The present invention relates to processes for activating a novel palladium catalyst system to be employed in the reduction of nitrogen oxides (NOx) in a gaseous stream, e.g., combustion exhaust, by selective catalytic reduction (SCR) using hydrogen (H2) as the reducing agent. The present invention also relates to the field of power generation, and more particularly to the control of NOx emissions produced during combustion of a fuel containing hydrogen to generate power, and specifically to the catalytic treatment of exhaust gases from a gas turbine at a coal gasification plant. However, the invention may also be employed in NOx abatement from other sources, such as emissions generated during manufacture of nitric acid, within internal combustion engines and the like.
Coal-based integrated gasification combined cycle plant (IGCC) technology enables production of electricity with a gas turbine utilizing a fuel that is rich in hydrogen and has a very limited amount of CO2. Combustion of the hydrogen-containing fuel requires an oxidizing source such as air, which contains nitrogen (N2). As a result, a by-product in exhaust gas stemming from hydrogen-containing fuel combustion is a significant amount of NOx. The NOx in the exhaust gas may be reduced by using selective catalytic reduction (SCR) systems along with low NOx combustors in the gas turbine. Since fuel produced and used at an IGCC plant contains hydrogen (H2), the fuel may also provide hydrogen as a reducing agent in the SCR process by introducing a small amount of H2 from the fuel supply into the SCR system. The use of hydrogen as a NOx reducing agent enables the elimination of typical reducing agents, for example, ammonia (NH3) and urea (N2H6CO) in the SCR system, and thus prevents discharge of ammonia slip into the ambient air, which is an inherent problem with current ammonia-based SCR technology.
Recently, a strong attempt to improve H2-SCR efficiency with respect to NOx removal and N2 selectivity under oxidizing conditions was made in U.S. patent application Ser. No. 12/122,116, the entirety of which is hereby incorporated by reference. As described in U.S. patent application Ser. No. 12/122,116, a palladium (Pd) catalyst showed a substantial increase in NOx reduction efficiency over a platinum (Pt) catalyst that was disclosed in U.S. Pat. No. 7,105,137, for example, under gas turbine exhaust conditions. In U.S. patent application Ser. No. 12/472,633, the entirety of which is also incorporated by reference herein, the Pd-based catalyst system was further modified by incorporating a pre-sulfated zirconium binder. While not wishing to be bound by any particular theory, the inventors believed that the pre-sulfated zirconia binder protects the palladium catalyst from degradation by binding sulfur to the defects in the crystalline zirconia structure, thereby minimizing further sulfur poisoning during contact with an exhaust gas containing SO2.
The invention is explained in the following description in view of the drawings that show:
The inventors have surprisingly found that by activating a catalyst system used for the reduction of NOx in an HRSG according to the activation process parameters described herein significantly increases the subsequent NOx reducing efficiency of the catalyst system. In the activation process, an activation gas stream comprising an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen is passed over the catalyst system, typically prior to use of the catalyst system to reduce an amount of NOx in an industrial (process) gas stream. In one advantageous embodiment, the temperature of the catalyst system is heated to a temperature of at least 180° C. at a heating rate of from 1-20°/min during the activation process. In another embodiment, since oxygen, water vapor, nitrogen oxides (NOx), and hydrogen may be present in a process gas stream (e.g., exhaust gas from combustion utilizing natural gas fuel), the process gas stream may advantageously be utilized to activate the catalyst system prior to utilizing the catalyst system at the optimum temperature for reducing an amount of NOx in the process gas stream. In the latter embodiment, hydrogen may be required to be added to the process gas stream during the activation process if there is initially an insufficient amount of hydrogen in the process gas stream.
Now referring to the figures,
In one embodiment, the H2-SCR bed 32 is in a geometric form that allows for high NOx reduction efficiency along with a minimal pressure drop. Although beads, extrudates, etc. are suitable geometric forms employed in commercial applications, a monolith is a preferred form. The monolithic form and the use of a monolith as a catalyst carrier are well known to one skilled in the art. A monolith consists of a series of straight, non-interconnecting channels. Onto the walls of the monolith are coated a thin layer of a catalyst-containing material, termed “washcoat” by the trade. It is within the pores of the washcoat that the catalytically active metals and binder are located. Thus, in one embodiment, a honeycomb monolith may be washcoated with a catalyst system as described herein.
In one embodiment, as shown in
In accordance with an aspect of the present invention, the catalyst system 38 of the H2-SCR bed 32 is activated by exposing the H2-SCR bed 32 to a flowing activation gas stream. For example, as shown in
As is shown in
From the results depicted in
It has also been found based on data presented in
In order to further determine if the catalyst system 38 (activated with the activation gas stream 48) is durable over long periods of time, the catalyst system 38 was tested for 2500 hours under the conditions described in the Example 3.
The activation of the catalyst system 38 may take place in the activation reactor 50, which may be the same reaction vessel that is used for NOx reduction of the process gas stream (e.g., turbine exhaust gas 29), or may be any other suitable vessel. An exemplary activation reactor 50 is the HRSG 31 downstream of the gas turbine 28. In one embodiment, as shown in
The activation gas stream 48 passing over the catalyst system 38 may be any gas stream comprising an amount of oxygen, water, nitrogen oxides, and hydrogen. By the term “passing over,” it is understood that the activation system may flow over, within, or through the structure, e.g. a monolith, comprising the catalyst system 38. In one embodiment, the activation gas stream may comprise oxygen in a concentration of from 1-15 vol. %, water vapor in a concentration of from 1-25 vol %, nitrogen oxides (NOx) in a concentration of from 10-100 ppm, and hydrogen in a concentration that provides a hydrogen/nitrogen oxides molar ratio of from 1-100. In a particular embodiment, the activation gas stream 48 may include, for example, 5-18% of O2, 1-5% of H2O, 10-50 ppm of NOx, up to 800 ppm of H2, and a balance of N2. Optionally, the activation gas stream 48 comprises an inert gas, e.g., nitrogen, as the balance. The inert gas may be any suitable component, which does not react with other gases in the activation gas stream 48 or the components of the catalyst system 38. It has been found that the composition of the activation gas stream 48 being introduced into the activation reactor 50 substantially affects the subsequent catalyst performance. As mentioned above, the presence of each of oxygen, water, nitrogen oxides, and hydrogen in the activation gas stream results has been found to be critical for the improved performance of the catalyst system 38 in reducing NOx from a subject gas stream after activation.
For example,
The temperature of the catalyst system 38 is increased during activation to a temperature that is typically higher than the normal (most desirable) operating temperature (e.g., 100-140° C.) of the catalyst system 38 to achieve high NOx removal efficiency for a subsequent process gas stream (e.g., turbine exhaust gas 29). Put another way, during activation, the catalyst system 38 is heated to a temperature greater than a temperature to which the catalyst system 38 will be heated during the intended and optimal use of the catalyst system 38 to remove NOx from the process gas stream. In one embodiment, during activation, the catalyst system 38 is heated to a maximum activation temperature in the range of 200-500° C., and in another embodiment, to a maximum activation temperature in the range of from 230-300° C. (as shown on
The catalyst system is typically heated to the maximum temperature from a starting temperature at a heating rate of from 1-20° C./min, and in one embodiment, from 2-10° C./min. The starting temperature is typically ambient temperature, e.g., about 25° C., but is not necessarily so. A higher heating rate reduces the duration of the activation process and, consequently, usage of gaseous components required for activation. In one embodiment, the temperature of the catalyst system 38 is brought to the required temperature by the flow of the activation gas stream 48 in the activation reactor 50 with the addition of H2 at a predetermined heating rate. The heat source 57 may add heat to the activation reactor 50 if necessary to arrive at the desired temperature. After the end of the activation process, the temperature of the catalyst system 38 can be lowered to normal optimal operating temperature (100-140° C.) to achieve high NO removal efficiency for the subject process gas stream, e.g., turbine exhaust gas 29. In this way, during activation, the catalyst system 38 is heated to a temperature above a normal operating temperature of the catalyst system 38 for the subsequent NOx reduction reaction. Once the catalyst system 38 is activated, no additional steps are needed for the duration of the usage of the catalyst system 38.
The amount of the activation gas stream 48 fed per hour per volume of the catalyst 40 (or the Gas Hourly Space Velocity (GHSV)) may be in the range of from 5,000-25,000 hr-1, and in another embodiment, from 10,000-15,000 hr-1. Typically, the activation gas stream 48 is passed over the catalyst system for an amount of time effective to activate the catalyst system 38, e.g., for a time sufficient for the catalyst system to remove NOx more effectively than if the catalyst had not been subject to the activation gas stream 48 at the temperatures described herein. In one embodiment, the activation gas stream 48 is passed over the catalyst system for a duration of at least 7 minutes, and in another embodiment, for at least 10 minutes, and in yet another embodiment, for at least an hour at a heating rate of between 1-20° C. During the activation process, the temperature of the catalyst system 38 is typically heated, e.g., ramped, to the maximum temperature. In one embodiment, the temperature of the catalyst system 38 may be held at the maximum temperature for a period of time, for example, from 1 to 300 minutes.
In one embodiment, the activation gas stream 48 may actually be an exhaust gas from fossil fuel combustion, e.g., turbine exhaust gas 29, having added amounts of hydrogen. The turbine exhaust gas 29 may be introduced into the activation reactor 50 and brought to the desired temperature for the duration of the activation process. Hydrogen may be introduced into the activation reactor from a suitable hydrogen source (not shown) as mentioned above.
In accordance with another aspect of the present invention, the flow of the activation gas stream 48 for the activation of the catalyst system 38 can be recycled (or at least partially recycled) from an outlet to an inlet of the activation reactor 50. As shown in
Referring now to
Referring to
Referring to
Although the above-invention was described in the context of the power generation field, with specific emphasis on the treatment of gas turbine exhaust, the novel process as described herein may be applied to other NOx pollution sources, such as for example nitric acid plants and stationary emissions sources. The below examples are provided to illustrate certain aspects of the present invention and are not intended to be limiting in any respect.
This example illustrates a method of synthesis of a Pd-based catalyst supported with pre-sulfated zirconia binder on ZrO2—SiO2 to form Pd/W (ZrO2—SiO2)SO4 with approximately 0.75-1.0 wt % Pd. To arrive at this catalyst system, 4.5 Kg of zirconium hydroxide was added to a 5 gallon pail with 4.5 L of deionized (DI) water and 750 g of a colloidal silica solution (40% SiO2). The pH of the zirconium hydroxide/silica solution was adjusted to about 3.0 with sulfuric acid and mixed overnight. The following morning, the solution was emptied into a pan and placed in an oven to dry at 110° C. until all the water was evaporated. Once dried, the resulting zirconia-silica-sulfate material was crushed below 40-mesh and calcined at 650° C. for 2 hrs.
The washcoat with binder was prepared by adding 21 g of said zirconia-silica-sulfate, 21 g of a zirconium oxynitrate solution (20% ZrO2), 0.266 g ammonium metatungstate (Aldrich) and 50 mL of DI water to a beaker. Monolith cores (230 cells per square inch (cpsi)) were dipped in the slurry with excess slurry blown from the channels using an air knife. Catalyst cores were calcined at 450° C. for 1 hour. The washcoat loading was approximately 110 g per liter of monolith. After calcining, the cores were cooled and dipped into a solution of 2 g sulfuric acid in 98 g deionized (DI) water yielding a 1.98% sulfuric acid loading (2% sulfuric acid per washcoat). Blocks were then dried in a microwave and calcined at 650° C. for 2 hours.
A palladium metal solution was prepared by adding to a beaker: 8.165 g palladium chloride solution (8.94-9.35% Pd); 2.2 g TEA (triethanolamine); and sufficient DI water to yield a 100 g total solution weight. Monolith blocks were dipped in the solution yielding a 0.78% Pd loading by washcoat (catalyst system) weight. Excess solution was blown from the channels using an air knife. Blocks were dried in a microwave oven for 2-10 minutes and then calcined at 450° C. for 2 hours to decompose the palladium complex.
This example illustrates the performance of the catalyst system developed according to Example 1 after activation by exposure of the catalyst system to simulated gas turbine combustion exhaust under different heating rates. The catalyst was prepared according to the procedure described in Example 1, with the concentration of Pd 0.75% (g Pd/g washcoat). Two blocks of the catalyst were placed in a glass reactor. The distance between the blocks was 10 mm. The simulated gas turbine exhaust comprised 10 vol. % O2, 800 ppm H2, 10 ppm NOx, 5-25 vol. % H2O, 5 ppm SO2, and N2 was the balance. The GHSV was 10,000 hr−1. The catalyst was exposed to the flow of the gas with the above mentioned composition by means of a programmed temperature treatment while increasing temperature by 2° C./min and 10° C./min up to 250° C. Then the gas temperature was reduced to 120-140° C. to conduct NOx reduction tests. These results are provided in Table 1 below.
This example illustrates the results of the performance of the developed catalyst system by continued exposure to the simulated gas turbine combustion exhaust after activation. The catalyst system was prepared according to the procedure described in Example 1, with the concentration of Pd 0.75% (g Pd/g washcoat). Two blocks of the catalyst system were placed in a glass reactor. The distance between the blocks was 10 mm. The simulated gas turbine exhaust had 10 vol. % O2, 800 ppm H2, 10 ppm NO, 5-25 vol. % H2O, 5 ppm SO2, and N2 was the balance. The GHSV was 10,000 hr−1. The catalyst system was exposed to the flow of the gas with the above mentioned composition by means of a programmed temperature treatment while increasing temperature by 2° C./min up to 250° C. Thereafter, the gas temperature was reduced to 120-140° C. to conduct NOx reduction tests under conditions with different gas compositions. Following 700 hours of testing, the catalyst system was periodically shutdown (every 200-300 hours) to simulate the real conditions of catalyst operation during a gas turbine run. During the shutdown process, the flow of the gases to the catalyst system was interrupted and the catalyst system was cooled down to a temperature of about 50° C. for 1-2 hours. Thereafter, the catalyst system was exposed to the simulated gas turbine exhaust and the flow and temperature were restored back to the aforementioned operating conditions for continuation of the testing process. The results are illustrated in
While various embodiments of the present invention have been shown and described herein, it will be obvious that such embodiments are provided by way of example only. Numerous variations, changes and substitutions may be made without departing from the invention herein. Accordingly, it is intended that the invention be limited only by the spirit and scope of the appended claims.
Development for this invention was supported in part by Contract No. DE-FC26-05NT42644, awarded by the United States Department of Energy. Accordingly, the United States Government may have certain rights in this invention.
Number | Name | Date | Kind |
---|---|---|---|
3032599 | Bailey et al. | May 1962 | A |
3098712 | Andersen et al. | Jul 1963 | A |
3360481 | McLaren | Dec 1967 | A |
3931045 | Rush | Jan 1976 | A |
4312638 | Koump | Jan 1982 | A |
5543124 | Yokota et al. | Aug 1996 | A |
5589142 | Gribbon | Dec 1996 | A |
5710085 | Absil et al. | Jan 1998 | A |
5753192 | Dobson et al. | May 1998 | A |
5891409 | Hsiao et al. | Apr 1999 | A |
5955039 | Dowdy | Sep 1999 | A |
6266957 | Nozawa et al. | Jul 2001 | B1 |
6267940 | Chang et al. | Jul 2001 | B1 |
6475943 | Hoek et al. | Nov 2002 | B1 |
6513319 | Nozawa et al. | Feb 2003 | B2 |
6689709 | Tran et al. | Feb 2004 | B1 |
7049261 | Nam et al. | May 2006 | B2 |
7096667 | Laster et al. | Aug 2006 | B2 |
7105137 | Efstathiou et al. | Sep 2006 | B2 |
7179426 | Hottovy et al. | Feb 2007 | B2 |
7247592 | Echigo et al. | Jul 2007 | B2 |
7371706 | Ohtsuka et al. | May 2008 | B2 |
7390471 | Sobolevskiy et al. | Jun 2008 | B2 |
7744840 | Sobolevskiy et al. | Jun 2010 | B2 |
20070110643 | Sobolevskiy et al. | May 2007 | A1 |
20070181854 | Briesch et al. | Aug 2007 | A1 |
20070289214 | Briesch et al. | Dec 2007 | A1 |
20080196388 | Johnson et al. | Aug 2008 | A1 |
20080299016 | Sobolevskiy et al. | Dec 2008 | A1 |
20090020410 | Niwa et al. | Jan 2009 | A1 |
20100061903 | Kohara et al. | Mar 2010 | A1 |
Number | Date | Country | |
---|---|---|---|
20110105314 A1 | May 2011 | US |