• 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:
    method and catalyst for simultaneous removal of carbon monoxide and nitrogen oxides from exhaust or exhaust gases. a method and a catalyst, where exhaust or exhaust gas containing carbon monoxide, organic compounds (cov) and harmful nox are contacted with a layered catalyst, in which a first layer comprises an oxidation catalyst and a layer underlying an rcs-nh3 catalyst for simultaneous removal of carbon monoxide and nox.
    公开号:BR112015019557B1
    申请号:R112015019557-1
    申请日:2014-02-03
    公开日:2021-06-29
    发明作者:Francesco Castellino；Viggo Lucassen Hansen
    申请人:Haldor Topsøe A/S；
    IPC主号:
    专利说明:

    [01] The present invention relates to a method and catalyst for the simultaneous removal of carbon monoxide and nitrogen oxides (NOx) contained in exhaust or exhaust gas.
    [02] More particularly, the invention provides a method in which exhaust or exhaust gas, containing carbon monoxide, organic compounds (VOC) and harmful NOx, is contacted with a layered catalyst, wherein a first layer comprises an oxidation catalyst and, in an underlying layer, an RCS-NH3 catalyst for simultaneous removal of carbon monoxide and NOx.
    [03] The removal of NOx, VOC and CO from exhaust or exhaust gas is conventionally carried out by using two different catalyst compositions, in which an oxidation catalyst is disposed upstream of a RCS catalyst with the injection of a reducing agent between the catalysts. Removal of NOx is typically carried out by selective catalytic reduction (RCS) with NH3 in vanadium oxide or zeolite-based catalysts in monolithic form. Ammonia is injected upstream of the RCS catalyst and reacts with NOx on the catalyst surface. An ideal temperature window for vanadium oxide based catalysts is 200-400°C, while zeolite based catalysts are most active at temperatures >400°C.
    [04] In the case of CO and VOC removal by catalytic oxidation, platinum metals are the most common choice due to their high reactivity already at temperatures >200°C.
    [05] As an example of an exhaust gas that contains both CO, VOCs and NOx, it is the exhaust gas from a turbine that runs on natural gas. Traditionally, in HRSG design, the CO oxidation catalyst, often based on Pt, is located upstream of the RCS catalyst and the ammonia injection network ("AIG"). This location was chosen mainly due to the fact that the oxidation catalyst is very active in oxidizing NH3 to NOx, which is highly undesirable. Having the CO oxidation catalyst located upstream of the AIG ensures that no NH3 is wasted, but all amounts of injected ammonia reach the RCS catalyst, limiting the utility's operating costs.
    [06] In an alternative configuration, the oxidation catalyst is disposed downstream of the RCS catalyst. When positioned in this way, the oxidation catalyst is operated at lower temperatures than in the conventional arrangement. The problem with this configuration is that, if not properly designed, the oxidation catalyst can oxidize the NH3 escape to NOx, thus reducing the overall NOx removal from the plant. Possibly, the oxidation catalyst can be designed in such a way that NH3 is converted to N2 instead, but such a catalyst is generally more expensive than a conventional oxidation catalyst due to both the type and amount of noble metals used for your production.
    [07] In the above configurations, the resulting reactor consists of two separate catalyst units, that is, an RCS catalyst unit and an oxidation catalyst unit. More precisely, the total volume of installed catalyst will be determined by the size of the RCS catalyst unit plus the size of the oxidation catalyst unit.
    [08] In order to reduce the size of the reactor, a combination of the two catalysts, partially on the same support, was tried and, in some cases, implemented.
    [09] US patent 7,390,471 describes an exhaust gas treatment apparatus for reducing the concentration of NOx, HC and CO in an exhaust gas stream. The treatment apparatus includes a multifunctional catalytic element having an upstream reduction only portion and a downstream reduction plus oxidation portion, which is located downstream of an ammonia injection apparatus. Selective catalytic reduction (RCS) of NOx is promoted in the upstream portion of the catalytic element by injecting ammonia, in excess of the stoichiometric concentration, with the resulting ammonia leakage being oxidized in the downstream portion of the catalytic element. Any additional NOx generated by the oxidation of ammonia is further further reduced in the downstream portion before being passed into the atmosphere. The reduction only catalyst may be vanadium/TiO2 and the reduction plus oxidation catalyst includes a reduction catalyst having 1.7 weight percent vanadium/TiO2 impregnated with 2.8 g/ft3 each of platinum and palladium.
    [010] However, the RCS activity of the oxidation catalyst is considerably lower than the RCS activity of an RCS catalyst alone, which means that the total volume of installed catalyst will be equal to the volume of oxidation catalyst plus the volume of RCS catalyst needed to compensate for the low RCS activity of the oxidation catalyst.
    [011] In gas turbine exhaust gas cleaning as an example, the number one priority, from a utility standpoint, is to reduce the total catalyst volume as much as possible. Large volumes, in fact, mean high pressure drop across the catalyst bed and lower overall HRSG efficiency. The pressure drop has a direct impact on the useful power achievable by the turbine and an indirect effect on the heat flow, ie the calories that can be extracted from the flue gas by the HRSG.
    [012] In order to reduce the catalyst volume to a minimum, the RCS activity of the oxidation catalyst has to be increased to the same high levels of an RCS catalyst alone. An essential condition to achieve this is the use of a catalyst that is very active in the oxidation of CO and VOC, but which does not react with NH3. Another important condition is that the oxidation catalyst must still have the same oxidation activity as an oxidation catalyst only.
    [013] By the present invention, these two conditions are met, the total volume of the resulting catalyst for the combined removal of both CO, NOx and VOC is equal to the volume of the largest catalyst between a dedicated oxidation catalyst and a dedicated RCS catalyst, which depend on the removal of CO, NOx and VOC required for a specific installation.
    [014] Thus, this invention provides a method for reducing amounts of carbon monoxide, volatile organic compounds and nitrogen oxides in exhaust or exhaust gas, said method comprising the steps of: introducing ammonia and/or a its precursor in the exhaust or exhaust gas; converting the precursor, if any, to ammonia; contacting the gas and ammonia, at a temperature of up to 350°C, with a layered catalyst comprising, in the gas flow direction, an upper first catalyst layer with an oxidation catalyst and an underlying second catalyst layer with an oxidation catalyst RCS-NH3 fully supporting the first oxidation layer and at least part of the amounts of carbon monoxide and volatile organic compounds in the top first layer without affecting the additional ammonia contained in the gas and reducing the amounts of nitrogen oxides in the second layer underlying catalyst by reaction with ammonia.
    [015] A CO, VOC oxidation catalyst not active in the oxidation of NH3 at temperatures up to 350°C for use in the method according to the present invention has been developed.
    [016] Thus, in an embodiment of the invention, the oxidation catalyst in the first layer consists of palladium, vanadium oxide and titanium oxide.
    [017] By coating this catalyst on a commercial RCS-NH3 catalyst, for example, on an RCS-NH3 catalyst comprising tungsten, molybdenum, vanadium and titanium oxides according to another embodiment of the invention, the resulting catalyst it consists of a first layer of oxidation catalyst from CO and VOC but not ammonia, and a second layer of catalyst from RCS-NH3 only.
    [018] Referring to Figure 1 of the drawings at gas temperatures up to 350°C, CO and VOC will be oxidized to CO2 in the first oxidation layer 2 of layer 1 catalyst, while all NH3 injected for NOx reduction will diffuse , simultaneously, through the oxidation layer 2 and will instead react on the underlying RCS catalyst layer 3.
    [019] By improving the pore structure and thickness of the first catalyst layer, both NOx and NH3 will easily access the underlying RCS catalyst and very limited RCS activity will be lost due to the rate of diffusion of reactants through the layer. of oxidation catalyst.
    [020] Thus, in another embodiment of the invention, the first catalyst layer has a layer thickness of between 10 and 200 µm, preferably between 10 and 50 µm.
    [021] In the method according to the invention as described above, the exhaust or exhaust gas can be further treated with an unconventional layered RCS catalyst, either upstream or downstream of the layered catalyst.
    [022] The invention additionally provides a catalyst for the simultaneous oxidation of carbon monoxide and volatile organic compounds and selective reduction of nitrogen oxides by reaction with ammonia, the catalyst comprises a first layer of an oxidation catalyst and a second layer of an RCS-NH3 catalyst fully supporting the first layer.
    [023] Preferably, the oxidation catalyst consists of palladium, vanadium oxide and titanium oxides.
    [024] The preferred oxidation catalyst, according to an embodiment of the invention, also has some RCS activity, due to the presence of both TiO2 and vanadium oxides. The total RCS activity is thus preserved without the need to increase the ammonia addition. In this way, the intended removal of both CO and NOx can be accomplished with a significantly reduced catalyst volume.
    [025] In an embodiment of the invention, the first catalyst layer has a layer thickness of between 10 and 200 µm, preferably between 10 and 50 µm.
    [026] When structuring the layered catalyst in monolithic form, the resulting monolithic catalyst will have a homogeneous catalyst composition over the entire length of monolith. Removal of CO, VOC and NOx proceeds simultaneously along the entire length of the monolith. EXAMPLE
    [027] A commercial V/Ti based RCS catalyst was coated with a catalyst consisting of 0.45% by weight of Pd, 4.5% by weight of V2O5 over TiO2. The NOx removal efficiency was measured and compared to the NOx removal efficiency of the same RCS catalyst not coated with the oxidation catalyst. The test results and conditions are shown in Table 1 below: TABLE 1
    Test conditions. Inlet gas composition: NOx at 50 ppmv, NH3 at 55 ppmv, CO at 100 ppmv, O2 at 15% vol, H2O at 10% vol, N2 in equilibrium. Space velocity of gas, NHSV = 27,000 h-1. Temperature: 350°C.
    [028] As is evident from Table 1, the same (within experimental uncertainty) NOx removal efficiency was obtained in both tests.
    权利要求:
    Claims (11)
    [0001]
    1. Method for reducing amounts of carbon monoxide, volatile organic compounds and nitrogen oxides in exhaust or exhaust gases CHARACTERIZED by understanding the steps of: introducing ammonia and/or its precursor into the exhaust or exhaust gas ; convert the precursor, if any, to ammonia; contacting the gas and ammonia at a temperature of up to 350°C, with a layered catalyst comprising a first top catalyst layer with an oxidation catalyst, in the direction of gas flow, consisting of palladium, vanadium oxide and titanium oxide and an underlying second catalyst layer with an RCS-NH3 catalyst that fully supports the first layer and oxidizes at least part of the amounts of carbon monoxide and volatile organic compounds in the upper first layer, without affecting the additional ammonia contained in the gas and reduces the amounts of nitrogen oxides in the underlying second catalyst layer by reacting with ammonia.
    [0002]
    2. Method according to claim 1, CHARACTERIZED by the fact that the oxidation catalyst consists of 0.45% by weight of palladium, 4.5% by weight of vanadium pentoxide and supported on titanium oxide.
    [0003]
    3. Method according to claim 1 or 2, CHARACTERIZED by the fact that the first catalyst layer has a layer thickness of between 10 and 200 µm.
    [0004]
    4. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the first catalyst layer has a layer thickness of between 10 and 50 µm.
    [0005]
    5. Method according to any one of claims 1 to 4, CHARACTERIZED by the fact that the RCS-NH3 catalyst in the second catalyst layer comprises oxides of tungsten, molybdenum, vanadium and titanium.
    [0006]
    6. Method according to any one of claims 1 to 5, CHARACTERIZED by the fact that the exhaust or exhaust gases are additionally treated with a conventional layerless RCS catalyst, both upstream and downstream of the layered catalyst .
    [0007]
    7. Catalyst for the simultaneous oxidation of carbon monoxide and volatile organic compounds and selective reduction of nitrogen oxides by reaction with ammonia, CHARACTERIZED by the fact that the catalyst comprises a first layer of an oxidation catalyst consisting of palladium, vanadium oxides and titanium oxides and a second layer downstream of an RCS-NH3 catalyst fully supporting the first layer.
    [0008]
    8. Catalyst according to claim 7, CHARACTERIZED by the fact that the oxidation catalyst consists of 0.45% by weight of palladium, 4.5% by weight of vanadium pentoxide and supported on titanium oxide.
    [0009]
    9. Catalyst according to claim 7 or 8, CHARACTERIZED by the fact that the first catalyst layer has a layer thickness of between 10 and 200 µm.
    [0010]
    10. Catalyst according to any one of claims 7 to 9, CHARACTERIZED by the fact that the first catalyst layer has a layer thickness of between 10 and 50 µm.
    [0011]
    11. Catalyst according to any one of claims 7 to 10, CHARACTERIZED by the fact that the RCS-NH3 catalyst in the second catalyst layer comprises oxides of tungsten, molybdenum, vanadium and titanium.
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DKPA201300091|2013-02-14|
    DKPA201300091|2013-02-14|
    PCT/EP2014/052043|WO2014124830A1|2013-02-14|2014-02-03|Method and catalyst for the simultaneous removal of carbon monoxide and nitrogen oxides from flue or exhaust gas|
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