1. Field of the Invention
This invention resides in the field of NOx emissions from combustion facilities, and methods and plant equipment using selective catalytic reduction (SCR) for controlling and reducing the emissions.
2. Description of the Prior Art
A widely used process for the reduction of NOx emissions from coal-fired utility boilers and in combustion flue gases in general is the process known as selective catalytic NOx reduction (SCR). In this process, the NOx in the flue gas is reacted with oxygen and ammonia over a solid catalyst which is either a metal such as titanium, vanadium or platinum, or a zeolite or a ceramic, to reduce the nitrogen in NOx to molecular nitrogen with water as a by-product. The utility industry has invested billions of dollars in SCR units, and these units collectively utilize a volume of catalyst that is on the order of 200,000 m2.
The performance of an SCR unit, as measured by the change in NOx concentration across the unit (ΔNOx), depends on the catalyst activity and the area velocity Av of the unit according to the relation
ΔNOx=1−e−K/A
A well-run boiler or combustion facility will have a catalyst management procedure for the SCR unit that will allow the facility to comply with the regulatory requirements for NOx and NH3 emissions, and yet conform to the outage schedule for the facility. Periodic monitoring of the catalyst provides the most efficient use of the catalyst and allows operators to maintain the facility in compliance with the regulations. Monitoring methods that are in current use introduce inefficiencies of their own, however.
One of these methods is by monitoring the ammonia slip. Another is by monitoring the ammonia content of the fly ash. Either method provides only an indirect indication of the catalyst activity, and only a gross or overall indication of any loss in activity. These methods will not differentiate between situations in which all catalyst layers are losing activity at approximately the same rate from those in which upstream layers are losing activity at a greater rate than those downstream. A further difficulty is that increases in the ammonia slip or in the ammonia content of the fly ash may be the result of factors other than catalyst activity, such as an ammonia injection grid that is not properly adjusted or any other irregularity in the ammonia injection system.
Another monitoring method is that in which samples of catalyst are removed from the reactor and transferred to a laboratory for direct determinations of the catalyst activity or the activity ratio K/Ko. This can also be done with catalyst coupons retained in the reactor in a special removable holder. Removal of the samples or coupons however usually requires that the unit be taken off-line. Unless the unit is expressly shut down for the sampling, the time interval between sampling opportunities will be dictated by the outage schedule of the unit rather than concerns over the catalyst activity and can be very long. For those units operating on a schedule that is designed to accommodate the ozone season, for example, outages may occur as seldom as once or twice a year. For units operating year-round, the sampling frequency may be even lower, such as once every other year. A further problem with the withdrawal of catalyst samples is that the analyses of these samples provide no information regarding how any observed decrease in catalyst activity occurred, i.e., whether the decrease occurred slowly and gradually over time or by a step change resulting from a boiler upset, a fuel change, or some other occurrence not related to the SCR unit itself.
The present invention resides in modules for monitoring catalytic activity on a localized basis in an SCR unit, methods of on-line monitoring of SCR catalyst activity utilizing such modules, and SCR units that contain such modules, all either reducing or eliminating the deficiencies of the prior art methods. Each module is sized to extend over a lateral area of a catalyst layer that is small relative to the full area of the layer as well as the cross section of the gas flow stream through the SCR reactor and includes a pair of sampling probes for drawing samples from the gas stream traversing the area both upstream and downstream of the catalyst plus a reductant supply probe for directing a fresh reductant stream to the area. Suitable reductants are ammonia gas, a mixture of ammonia and air, and aqueous urea. The module is constructed and mounted in such a way that it does not disrupt, block, or interfere with the bulk flow through the SCR unit, and can be activated and deactivated at will without shutting down the unit. The reductant is fed through the reductant supply probe at a rate sufficient to achieve an excess (on a mole basis) of reductant over the NOx entering the catalyst area that the module is positioned over, while the samples from the sampling probes are directed to analyzers and a data processing unit that determine the NOx levels in each probe and calculate the catalyst activity from the difference in NOx levels and the area flow rate according to the following relation, which is derived from Equation (1) above:
K=Avln(1−ΔNOx) (3)
In preferred embodiments of the invention, the module further includes a temperature sensor and, in certain embodiments, a gas velocity sensor. Further modules within the scope of the invention also include an air inlet for blowing soot from the catalyst in the module area, and miscellaneous flow control components such as an ammonia injection grid when ammonia is used as the reductant, the grid is sized to distribute the added ammonia over the catalyst in the module area, a static mixer to promote uniform mixing of the added reductant into the gas stream in the module area, and lateral barriers or shrouds sized to surround the catalyst to prevent the divergence of gas flows from the catalyst area to adjacent areas or vice versa.
In preferred embodiments as well, the SCR unit contains two or more, and in general a plurality, of these test modules distributed at strategic locations across the width of a single catalyst layer or among different catalyst layers, or both, to provide localized analyses at different locations. With a plurality of modules, a common source of reductant and a common analyzer for all modules can be used, with appropriate switching valves for supplying reductant and drawing samples from individual modules in sequence, either periodically or at the will of the operator. In still further embodiments, the modules are mounted on a movable support permitting lateral movement or re-positioning of individual modules to achieve localized activity information at various locations from a single module.
The modules, methods and systems of the present invention permit the monitoring of the catalyst activity to be performed independently of any outage schedule for the SCR unit or the facility as a whole and without interfering with the operation of the unit or the facility. Further advantages, embodiments, and objects of the invention will be apparent from the description that follows.
The terms “reactor” and “SCR unit” are used interchangeably to refer to a continuous flow-through reactor in which an NOx-containing gas is combined with ammonia and contacted with catalyst to undergo any of various reactions in which the nitrogen in the NOx is reduced to molecular nitrogen.
The term “solid catalyst layer” as used herein denotes a body of catalyst in solid form, either as a bed of catalyst particles or a unitary piece of solid catalytic material, that is immobile and substantially flat, with lateral dimensions that significantly exceed its thickness, and contains pores or though-passages that allow the NOx-containing gas to flow through the body of catalyst in intimate contact with the catalyst surface area. When the catalyst is in particulate form, the particles can be retained on a tray or mesh support, and when the catalyst is a unitary block of material such as a honeycomb ceramic block or a stack of plates with corrugated profiles, the block or stack of plates can be supported in the reactor by beams, support grids, or other conventional construction components. Typically, the catalyst layer will span the cross section of the SCR unit, forcing the gas stream to pass through the catalyst layer in intimate contact with the catalyst and preventing bypass.
The terms “lateral,” “lateral area,” and “laterally delineated section” as used herein refer to spatial regions of the internal volume of the reactor, and denote the dimensions or the extremities or boundaries of these regions along the x- and y-axes, i.e., the axes that are transverse to the direction of gas flow through the reactor (which is referred to herein as the z-axis). When used in reference to a section of a catalyst layer, these terms refer to the lateral dimensions of the section rather than the thickness of the layer. While the spatial regions referred to will generally be occupied by catalyst, the word “area” when included in these terms does not refer to the surface area of the catalyst.
The terms “upstream” and “downstream” as used herein refer to locations relative to the direction of gas flow through the reactor.
The term “substantially parallel flow direction” as used herein in reference to a gas flow stream denotes a stream that is substantially both non-diverging and non-converging along its direction of flow.
The term “ammonia gas” is used herein to include both undiluted ammonia and ammonia mixed with air or an inert gas such as nitrogen. In the preferred practice of this invention, the ammonia will be fed as a mixture with air, at proportions ranging from about 1% ammonia by volume to about 80% ammonia by volume, or more preferably from about 5% to about 60%.
The term “aqueous urea” is used herein to mean urea dissolved in water. In the preferred use of aqueous urea in the practice of this invention, the aqueous urea will contain from about 1% to about 50% urea by weight, or more preferably from about 2% to about 25% by weight, and will be sprayed into the flue gas through an atomizer.
The term “selectively strike” as used herein in reference to an air or gas stream directed to a section of the catalyst bed denotes that the entire stream is confined to the area with the lateral extremities of the section and does not diverge outside those extremities.
The terms “a” and “an” as used herein mean “one or more,” and are therefore broader in scope than the term “plurality.”
While this invention is capable of implementation in a wide range of constructions, applications, and embodiments, a thorough understanding will be gained by a detailed examination of a specific embodiment. Such an embodiment is shown in the drawings and explained below.
The ammonia supply probe 17 is a component of the module, and in the embodiment shown in the Figure the probe incorporates an ammonia injection grid and is positioned directly upstream of (above) the designated area 14 of the catalyst bed in which the activity determination is to be performed. The probe and grid are selected and arranged to produce an ammonia stream that selectively strikes the designated area 14 and preferably strikes substantially the entire area. The height of the probe and grid above the catalyst bed will vary depending on the grid configuration and any other components included in the module. In most cases, a height of from about 1 foot to about 8 feet (0.3 to 2.4 meters), and preferably from about 2 feet to about 6 feet (0.6 to 1.8 meters), will provide the best results, depending on any additional components that might be placed between the grid and the catalyst surface.
The inlet sampling probe 21 is likewise positioned upstream of the designated area 14 of the catalyst bed, and the outlet sampling probe 22 is positioned downstream of the designated area. In this embodiment, the inlet sampling probe 21 is positioned upstream of the ammonia injection grid 17 to assure that the analysis of the sample drawn through this probe is representative of the gas stream flowing through the unit at that level. Both sampling probes preferably include a filter incorporated into the probe to prevent soot or solid matter in general from entering the lines leading to the analyzer(s).
The mounting structures 23, 24 for the ammonia supply probe and grid 17 and for the inlet and outlet sampling probes 21, 22 and all other components of the module are any conventional supports, beams, frames, brackets, or the like that will secure the components in place without disrupting or interfering with the gas flow through the SCR unit as a whole. The mounting structures may range from simple angle irons to which the components are bolted or welded in fixed positions, to rails along which the components are slid so that they can be positioned at different locations along a particular catalyst layer. The mounting structures can be combined to make the module a unitary piece of equipment with all components attached, or they can be individual beams or rails for individual components of the module. Accordingly, the module can be manufactured as a separate piece of equipment or constructed as part of the SCR unit itself from individual components.
Further components for optional, and in certain cases preferred, inclusion in a module of the present invention, as mentioned above, are a temperature sensor, a soot blower, a flow rectifier to guide the NOx-containing gas entering the module into a substantially parallel flow direction, a static mixer downstream of the ammonia probe and ammonia injection grid to promote the uniform mixing of the ammonia with the gas flow stream, and a shroud or lateral enclosure wall as further assurance against lateral diffusion of gases or interfering materials between the catalyst area addressed by the module and adjacent catalyst areas. These optional components can be included individually or in any combination, and all can be mounted to module by conventional mounting fixtures.
In the embodiment shown in
The module of
A still further component shown in the module of
Also included as part of the module of
The number of modules used in a single SCR unit is not critical to the invention and can vary. Preferably, a plurality of modules are used so that localized catalyst activity can be monitored at different sites along the flow path of the gas being treated in the unit. Movable moldules, as described above, can also serve to provide localized monitoring data over wide areas. Typical configurations of the catalyst layers in an SCR unit are shown in
The peripheral equipment and components used in association with the modules of the present invention are conventional components that are known in the boiler and power plant industry and readily available from commercial suppliers. The primary peripheral comments include pumps for drawing samples through the sample probes, flow controllers for the supply lines for ammonia and air, NOx analyzers, and, if desired, oxygen analyzers. For NOx analyses other than by the use of the portable analyzers mentioned above, chemiluminescence NOx analyzers are of particular interest. Examples are Brand-Gaus Chemiluminescence NOx Analyzers (Brand-Gaus, LLC, Pflugerville, Tex., USA), ECO PHYSICS Chemiluminescence NOx Analyzers (ECO PHYSICS, INC., Ann Arbor, Mich., USA), and Environmental Analytical Systems' Model 400 CLD and Model 400 HCLD Chemiluminescent NO/NOx Analyzers (Environmental Analytical Systems, Barry's Bay, Ontario, Canada). Analyzers for molecular oxygen are also included in certain embodiments of the invention for the purpose of detecting leaks in the sampling system. Examples of oxygen analyzers are the Series 800 Zirconia Oxygen Analyzer of Illinois Instruments, Inc. (Johnsburg, Ill., USA), the Integrated Type In Situ Zirconia Oxygen Analyzer Model ZR202G of Yokogawa Corporation of America (Newnan, Ga., USA), and the CGA351 Zirconia Oxygen Analyzer of GE Panametrics (Gymea, New South Wales, Australia).
Monitoring systems in accordance with this invention can be designed for manual operation or automated operation. Manually operated systems will be those with manually controlled sample pumps, manually controlled analyzers, and manual controls in general for energizing individual modules or positioning movable modules. An example of an automated system for six test modules in a single SCR unit is shown in
The system of
The monitoring of localized catalyst activity with the use of the modules described above can be performed while the SCR unit is in full operation, and is preferably performed while the unit is operating at full load. The typical SCR unit has either two, three, or four catalyst bed layers, each layer being approximately 40 to 60 square feet (3.7 to 5.5 square meters) in lateral area and approximately 3 feet (1 meter) in depth. A typical gas velocity through an SCR unit is approximately 15 feet per second (4.6 meters per second) at an operating temperature of approximately 700° F. (370° C.). A presently preferred module area is a section that is square in shape with each side measuring 2 feet (0.61 meter) in length. The amount of ammonia fed to the module to pass through the catalyst area covered by the module will be any amount that is in molar excess relative to the NOx entering the catalyst at that area. The amount of NOx entering the area is readily determined by analysis of a sample drawn the inlet sampling probe, thereby allowing a determination of the appropriate amount of ammonia feed. As noted above, molar ratios in excess of 1.0 are preferred. In a presently preferred method, a mixture of ammonia and air at an air: ammonia volume ratio of 20:5 is fed at a rate of 0.08 lb/min (0.36 g/min) upstream of the first catalyst layer. For a multi-layer catalyst system, the optimal amount of ammonia will vary with the layer that the module is positioned to monitor.
It is further preferred that the reactions in the module be allowed to stabilize before monitoring data is taken. The ammonia feed will thus be allowed to continue for several minutes, perhaps 10 to 20 minutes, following its initiation, before the resulting data is used for activity monitoring purposes. Variations of these procedures will be made at the discretion of the operator according to the needs of the particular system. The optimum procedure for any system will be readily determinable by routine tests that are within the skill of the average engineer or system operator.
An example of a three-layer SCR unit is one that has flue gas flowing through the unit at a space velocity of 2,500 hour−1 (the volumetric flow rate of the gas at standard temperature and pressure divided by the catalyst volume) and a linear gas velocity of 15 ft/sec (4.6 m/sec), and whose inlet NOx level is 0.41 lb/106 Btu (300 ppm at 3% 02), whose inlet NH3/NOx mole ratio is 0.9, and whose temperature is 700° F. (370° C.). The gas flowing across the individual catalyst layers has the following composition parameters:
With modules on each of the three layers, each module being 2 feet square (0.4 square meter), the ammonia added to the module in each layer is as follows:
The foregoing is offered primarily for purposes of illustration. Further modifications, substitutions, and variations that still utilize the central concepts of the invention will be readily apparent to those skilled in the art.
This application is related to U.S. Provisional Patent Application No. 60/571,100, filed May 14, 2004, and claims all benefits legally capable of being offered by the provisional patent application. The entire contents of the provisional patent application are incorporated herein by reference.
Number | Date | Country | |
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60571100 | May 2004 | US |