of the step DeN2O has an N2O content of less than 100 ppmv, preferably less than 50 ppmv, more preferably less than 30 ppmv and, even more preferably, less than 15 ppmv.
[0015]
PROCESS, according to claim 11, characterized by the addition of a reducing agent for NOx to be regulated by the fact that through the measurement point G) the NOx content is measured at the exit of the DeN2O step and through a regulation unit H ) a regulating device I) is controlled for the dosing of the reducing agent so that the desired NOx content is regulated at the exit of the DeN2O step and / or the addition of NOx reducing agent is controlled by the fact that the NOx and the flow or amount of gas to be measured before entering the DeNOx step and from these values via a control unit H) with specification of an appropriate ratio of the quantities of reducing agent and NOx to determine the required amount reducing agent and regulating device I) to be adjusted accordingly.
[0016]
PROCESS, according to claim 11, characterized in that the temperature in the DeNOx stage and in the DeN2Ü stage is between 300 ° C and 600 ° C, preferably between 350 ° C and 550 ° C and, more preferably, between 400 ° C and 550 ° C, and, where the temperature of the DeN2Ü step does not differ by more than 50 ° C, preferably not more than 20 ° C from the temperature in the DeNOx step and / or where the pressure in the DeNOx step and the DeN2Ü step is comprised in the range of 1 absolute bar to 50 absolute bars, preferably from 1 absolute bar to 25 absolute bars, more preferably from 4 absolute bars to 15 absolute bars and / or where the process in the DeNOx step is carried out at a spatial speed of 5,000 h-1 to 200,000 h-1, preferably from 10,000 h-1 to 100,000 h-1 and, more preferably, from 20,000 h-1 to 60,000 h-1.
[0017]
PROCESS according to claim 11, characterized in that the process in the DeN2O step is carried out at a spatial speed of 2,000 h-1 to 50, 000 h-1, preferably from 2,500 h-1 to 25, 000 h-1 and, more preferably , from 3,000 h-1 to 20,000 h-1.

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WO2021170756A1|2020-02-25|2021-09-02|Thyssenkrupp Industrial Solutions Ag|Reactor for the catalytic treatment of a gas stream|

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BE1027663B1|2020-02-25|2021-05-06|Thyssenkrupp Ind Solutions Ag|Reactor for the catalytic treatment of a gas stream|

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WO2021198150A1|2020-04-01|2021-10-07|Haldor Topsøe A/S|A PROCESS FOR THE REMOVAL OF NOx AND DINITROGEN OXIDE IN PROCESS OFF-GAS|

法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-07-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-10-05| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

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2022-01-25| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2648 DE 05-10-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102011121188.1|2011-12-16|

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DE102011121188A|DE102011121188A1|2011-12-16|2011-12-16|Apparatus and method for removing NOx and N20|

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PCT/EP2012/005082|WO2013087181A2|2011-12-16|2012-12-08|Device and method for eliminating nox and n2o|

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