### The Rapid Growth of Composites in Flue Gas Desulfurization (FGD) Processes

Don Kelley Ashland Performance Materials 5200 Blazer Parkway

Dublin, OH 43017

ABSTRACT

The demand for corrosion resistant compos ites made from epoxy vinyl ester resins increased significantly starting in 2006 when nickel prices increased from $6/lb to $15/lb. This price increase continued in 2007 when nickel hi t a high of $24/lb. With a 30-year reputation for low maintenance and relatively stable cost, fibe rglass reinforced plastic (FRP) provides process engineers with a reliable, cost effective constr uction material that can be employed in numerous applications that are corrosive to stainless steel at a price much lower than high alloy clad steel. Although some other materials may be cost compe titive with FRP, their use typically results in higher life cycle costs due to maintenance.

The purpose of this paper will be to compar e FRP with high nickel alloy and austenitic stainless steel in “wet process” Flue Gas Desulfurization (FGD) environments. Relative cost and corrosion data will be presented to provide the information nece ssary for process engineers to facilitate future decisions concer ning material of construction.

Keywords: corrosion, desulfurization, epoxy vinyl este r resin,, fiberglass-reinforced, flue gas, high nickel alloy, plastic, reinforced thermo set plastic, sulfuric, vinyl ester resin

INTRODUCTION

The cost of high nickel all oys increased significantly in 2006 and 2007, making corrosion resistant process equipment made with high nick el alloy very expensiv e relative to other materials. This has created a great demand for alternative, less expensive materials that have similar corrosion resistance. Prior to 2006, high nick el alloy was the materi al of choice for many “wet process” FGD environments found in coal fired electric power plan ts. These environments often contain high chloride and fluoride levels th at are highly corrosive to stainless steel.

1Since FGD construction is expected to con tinue at current levels to 2015 and beyond, there will be a significant need for new corrosion re sistant equipment in these plants. The cost of new equipment will depend greatly upon the material s of construction. Materials such as high nickel alloy is expensive, and has created a demand for less expensive materials with proven performance in wet FGD processes such as FRP.

FRP has a long history of success in wet FGD processes that are highly corrosive to stainless steel. Typical applications include stack liner, lime slurry piping and low pH/ high chloride scrubber systems. FGD equipment made from FRP is re latively inexpensive and case histories supporting its use date back to 1973 an d support its successful use in FGD applications.

Alternative materials for wet FGD environments , in addition to high nickel alloy, include austenitic stainless steel, rubber-lined carbon steel, acid bric k-lined carbon steel, and resin-coated carbon steel, which can be used in wet FGD envi ronments. However, these materials do not all have the same service life expectancy, nor do they have the same cost. In this paper, FRP will be used as a reference material compared to other materials for service life and cost in FGD

processes.

FRP COST VERSUS OTHER MATERIALS OF CONSTRUCTION

With the rising cost of nickel, FRP has become a very competitive material of construction. The total installe d cost for FRP ranges from about $100 to $150 per sq uare foot in North America (prices may vary in other countries). It is less expensive than 2205 stainless steel (Table 1) and much less expensive than C-276 a lloy clad carbon steel an d has a longer service life in high chloride and fluoride applications

TABLE 1 COST COMPARISON OF CONSTRUCTION MATERIALS*

Construction Material Installed Cost Cost Ratio

Shop Fabricated FRP $100 / Sq. Ft. 1.00

Field Fabricated FRP $150 / Sq. Ft 1.50

2205 stainless steel 1⁄4 inch plate $188 / Sq. Ft. 1.88

C-276 clad carbon steel $330 / Sq. Ft. 3.30

*Cost obtained from a major FRP supplier in North America.

2FRP CHEMICAL RESISTANCE VERSUS METALS

Chemical resistance is a key pr edictor of service life in wet FGD processes. Compared to metals (Table 2), FRP made from epoxy vinyl ester resin has as good or better chemical resistance than Alloy C-276 and is superior to 2205 stainless steel. FRP has unusual resistance to chlorides and is superior to all oys in high chloride environments. Based on more than 30 years of experience and testing in wet FGD processes, FRP made from epoxy vinyl ester resin has the chemical resistance necessary for long-term service life.

TABLE 2 EPOXY VINYL ESTER RESIN CHEMICAL RESISTANCE COMPARED TO METAL

Materials Sulfuric Acid Hydrochloric Acid Acid Chloride Salts

FRP made with epoxy vinyl ester resin 100 ° C to 30% 80 ° C to 15% 100 ° C All conc.

2205 Stainless Steel 30 ° C to 30% 60 ° C to 1% 65 ° C to 2000 ppm @ low Ph

Alloy C-276 100 ° C to 30% 80 ° C to 15% 65 ° C to 50M ppm @ low Ph

FIBERGLASS-REINFORCED PLASTIC (FRP)

FRP is a laminate of E-glass fiber and ther moset resin as shown in Figure 1. Corrosion resistant FRP is made from a premium thermo set resin. The corrosion barrier (CB), on the process side of the laminate, has high resin cont ent for corrosion resistance. The structural layers have high glass content for strength and stiffness.

Exterior “Top Coat” or

FIGURE 1: Typical Corrosion Resi stant FRP Laminate Construction 2 Ply 1.5 oz./ft. 2 Glass Mat 75% Resin

0.25 mm Veil 90% Resin Veil as Required

One Mat Ply or More for Corrosion Allowance as Required

Corrosion Barrier Portion (CB) Structural Portion Mat Alternating with 

### Process Side Woven Roving or Filament Winding as Required

2.7 mm (100 mils) minimum 6.4 mm (250 mils) minimum thickness E-glass or ECR glass

3For most wet applications, the maximum operating temperature is 100 o C (212 o F) with excursions up to 120 o C (248 o F). Dry environments can operate at 177°C (350°F) with excursions up to 204°C (400°F). Because not all resins are suitable for processes that have thermal cycling or high temperature excursions, it is important to consult the resin manufacturer when choosing a resin for these types of applications.

FRP GROWTH IN WET FGD APPLICATIONS

The rapid growth of FRP in wet FGD proce sses is clearly shown in Table 3. In 2004 and 2005, only eight stack liner projects were kicked off. Thirty eight were kicked off in 2006, forty nine in 2007, and so far thirty nine are scheduled for 2008.

TABLE 3 – FRP STACK LINERS WITH KICKOFF DATES FR OM 2004 TO 2008

Utility Station/Location Kick off Year Progress Energy Asheville #1,2/Arden, NC 2004 AEP Mitchell #1,2, Moundsville, WV 2004 WE Energies Pleasant Prairie, WI 2004

Dominion Chesterfield #6, Chester, VA 2005 Progress Energy Roxboro #3, Semora, NC 2005 DP&L Stuart #3, Aberdeen, OH 2005

PPL Montour #1,2, Washingtonville, PA 2005 AEP Mountaineer, New Haven, WV 2005 Southern Bowen #4,Cartersville, GA 2006

TVA Bull Run #1, Clinton, TN 2006 Duke Power Belews Creek #2, Walnut Cove, NC 2006 AEP Amos #3, Winfield, WV 2006 AEP Cardinal #1, Brilliant, OH 2006 AEP Cardinal #2, Brilliant, OH 2006 DP&L Stuart #2, Aberdeen, OH 2006 Indianapolis P&L Harding Street #7, Indianapolis, IN 2006 Kentucky Utilities Ghent #3, KY 2006 Progress Energy Roxboro #4, Semora, NC 2006 Southern Gorgas #8,9,10, Parrish, AL 2006 Duke Power Belews Creek #1, Walnut Cove, NC 2006 Progress Energy Roxboro #1, Semora, NC 2006 AEP Amos #1, Winfield, WV 2006 PPL Brunner Island #3, York Haven, PA 2006 Ohio Edison Sammis #6, Stratton, OH 2006 Allegheny Energy Hatsfield Ferry #1,2, Masontown, PA 2006 AEP Amos #2, Winfield, WV 2006 AEP Muskingum River #5, Waterford, OH 2006 Duke Power Allen #1-5, Belmont, NC 2006 Kentucky Utilities Ghent #2, KY 2006

WE Energies Elm Road #5,6, WI 2006 Alcoa Warrick #2,3, Newburgh, IN 2006 Indianapolis Power & Light Petersburg #3, Indiana 2006

Cinergy/PSI Energy, Inc. Gibson #1, 2, & 3, Owensville, IN 2006

4Utility Kick Station/Location off Year Dayton Power & Light J.M. Stuart Unit 1,2,3,& 4 Aberdeen, OH 2006 DTE Energy Monroe Units 3 & 4, Monroe, MI 2006 Duke Energy Belews Creek #1, & 2 2006 PPL Corporation Montour Station Washingtonville, PA 2006

Santee Cooper Winyah #1 & 2 2006 Southern Company Alabama Power E.C. Gaston Unit 5 Wilsonville, AL 2006 Southern Company Alabama Power Gorgas Units 8, 9, & 10 Parrish, AL 2006 Southern Company Georgia Power Bowen #1 & 2, Cartersville, GA 2006 TVA Bull Run, Tennessee 2006 We Energies Elm Road #1 & 2, Oak Creek, WI 2006 Allegheny Energy Greensberg, PA Hatfield's Ferry Units 1,2,3 Masontown, PA 2006 AmerenUE, St Louis Sioux Power Plant, West Alton, Missouri 2006 AEP Conesville #4, OH 2007 DP&L Stuart #1, Aberdeen, OH 2007 Kentucky Utilities Ghent #1, KY 2007 Lower CO River Auth. Fayette #1, LaGrange, TX 2007 Lower CO River Auth. Fayette #2, LaGrange, TX 2007 Ohio Edison Sammis #1-4, Stratton, OH 2007 Progress Energy Roxboro #2, Semora, NC 2007 Southern Wansley #1, 2, Roopville, GA 2007

Alcoa Warrick #1,4, Newburgh, IN 2007 Detroit Edison Monroe #3, 4, MI 2007

Ohio Edison Sammis #7, Stratton, OH 2007 Basin Electric Coop. / Sargent Lundy Leland Olds Units 1 & 2, Stanton, ND 2007 Cinergy/PSI Energy, Inc. Div. Cayuga #1, & 2,Terre Haute, IN 2007 Cinergy/PSI Energy, Inc. Div. Miami Fort Units 7 & 8, North Bend, OH 2007 CPS Energy J.K. Spruce Plant Unit 2, San Antonio, TX 2007 Duke Energy C.G. Allen #1, 2, 3, 4, 5, Gaston County, NC 2007 Dynegy Midwest / Sargent Lundy Havana Unit 6, Havana, IL 2007 Dynegy Midwest / Sargent Lundy Baldwin #1, 2, & 3, Baldwin, IL 2007 Gainsville Regional Utilities (GRU) Deerhaven Generating Station, Unit # 2, Gainsville, FL 2007

GenPower, LLC Nedham, MA Longview Power Station Maidsville, WV 2007

Indianapolis Power & Light Harding Street Station Indianapolis, IN 2007 LG&E -KUC E.W. Brown Unit 3 2007 LG&E -KUC Ghent Station Unit 1, 3 & 4, Ghent, KY 2007 LG&E -KUC Cummins & Barnard Trimble County Unit #2, Bedford, KY 2007 Minnesota Power, Duluth, MN Bosw ell, Unit 3, Cohasset, Minn. 2007 PacifiCorp - Utah Power Huntington Canyon Plant Unit #2, Huntington, Utah 2007 Plumb Point Power (LS Power) Plumb Point Energy Station Osceola, AR 2007 PPL Corporation Brunner Island #3,York County, PA 2007 Progress Energy Lee, Goldsboro, NC 2007 Progress Energy / Worley Parsons Mayo #1 & 2, Roxboro, NC 2007 Progress Energy / Worley Parsons Crystal Rive r Units 4 & 5 Crystal River, FL 2007 Reliant Energy Cheswick Power Station Springdale, PA 2007 Reliant Energy Keystone Station Units #1 & 2 Shelocta, PA 2007 Salt River Project Washington Group Springerville Station, Unit 4 Springerville, AZ 2007 SCE&G a SCANA Corp. Wateree Units 1 & 2, Eastover, SC 2007

Southern Company Georgia Power Hammond #1, 2, 3, & 4, Coosa, GA 2007 TVA Kingston, Tennessee 2007 TVA Colbert, Alabama 2007

5Utility Kick Station/Location off Year TXU Corp. Sandow Plant, Unit 5, Milam County, TX 2007 TXU Corp. - Oak Grove Mgt. Co. Oak Grove, Units 1 & 2, Robertson County, TX 2007 Western Farmers & Brazos Elec. Co-op Hugo Unit 2, Anadarko, OK 2007 AEP Conesville Plant Unit #4, Conesville, OH 2007 AEP Kyger Creek 1 – 5, Gallipolis, OH 2007 AEP Cliffy Creek 1 – 5, Madison, IN 2007 Allegheny Energy Greensberg, PA Fort Martin Units 1&2, Maidsville, WV 2007 Ameren Coffeen Plan t, Coffeen, IL 2007 Ameren Duck Creek Plant, Canton, IL 2007 Constellation Energy Brandon Shores Units 1&2, Baltimore, MD 2007 Dominion Chesterfield Unit # 6, Chester, VA 2007 Alabama Electric Coop Lowman Station, Leroy, AL 2008 Allegheny Energy Pleasants, Pleasants WV 2008 DP&L Stuart #4, Aberdeen, OH 2008 Duke Power Marshall, Terrel, NC 2008 City of Sringfield, IL Dallman, Springfield, IL 2008 Alabama Power Gaston #1, Wilsonville, AL 2008 Kentucky Utilities Ghent #4, KY 2008 Duke Energy Cliffside Plant Units 6 & 7, Cliffside, NC 2008 LS Power East Brunswick, NJ Long Leaf Project, Early County, GA 2008 NRG Energy Big Cajun II Unit 4, New Roads, LA 2008 Ohio Valley Electric Corp. Kyger Creek, Cheshire, Ohio 2008 Progress Energy Cape Fear Units 1 & 2, Siler City, NC 2008 Progress Energy L.V. Sutton, Wilmington, NC 2008 Public Service Electric & Gas Co. Hu dson Unit #2, Jersey City, NJ 2008 Public Service Electric & Gas Co. Mercer Plant Units 1 & 2, Trenton, NJ 2008 SCE&G. Williams Station, Charleston, SC 2008 Southern Company Alabama Powe r Plant Barry, Bucks, AL 2008 Southern Company Alabama Power J.H. Miller Units 3, & 4, West Jefferson, AL 2008 Southern Company Georgia Power McDonough/ Atkinson #1, 2, Smyrna, GA 2008 Sunbury Generation LLC Sunbury Units 1 & 2, Shamokin Dam, PA 2008 Wisconsin Public Service Corp. Weston Plant, Unit #3, Wausau, WI 2008 XcelEnergy Comanche Unit #3, Pueblo, CO 2008 Alliant Energy - IP&L Sutherland Plant - Unit 4, Marshalltown, IA 2008 Alliant Energy - Wisconsin Power & Light Co lumbia Energy Center, Portage, WI 2008 CWLP, Springfield, IL Dallman Station, Unit # 4, Springfield, IL 2008

East Kentucky Power John Sherman Cooper Plant, Unit 2, Burnside, KY 2008 LS Power East Brunswick, NJ Elk Run Power Plant, Waterloo, Iowa 2008 Otter Tail Power Co. Big Stone II, Milbank, SD 2008 Public Service of New Hampshire Merrimack Station, Units 1 & 2, Bow, NH 2008 Salt River Project / Sargent & Lundy SRP Coronado Plant, Saint Johns, AZ 2008 Sithe Global Power, LLC Houston, TX Desert Rock Energy Co., Farmington, NM 2008 We Energies South Oak Creek Retrofit, Units 7 & 8, Oak Creek, WI 2008 XcelEnergy Sherco Plant Un its 1&2, Becker, Minn. 2008 American Municipal Power American Munici pal Power Station, Letart Falls, OH 2008 NRG Energy Indian River Units 1,2,3 & 4, Millsboro, DE 2008 Power4Georgians Coop Washington County Power Station, Sanderville, GA 2008 Southern Company, Georgia Power Plant Branch #1, 2, 3, 4, Milledgeville, GA 2008 Southern Company, Georgia Power Scherer Plant Units 1,2,3,4, Juliette, GA 2008 CMS Energy Karn / Weadock Complex, Bay City, MI 2008

6The service life of stack liners made from FRP is expected to be the life of the plant as are C-276 clad steel stack liners. Organic coatings usually have to be replaced after 20 to 25 years. Brick lined stacks have a history of more maintenance compared to FRP stack liners.

FGD CASE HISTORIES

Case histories of FRP for wet FGD processes include absorber towers or vessels, slurry piping, ductwork, and stacks liners. The use of FR P in FGD processes dates back to the early 1970s. With an abrasion-resistant liner, FRP pi pe based on epoxy vinyl ester resin has been successful in numerous plant sites for more th an 35 years. The use of FRP and FRP awarded projects grew rapidly in 2006 and 2007, and the trend continues in 2008. The driving force for this growth is the rapid incr ease in the cost of metals, re duced metal availability, and the relatively stable cost of FRP.

FRP case histories date back to the early 1970’s . The most prominent applications are lime slurry piping followed by stack liners. The most common material of construction for slurry piping (Fig. 2) in wet FGD syst ems is FRP based on epoxy vinyl ester resin. With an abrasionresistant liner, FRP pipe based on epoxy vinyl este r resin has been successful in more than 150 plant sites dating back to 1977.

FIGURE 2: Lime slurry piping for an FGD process in a power plant in the Eastern United States

7The use of FRP in wet FGD stack liners da tes back to 1977. A nu mber of FRP stack liners were installed in the 1980s and are still in service today as shown in Table 4. Two were replaced with acid brick linings and five were re lined. Fabrication errors were the root cause for these stack liner difficulties. The rest, that we re fabricated properly, are in good to excellent condition and require minimum main tenance. Poor fabrication and lack of inspection led to the demise of company “A” shown in Table 4. With a reputation for excellence, company “B” has become the largest FRP fabricator in the world.

TABLE 4 FRP STACK LINERS IN FGD SE RVICE INSTALLED BETWEEN 1977 AND 2001

Station/Unit Year in Service Fabricator Original Resin Status as of 2007

Spurlock 1 1977 A Chlorendic Polyester relined in 1988 Coronado 1 1979 B Chlorendic Polyester min. maintenance

Winyah 3 1980 B Chlorendic Polyester min. maintenance Coronado 2 1980 B Chlorendic Polyester min. maintenance Spurlock 2 1981 A Chlorendic Polyester replaced with brick Winyah 4 1981 B Chlorendic Polyester min. maintenance Merom 2 1981 A Chlorendic Polyester relined with 510N Merom 1 1982 A Chlorendic Polyester relined with 510N Laramie R. 3 1982 B Chlorendic Polyester little maintenance

Holcomb 1 1983 B Chlorendic Polyester min. maintenance

Cross 2 1983 B Chlorendic Polyester excellent condition Antelope Valley 1 1984 A Chlorendic Polyester replaced with brick

North Valme 2 1985 B Chlorendic Polyester no maintenance Antelope Valley 2 1986 A Chlorendic Polyester relined with 510N

Intermountain 1 1986 B Brominated Polyester min. maintenance Intermountain 2 1986 B Brominated Polyester min. maintenance Sarnia 1992 C Brominated Polyester relined with 510N Milliken 1994 D Bominated Epoxy Vinyl Ester min. maintenance Ingolstadt 1994 E Novolac Epoxy Vinyl Ester min. maintenance Simmering 2000 F Novolac Epoxy Vinyl Ester excellent condition Eggborough 2001 G Bis A Epoxy Vinyl Ester excellent condition

The experience above has led the engineering community to be much more careful in choosing fabricators who are qualified to take on stack liner projects that require field fabrication. In addition, engineer s have become more aware of the importance of inspection and workmanship and are willing to take the necessary steps to promote the use of best practices to avoid the mistakes of the past. Consequently, there have been very few problems with stack liners that were fabricated in the 1990’s, a nd the trend of success has continued through 2007.

Some of the stack liners, dating from 1994, are shown in Figures 3, 4 and 5. They are located in New York, Germa ny, and Austria respectively.

8FIGURE 3: Milliken power station stack line rs operating in Western New York since 1994.

FIGURE 4: Two FRP liners operating in Ingolstadt, Germany since 1994.

9FIGURE 5: FRP stack liners opera ting in Vienna, Austria since 2000.

The use of FRP in North American power plants increased dramatically in 2006. That year 63 FRP stack liners were awarded for construction at 49 power plant sites. With more than three million square feet of laminate, this was the largest award of FRP stack liners in the history of the power industry. Figure 6 shows the installati on of two stack liners in the eastern United States.

FIGURE 6: Stack liner installation in a power plant on the East Coast

10In addition to the rapid growth of FRP in wet FGD stack liners, FRP ductwork for transporting scrubbed flue gas to the FRP stack liners has also gr own dramatically. Historically, FRP ductwork in power plants has been very successful dating back to the 1970s. Figure 3 shows the FRP ductwork, made with brominated e poxy vinyl ester resin in a 550MW power plant. Brominated resins are used when stack and duct specifications call for fire retardancy.

Figure 3: Ductwork in a 550 MW powe r plant in the Eastern United States

The construction of FRP absorber vessels and internal components grew rapidly starting in 2006. The most common FRP absorber vessel s are known as jet bubblin g reactors (JBR). A JBR is part of a limestone slurry FGD process th at has all the chemical reactions taking place in one vessel to produce high quality gypsum. One of the largest FR P scrubbers in North America started up in June 2007 at a power plant on the Ohio River. Figure 4 shows the massive JBR that is 88 feet in diameter and 77 feet tall. Th is JBR is currenlty removing 99% of the SO 2 from high sulfur coal flue gas.

FIGURE 4: A large FRP flue gas sc rubber in a 600MW power plant.

11Another rapidly growing use of FRP in power plants is for coo ling towers. While wood has been the predominant material used for thes e towers, FRP is fast becoming the material of choice for these towers instead. The primary reason is that FRP structures are anticipated to last more than twice as long as wood structures (50 years plus versus 25 years for wood). FRP requires little or no maintenance over its lifespan while wood towers often require a considerable amount of maintenance. FRP is not subject to in ternal deterioration or biological attack, and it can withstand almost any chemical exposur e by choosing a suitable resin. Because FRP structural members can be manu factured in lengths up to 60 f eet long and beyond, labor costs are reduced compared to lumber that requires splicing in 20 foot lengths. Figure 6 shows two six cell FRP towers in a 700 MW power station in the Midwest.

Figure 6: FRP cooling towers at 700 MW Midwest Power Plant.

CONCLUSIONS

FRP made with DERAKANE® and HETRON® epoxy vinyl ester resins is an ideal material of construction for lime slurry piping, stack lin ers, absorber vessels and ductwork with the following advantages:

• Proven performance for more than 30 years

• Much lower cost than Alloy C-276 clad carbon steel

• Less maintenance than other materials

NOTICE

The information in this pub lication is presented in good fa ith, but no warranty is given, expressed or implied, nor is freedom from any patent to be inferred. Also, it is intended for use

1213 by persons skilled in the fiber reinforced plas tics industry, acting on thei r own risk, and assuming the entire responsibility for the selection of ma terials, the design, the cure and fabrication, and the installation of the equipment. Having no control over these opera tions, ASHLAND does not guarantee the quality of the end product. NO WARRANTIES ARE GIVEN: ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR USE ARE EXPRESSLY EXCLUDED.

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