Systems and method for SO.SUB.3 .mitigation at high temperature injection locations

Abstract

Systems and methods for the use of highly reactive hydrated lime (HRH) in high temperature flue gas streams, namely those at greater than 400° F., such as are present before an air preheater (APH) to remove sulfur trioxide (SO.sub.3) from the flue gas.

Claims

1. A method for removal of sulfur trioxide from a flue gas, the method comprising: providing a flue gas duct including, in downstream order, a selected catalytic reduction (SCR) system, an air preheater (APH), a particulate collector selected from the group consisting of: a fabric filter baghouse (BH) or an electrostatic precipitator (ESP), a flue gas desulfurization (FGD) unit (109), and an exhaust stack (111); and after said SCR and prior to said APH, injecting a dry highly reactive lime hydrate (HRH) into said flue gas; wherein said HRH has: an available calcium hydroxide concentration of greater than 92%; a D90 of less than or equal to 10 microns and greater than or equal to 4 microns in size; a ratio of D90 to D10 of less than 8; and said particles having a BET surface area of about 18 m.sup.2/g or greater;  wherein a temperature of said flue gas at said injection is greater than 400° F.; and  wherein said injection after said SCR and prior to said APH is the only injection of lime hydrate into said flue gas duct.

2. The method of claim 1 wherein said temperature is greater than 550° F.

3. The method of claim 1 wherein said temperature is greater than 600° F.

4. The method of claim 1 wherein said HRH is injected at a rate of less than 1750 lb/hr and the SO.sub.3 level of the flue gas after injection is less than 45 ppm.

5. The method of claim 1 wherein said HRH is injected at a rate of less than 1750 lb/hr and the SO.sub.3 level of the flue gas after injection is less than 25 ppm.

6. The method of claim 1 wherein said HRH is injected at a rate of less than 1750 lb/hr and the SO.sub.3 level of the flue gas after injection is less than 20 ppm.

7. The method of claim 1 wherein the ratio is less than about 6.

8. The method of claim 1 wherein the ratio is between about 4 and about 7.

9. The method of claim 1 wherein the ratio is between about 5 and about 6.

10. The method of claim 1 wherein the D90 is less than or equal to about 8 microns and greater than or equal to about 4 microns.

11. The method of claim 1 wherein the D90 is less than or equal to about 6 microns and greater than or equal to about 4 microns.

12. The method of claim 1 wherein the D90 is less than or equal to about 5 microns and greater than or equal to about 4 microns.

13. The method of claim 1 wherein the particles have a BET surface area of about 20 m.sup.2/g or greater.

14. The method of claim 1 wherein a D50 less than or equal to about 4 microns.

15. The method of claim 1 wherein a D50 less than or equal to about 2 microns.

16. A method for removal of sulfur trioxide from a flue gas, the method comprising: providing a flue gas duct including, in downstream order, a selected catalytic reduction (SCR) system, an air preheater (APH), a particulate collector selected from the group consisting of: a fabric filter baghouse (BH) or an electrostatic precipitator (ESP), a flue gas desulfurization (FGD) unit (109), and an exhaust stack (111); and after said SCR and prior to said APH, injecting a dry lime hydrate into said flue gas; wherein said HRH has: an available calcium hydroxide concentration of greater than 92%; a D90 of less than or equal to 10 microns and greater than or equal to 4 microns in size; a ratio of D90 to D10 of a less than 8; and said particles having a BET surface area of about 18 m.sup.2/g or greater; wherein a temperature of said flue gas at said injection is greater than 400° F.; and wherein said lime hydrate reacts with SO.sub.3 in-flight in said flue gas duct prior to said particulate collector; and wherein said lime hydrate reacts with SO3 in-flight in said flue gas duct prior to said particulate collector; and wherein said lime hydrate injected after said SCR and prior to said APH is the only injection of lime hydrate into said flue gas duct and is injected at a rate of less than 1750 lb/hr and the SOs level of the flue gas prior to the particulate collector is less than 45 ppm.

17. The method of claim 16 wherein said temperature is greater than 550° F.

18. The method of claim 16 wherein said SO.sub.3 level of the flue gas prior to the particulate collector is less than 20 ppm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 provides a conceptual block diagram of an embodiment of a flue gas duct system as may be used in, for example, a coal fired power plant.

(2) FIG. 2 provides a table illustrating increased reduction of SO.sub.3 with a high reactivity lime hydrate compared to a more traditional hydrated lime composition.

(3) FIG. 3 provides a conceptual block diagram of an embodiment of a flue gas duct system using Hot-Side ESP as may be used in, for example, a coal fired power plant.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

(4) While most flue gas scrubbing systems are commonly focused on making sure that certain materials do not leave the flue stack and disperse in the air for environmental reasons, there are a number of benefits for removing SO.sub.3 earlier in the process. FIG. 1 shows a loose block diagram of an arrangement of a flue gas duct system such as can be used in a coal fired power plant. Generally, major components include the boiler (101), a selected catalytic reduction (SCR) system for reducing NO.sub.x emissions (103), an air preheater (APH) (105), particulate collector (107) such as, but not limited to, a bag house or electrostatic precipitator (ESP), a Flue Gas Desulfurization (FGD) unit (109), and then the exhaust stack (111). Hydrated lime is typically injected after the APH (105) and prior to the ESP (107) at point (205), or prior to the FGD (109) at point (203) for SO.sub.3 reduction. The latter is contemplated, for example, in U.S. Utility patent application Ser. No. 10/315,837, the entire disclosure of which is herein incorporated by reference. There is, however, indications that it would be desirable to provide treatment of flue gases prior to the APH (105) at point (201). In a first instance, such a location clearly provides for earlier (and therefore increased) corrosion protection from SO.sub.3 interacting with components of the flue system downstream from the injection point (201). Secondly, earlier treatment provides capture of SO.sub.3 prior to injection of a mercury sorbent. The presence of high amounts (greater than 5 ppm SO.sub.3) at a mercury sorbent injection site will negatively affect the mercury capture rate of the sorbent, at an economic disadvantage. Further, a reduced SO.sub.3 content in the flue gas at the APH (105) outlet (e.g. point (205)) allows the user to reduce the outlet temperature of the APH (105). This means that more heat can be recaptured in the APH (105) and returned to the boiler (101). This improves efficiency in the furnace (heat rate), offering a cost savings on fuel. A reduced fuel consumption for the same power generation (improved heat recapture), also creates a cascade effect of further reducing emissions as less SO.sub.3 is generated in the first place.

(5) One of the primary reasons to want to reduce SO.sub.3 concentration earlier in the process is that controlling SO.sub.3 prior to the APH (105) inlet at point (201) will reduce instances of forced outages for APH (105) cleaning due to Ammonium Bisulfate (AbS) buildup in the APH (105). Ammonia is typically injected in the SCR (103) for NO.sub.x reduction. However, lack of full efficiency at the SCR (103) and a desire to run a slight excess of ammonia generally yields excess ammonia (commonly referred to as “ammonia slip”) in the flue gas exiting the SCR (103). This ammonia then reacts with SO.sub.3 to produce ammonium bisulfate. While this reaction helps to reduce the acid gas concentration in the flue gas by reacting out SO.sub.3, it creates an additional problem. Ammonium bisulfate is gaseous at temperatures prior to the APH. However, in the APH (105) the ammonium bisulfate will condense and solidify in the APH (105) internals as those internals cool. This will often form a sticky residue that clogs the APH (105), causes a pressure buildup, and eventually requires downtime for cleaning to allow for improved air passage.

(6) However, injection of hydrated lime prior to the APH (105) is considered a high temperature injection (that is, greater than 400° F.) location which was seen as presenting its own concerns. As the purpose of the APH (105) is to recapture heat in the flue gas for improved efficiency, the flue gas entering an APH (105) is generally at a much higher temperature than that leaving the APH (105). Sorbent injections prior the APH (105) typically did not use hydrated lime, but focused on use of sodium bisulfate (soda ash) or trisodium hydrogendicarbonate dihydrate (trona), to insure that the reaction was complete prior to the gas going into the APH (103).

(7) With the development of a highly reactive lime hydrate (HRH) with properties designed to significantly improve the speed of reaction with acid gases present in flue gas, it became a possibility that HRH may be useable at a high temperature injection point (201) prior to the APH (105). HRH can be manufactured in accordance with a number of processes, but is contemplated herein as material manufactured in accordance with, and having the properties discussed in, U.S. patent application Ser. Nos. 14/180,128 and 14/289,278, the entire disclosure of both of which is herein incorporated by reference. HRH is notably different from other hydrated lime as it has an improved removal rate of acidic pollutants present in the flue gas where the sorbent is delivered and the rate of removal is generally substantially higher. The use of a high purity, highly reactive hydrated lime such as HRH will have faster neutralization of acidic species.

(8) While it may be provided in a variety of forms, in an embodiment, the HRH is a dry solid free of excess moisture. The product used may be described by having citric acid reactivity of less than 15 sec, preferentially less than 10 sec, optimally less than 7 sec. The product used may also be described by having available calcium hydroxide concentration of greater than 92% wt, preferentially greater than 94%, and optimally greater than 95%. The product used may also be described by having at least 90% of particles less than 10 microns, preferentially less than 8 microns. At least 50% of the particles are less than 4 microns, preferentially less than 3 microns. The product may also be described as having a BET surface area of at least 18 m.sup.2/g, preferentially at least 19 m.sup.2/g, 20 m.sup.2/g, or 30 m.sup.2/g.

(9) HRH is generally used as part of dry sorbent injection system into the off gas of an industrial plant, incinerator, or boiler that combusts sulfur and/or halogenated fuels. The dry sorbent system consists of a storage silo, feed valve, and a means of conveyance of the product that could use pressurized gas or vacuum. The conveying gas/hydrate mixture is conveyed within a pipe and fed into the flue gas stream to be treated. There can be one or multiple feed points into the flue gas. The hydrated lime can be injected at temperatures below 2400° F. for capture of SO.sub.2. The hydrated lime can be injected at temps below 1100° F. for capture of SO.sub.3 and/or halogenated acids.

(10) The reactivity enhancement of HRH is beneficial especially when the end user can capitalize on the hydrated lime's ability to rapidly neutralize the acid gases in flight, i.e., prior to forming a bed upon a bags of a fabric filter or plates of an electrostatic precipitator (ESP). This is commonly the case with injection prior to the APH (105). The use of high purity, highly reactive hydrated in high temperature (greater than 370° or 400° F.) applications leads to significantly improved neutralization of acidic components of flue gas. The removal rates are improved even when compared to the typical benefits seen when injecting high purity, highly reactive hydrated lime at lower temperatures (less than 370° F.).

(11) In an exemplary embodiment, a coal fired boiler (101) equipped with an SCR (103), APH (105), ESP (107), and FGD (109) used hydrated lime to control SO.sub.3/H.sub.2SO.sub.4 emissions. The unit was fed and evaluated using both HRH and conventional hydrated lime injected at the outlet of the SCR (103) and prior to the APH (105) (e.g. point (201)), where flue gas temperature generally averages greater than 600° F. A dew point monitor was used to determine the flue gas dew point, and by extension sulfuric acid/ammonia bisulfate content when using each of the different type of hydrated lime. At varying feed rates and varying unit loads, the HRH exhibited exceptional performance compared to the conventional (traditional) hydrated lime.

(12) The results are shown in FIG. 2 which makes apparent that at high temperatures (namely temperatures greater than 400° F. and preferably greater than 550° F.), there was an un-expectedly larger reduction in SO.sub.3 than in cold (below 400° F.) applications. Use of HRH at a low temperature injection location, namely post APH (105) at point (205) where the temperature is less than 400° F., has been previously shown to provide for only a reduction of about 30% in use over conventional hydrated lime, while in the high temperature location the reduction could be more than double. These results are partially tabulated in Table 1 below which shows the different feed rates and relative reductions of SO.sub.3:

(13) TABLE-US-00001 TABLE 1 Traditional Standard Standard Hydrated Deviation HRH Deviation Lime of SO.sub.3 Average of Feed Rate Average SO.sub.3 (Traditional) SO.sub.3 SO.sub.3 (HRH) Between 1250 49 ppm SO.sub.3 20 23 ppm SO.sub.3 ±12 and 1750 lb/hr Over 1750 lb/hr 45 ppm SO.sub.3 18 17 ppm SO.sub.3 ±8

(14) HRH also appears to have a maximum in-flight removal of SO.sub.3 within a short period of time specifically less than 3 seconds. Compared to conventional hydrate, near maximum reduction levels are attained within a much shorter time as illustrated in the following Table 2. Table 2 provides that the lime injection occurs at the SCR (103) outlet allowing the entire distance from the SCR (103) to the APH (105) to be used for reaction. The amount of SO.sub.3 was then determined at the APH (105) inlet and at the APH (103) outlet indicating how much more reaction occurred in the APH (105).

(15) TABLE-US-00002 TABLE 2 Additional Average Additional Average SO.sub.3 Removal SO.sub.3 Removal APH inlet APH inlet to APH outlet to APH outlet Feed Rate (Traditional) (HRH) Less than 1250 lb/hr 10 ppm SO.sub.3 4 ppm SO.sub.3 Between 1250 and 31 ppm SO.sub.3 8 ppm SO.sub.3 1750 lb/hr Greater than 1750 lb/hr 33 ppm SO.sub.3 5 ppm SO.sub.3

(16) The relatively small amount of additional reduction in SO.sub.3 between the APH inlet and APH outlet when HRH is used indicates that HRH as a sorbent is significantly exhausted by the time it reaches the APH (105). Thus, the reaction time is completed substantially during the flue gas's presence between the SCR (103) and APH (105).

(17) While not intending to be bound by any particular theory of operation, competing reactions with carbon dioxide and, to a lesser extent, SO.sub.2 are believed to contribute to the loss in effectiveness of any hydrated lime in its targeted reaction with SO.sub.3 which is being measured here, Additionally, the effectiveness of the sorbent conveying and flue gas distribution system factors into the amount of excess sorbent that is necessary to meet emissions targets. This is why the further reduction will likely never be zero. However, the data show that HRH is much more effective that traditional lime at reducing SO.sub.3 concentration in high temperature or pre-APH (105) applications.

(18) While the above has focused on a particular layout of flue gas duct components, FIG. 3 provides for an alternative arrangement of flue duct with the particulate collector (107) (generally an ESP in this arrangement) is positioned prior to the APH (105). This arrangement is often referred to as “Hot Side ESP”. In this arrangement, the HRH will typically be injected at point (211) between the ESP as opposed to points (217) or (213) and is believed to provide for a similar unexpected reduction as contemplated above.

(19) The use of HRH can also provide for reduced variation in sulfuric acid content of the flue gas. Coal-fired boilers experience fluctuations in SO.sub.3 content based on a variety of factors, including coal sulfur content, SCR (103) catalyst variability, iron content of coal, and changes in load. These variations can cause significant swings in content of flue gas acids which may require additional downstream control mechanisms or overly conservative operating conditions and/or feed rates of the sorbents used to minimize the SO.sub.3 levels.

(20) HRH can also provide benefit where a user needs to achieve high level removal in a short time and does not have the luxury of a long duct run. This can be particularly valuable where there is co-injection with a mercury sorbent where SO.sub.3 must be removed prior to the mercury sorbent, and in applications with a short residence time prior to a small ESP (e.g. where point (205) is part of a short duct).

(21) If a site with a short residence at point (205) has to reduce acid gas to a predetermined level, a more reactive hydrate requires 10-30% less sorbent. In many cases, units have to feed a stoichiometric ratios well beyond equimolar (1 mole hydrated lime/1 mole SO.sub.3) or even industry typical (3-5 mole hydrated lime/1 mole SO.sub.3); as much as 6-10 mole hydrated lime/1 mole SO.sub.3. A hydrate that is able to more effectively capture acid gas in a short span will reduce ash loading on the ESP from unreacted material.

(22) While removal rates for traditional lime are generally constant across temperature ranges, HRH removal rates are unexpectedly better at high temperatures. While HRH is expected to have a better removal rate across residence times (as it is simply more reactive), comparatively the HRH removal rate performance difference increases as the residence time is reduced providing yet another unexpected result. Further, HRH is unexpectedly more efficient at low stoichiometry ratios as compared to traditional hydrated lime. Not only does the aggregate removal rate improve at high temperatures with the use of HRH as compared to traditional lime but the standard deviation of the remaining acid gas content is also reduced more than expected.

(23) While the invention has been disclosed in conjunction with a description of certain embodiments, including those that are currently believed to be the preferred embodiments, the detailed description is intended to be illustrative and should not be understood to limit the scope of the present disclosure. As would be understood by one of ordinary skill in the art, embodiments other than those described in detail herein are encompassed by the present invention. Modifications and variations of the described embodiments may be made without departing from the spirit and scope of the invention.

(24) It will further be understood that any of the ranges, values, properties, or characteristics given for any single component of the present disclosure can be used interchangeably with any ranges, values, properties, or characteristics given for any of the other components of the disclosure, where compatible, to form an embodiment having defined values for each of the components, as given herein throughout. Further, ranges provided for a genus or a category can also be applied to species within the genus or members of the category unless otherwise noted.