APPLICATIONS FOR CORROSION-RESISTANT FIBERGLASS REINFORCED PLASTIC EQUIPMENT IN THE PULP AND PAPER INDUSTRY Terry W.

Cowley Development Leader The Dow Chemical Company Freeport, Texas

manufacture of odd sized and shaped parts used in the mills.

DISCUSSION From Wood to Fiber Paper is made from cellulose fibers and cellulose fibers are obtained from the pulping or digestion of wood chips. As the cellulose fibers leave the pulping area, they are collected on screens and washed. The washed fibers then proceed to the bleaching process for brightening and are subsequently collected and washed again before being transferred to the paper manufacturing area. The used pulping liquor and its wash water are sent to a reclamation area to recover useable chemicals. The bleaching solutions and their wash water are recycled where possible and finally sent to the pollution control area for clean up.

ABSTRACT ________________________________________________ Fiberglass reinforced plastic (FRP) equipment is being used in a wide variety of ways for corrosion-resistant protection throughout the pulp and paper process. This paper describes the major process areas of a pulp mill and presents examples of where FRP equipment is being used or can be used. Environmental concerns and stiffer environmental regulations have made pollution control and abatement an area of major emphasis in the pulp and paper industry. The pulp and paper industry is recycling more process streams and in greater amounts yearly. Recycling these process streams increases the industrys already severe corrosion problems, and that is where FRP materials enter the picture - corrosion-resistant protection at an affordable cost. ________________________________________________

The Pulping Process Pulp is manufactured from a wide variety of raw materials including softwoods, hardwoods, grasses, wheat straw, bamboo and bagasse. Because of North Americas abundant forest, about 98% of the pulp produced is from wood. Wood is made of cellulose, lignin, carbohydrates, protein, resins and fats. Lignin is the glue that holds the tree together and the pulping or digesting of wood chips is what separates the lignin from the cellulose fibers, the major constituent of paper. There are several pulping processes in use today. The various processes with their required chemicals are listed below, in decreasing order of their use. Process 1. Kraft 2. Sulfite a) Acid Sulfite b) Bisulfite c) Neutral Sulfite d) Alkaline Sulfite e) N. S. S. C. 3. Soda 4. Mechanical Chemicals Used Sodium hydroxide (NaOH) Sodium sulfite (Na2SO3) H2SO3, SO2, XHSO3, pH = 1-2 XHSO3, pH = 2-6 XSO3, XCO3, pH = 6-9+ XSO3, XOH, pH = 10+ Neutral Sulfite Semichemical NaOH

INTRODUCTION The chemicals required for the production of paper from wood are extremely corrosive in nature and engineers of pulp and paper mills are constantly in the struggle of keeping their mills running because of equipment breakdown and failure due to corrosion. Fighting the war on corrosion can be expensive because of the high cost of exotic metals required to withstand the corrosive process streams. Even stainless steel is not satisfactory in many cases because of high concentration of chloride ions in the process streams, which leads to chloride stress cracking. A viable answer which meets the corrosion resistant requirements at an affordable cost is FRP equipment fabricated with epoxy vinyl ester resin composites. There is a wide array of epoxy vinyl ester resin types with varying properties on the market today. With proper fabrication techniques, catalyst systems, and reinforcement materials, FRP composite systems can be built to meet specific temperature and corrosion-resistant requirements normally found in pulp and paper mills. Also, the nature of FRP fabrication allows for the relatively easy

In processes 1, 2a through 2d and 3, wood chips are cooked in the respective chemical mixture (called White Liquor in the Kraft process) at about 170C and 100 lbs. steam pressure for 2-3 hours. The temperature, pressure and

cooking time vary depending on the process, the desired end product, and the type of material being digested. Pulping can be carried out in continuous or batch type digesters. At the end of the cooking time, the softened wood chips are blown under pressure in a blow tank, which causes the wood chips to break up into individual fibers or pulp. The pulp is first deknotted and later washed to remove the solubilized lignin and other impurities. Knots of undigested wood are removed from the pulp to be recycled back to the digester for additional treatment. Washing the pulp not only cleans the pulp, but reclaims the chemicals used in the digestion process and the dissolved lignin. A minimum of wash water is used to prevent too great a dilution effect. During the wash cycle, the pulp is collected on fiber screens and sent to the bleach plant or directly to the paper mill, depending on the grades of pulp and paper being produced. The washed pulp is called Brown Stock due to its color. The filtrate or wash water from the washers is called Black Liquor because of its color. Processes 2e and 4 are primarily mechanical in nature. Mechanical pulping is simply the grinding of wood chips. In Process 2e, N. S. S. C., wood chips are digested for a short time in a neutral sulfite system and subsequently defibrilized by mechanical means. TMP - thermal mechanical pulping - is the process by which wood chips are first steam cooked and then defibrilized mechanically. Process 2e is often called chemical thermal mechanical pulping - CTMP [1]. Also being studied is solvent pulping - the cooking of wood in the presence of organic solvents at relatively high temperatures [2]. Epoxy vinyl ester resins are used to fabricate new fiberglass reinforced plastic (FRP) equipment or laminate linings and coatings for existing equipment for corrosion-resistant protection in the pulping and pulp washing areas. Figure 1 is a diagram of the pulping process in combination with a reclamation area [3]. Table 1 describes areas where FRP equipment and laminate linings can be utilized in the pulping process and the recommended epoxy vinyl ester resin types suitable for service in each area. FRP equipment has many advantages over traditional materials of construction. Some are as follows: 1.) FRP equipment made with epoxy vinyl ester resins provides corrosion resistance to a wide array of harsh chemical environments. 2.) FRP equipment provides a higher strength-to-weight ratio than metals, such as carbon steel, stainless steel, and Hastelloy C alloys.

3.) FRP equipment costs less to build, ship, install and maintain than comparable equipment made from stainless steel and more expensive alloys. Table 2 compares the typical historical cost of installed straight run FRP pipe made from an epoxy vinyl ester resin. [4]. FRP pipe can be even more economical because of its smooth interior bore, which allows the engineer to downsize the pipe for many applications without altering the flow. Furthermore, FRP pipe having the same diameter of metal pipe consumes less pump horsepower for a given flow. Generally for steel pipe, pump power consumption goes up over the pipes life cycle due to increased flow resistance caused by internal corrosion. New FRP pipe has a Hazen-Williams roughness coefficient (C) value of 160-165. Carbon steel has a value of C = 120 when new, degrading to C = 65 when used. The degradation is the result of the build up of surface oxidation (scale) on the interior surface of the pipe [5]. The smooth interior bore of FRP pipe provides improved flow of pulp stocks throughout the mill. The EPAs proposed regulations (Cluster Rules) requiring a large reduction in air and water pollutants for the pulp and paper industry should have a significant impact on the pulping area. Traditionally, the pulping area has operated with an open air policy. In other words, most emissions were allowed to escape to the atmosphere at vents and washer drums. One of the hazardous air pollutants (HAP) that has been allowed to escape is methanol, which is high on the Cluster Rules hit list of air pollutants that must be greatly reduced. This will require enclosing all washer drums and joining vents to common disposal areas. Washer hoods and vent ducting for the pulping area can be easily fabricated from FRP. The epoxy novolac (Ep Nov) vinyl ester resin has been shown to resist the attack of liquid organic compounds, such as methanol and other organic byproducts from the wood pulping process [6]. Table 3 lists some of the organic HAPs targeted by the EPA and the maximum recommended temperature for those HAPs in the liquid state for the Ep Nov vinyl ester resin. Of course, the same HAPs in the hot vapor phase have virtually no effect on laminates made with the Ep Nov vinyl ester resin. The Ep Nov vinyl ester resin can be used to fabricate FRP steam stripping towers that will be required to reduce water soluble HAPs from wastewater streams to acceptable levels before the wastewater is allowed to exit the mills [7].

Table 3. Resistance of Epoxy Novolac Vinyl Ester Resin to Some Hazardous Air Pollutants in Liquid Form Max. Recommended Temperature, C 38 71 49 21 65

Compound Methanol Hexane Toluene Methyl Ethyl Ketone Formaldehyde

Liquor. The White Liquor is now ready to be reused in the pulping process. The CaCO3 precipitate is concentrated and oxidized by burning in a kiln to form calcium oxide (CaO), which is later converted to Ca(OH)2 for reuse in converting the Na2CO3 from the Black Liquor to NaOH. Saltcake (Na2SO4) is added to the Black Liquor ahead of the recovery furnace to make up for the normal sodium and sulfur losses. Na2SO4 is reduced to Na2S in the recovery furnace. If sulfur losses are negligible, sodium make up is accomplished by the addition of NaOH and Na2CO3 to the Black Liquor just prior to the recovery furnace. Epoxy vinyl ester resins can be readily used for corrosionresistant piping and storage tanks for weak Black Liquor, Green Liquor and White Liquor in the Reclamation area, where temperatures are not prohibitive. In a recent study, an optimized Bis A epoxy vinyl ester resin had only a 0.5% weight change after exposure to 5% NaOH at 82C for twelve months. Figure 2 show the percent retention of the flexural modulus and strength of the test coupons throughout the twelve month test period.

The Reclamation Process Concentrating Black Liquor. Since the Kraft process is presently by far the preferred pulping process, only the reclamation process for Kraft Black Liquor to White Liquor process will be discussed. The Black Liquor as it exits the washer area has a solids content of about 15%. The solid is composed of the inorganic material present in the White Liquor and dissolved material (lignin and other organic matter) obtained during the digestion process. To recover the inorganic materials for reuse and dispose of the lignin and other organic matter in the Black Liquor, the solid content must be increased to approximately 65-75%. The increase in solid content is accomplished by the use of multiple stage water evaporators. Combustion of Black Liquor. The 65-75% solids in the Black Liquor are now able to support combustion. The Black Liquor is sprayed into a recovery furnace where the lignin and other organic matter are burned, thus producing energy for steam production and carbon dioxide (CO2), which is absorbed by the residual caustic to produce sodium carbonate (Na2CO3). Limiting the oxygen supply to the furnace will result in the reduction of caustic/sulfur compounds to Na2S. Green Liquor. The Na2CO3 and Na2S form a smelt which flows from the furnace into a tank containing water, where an aqueous solution is formed called Green Liquor. The Green Liquor is cleaned and sent to a reactor where it is mixed with calcium hydroxide [Ca(OH)2]; the Na2CO3 is converted to NaOH and the Ca(OH)2 is converted to the white calcium carbonate (CaCO3) precipitate. About 10 to 20% of the Na2CO3 is not converted, and goes through the pulping and recovery process again. White Liquor. The aqueous mixture is then sent to a clarifier to allow the CaCO3 to settle out. The clarified liquor contains NaOH, Na2S and Na2CO3, which is White

Fig. 2. Percent Retention of Flexural Modulus and Strength of Optimized Bisphenol A Epoxy Vinyl Ester Resin After Exposure to 5% NaOH at 82C
100 Percent Retention 80 60 40 20 0 30 90 180 Days Exposure 360 Flexural Modulus Flexural Strength

Fig. 2.

After the twelve month exposure test period, the optimized Bis A epoxy vinyl ester resin test coupons retained over 80% of their flexural modulus, while retaining just over 30% of the original flexural strength. The resulting flexural strength should not be interpreted as unsatisfactory service. The coupons represent a 100 - 110-mil corrosion-resistant liner of a FRP tank. The function of a corrosion-resistant liner is to provide protection against chemical attack. The design strength of an FRP tank is essentially due to its structural wall, and it is recommended that a corrosionresistant liner not be part of the design strength of a FRP tank. It is suggested that corrosion-resistant liners, ranging from 100 to 250-mils thick, be treated as the maximum

thickness loss allowable before relining a FRP tank. This is much like the maximum allowable thickness loss for a metal tank before it is replaced. There appears to be some confusion about the relationship of pH to caustic concentration. A 5% NaOH solution has an immeasurable pH, since it has a normality greater than 1. A 1 normal(N) NaOH solution (4 wt%) has a pH of 14. A 0.1N (0.4%) NaOH solution is equal to a pH of 13. The pH of a solution is the negative log of the hydrogen ion concentration in normality, see equation 1. pH = - log [H ]
+

whiteness or brightness of the pulp. The pulping process removes about 90% of the lignin present in the wood chips. However, about 10 % lignin remains with the pulp after washing (Brown Stock). Bleaching removes the remaining lignin and impurities and increases the whiteness of the pulp for the subsequent manufacture of printing paper. The bleaching process is carried out so that a stable brightness is achieved that will be retained during aging and exposure to heat and light. The molecular weight of cellulose is also regulated and adjusted by the bleaching process. Thus, the bleaching process can be viewed as two operations - purification and oxidation. Alkaline extraction, and to a lesser extent, chlorine dioxide, perform the purification operation by removing most of the lignin and impurities remaining in the pulp. The oxidation operation whitens the pulp and stabilizes the brightness, and is accomplished by the use of chlorine dioxide and peroxide - oxidizing agents. Bleaching is carried out in several separate, sequential chemical treatment stages. Each stage consists of a pulp mixer for blending pulp, chemicals, and steam and a tall cylindrical tower where the bleaching reaction is carried out. Usually, the pulp flows up the tower and out to a water wash stage where the fibers are separated from waste materials. The time spent in each tower, one to five hours, depends on the chemical treatment used so that maximum reaction occurs with a minimum of cellulose degradation (oxidation). Temperatures in the towers may be as high as 180F and higher. In the past, most commercial Kraft bleaching operations began the bleaching sequence with the chlorination (C) of pulp followed by alkaline extraction (E) to remove chlorinated lignin and minimize the need for brightening agents in later stages. Subsequent stages could have been multiples of hypochlorite (H), chlorine dioxide (D) and alkaline extractions. Typical bleaching sequences that have been used to obtain high brightness pulp are CEHDED and CEDED; typical bleaching sequences that have been used for low brightness pulp are CEH and CEHD. However, because of environmental concerns and government regulations, the bleaching sequence for pulp fibers is now in a rapid transitional phase from chlorine and hypochlorite use to elemental chlorine free (ECF) to possibly total chlorine free (TCF) in some mills. Chlorine and hypochlorite are thought to form pollutants, such as chloroform, dioxins and other organochlorine compounds of environmental concern [8]. Chlorine dioxide is a major bleach agent in ECF bleaching, while alkaline hydrogen

eq. 1.

For a caustic solution, pH can be calculated by subtracting the negative log of the hydroxide ion concentration in normality from 14, see equation 2. pH = 14 - (-log [OH ])
-

eq. 2.

Figure 3 shows the relationship of weight percent vs. pH for some common caustic solutions. As the graphs show, a high pH is not indicative of a high weight percent caustic solution.

Fig. 3. Weight Percent of Caustic Solutions vs. pH

10 Wt% of Caustic Solutions 1 0.1 0.01 0.001 0.0001 0.00001 9 10 11 12 13 14

pH of Solutions Sodium hydroxide Potassium hydroxide

Fig. 3.

Refer to Figure 1 for a diagram of a reclamation process [3]. Table 4 lists the recommended epoxy vinyl ester resin types for FRP applications in the reclamation area.

The Bleaching Process The goal of bleaching is to obtain a pulp with stable, desired optical properties. Primarily, optical properties refer to the

peroxide (P) is used in TCF bleaching. Use of chlorine dioxide has increased because of its ability to react selectively with lignin, causing no degradation of the cellulose fibers and yielding a quality pulp of higher brightness [1]. Other bleaching agents, such as enzymes and ozone (Z), are being trialed in various research labs and pilot plants throughout the industry [9,10]. Some mills use what is called oxygen delignification (O) prior to the bleaching process, for a higher level of lignin removal [11]. Since hydrogen peroxide is decomposed by even traces of most heavy metal ions, pulp stock usually undergoes a metal chelating treatment (Q) prior to peroxide bleaching . A possible evolution of the bleaching sequences over the next several years may be something like that shown in Table 5.

the first fourteen months, after which time the mill switched to all alkaline peroxide [13]. If time allows, in situ (in place) coupon testing will enable a pulp mill to determine which resin is best suited for all of its bleach process streams. Resin manufacturers will gladly supply their respective coupons and perform the required testing to determine the most suitable corrosion-resistant resin composite. When requested, FRP fabricators will make pipe test spools from different resins that can be installed in actual process streams for in situ testing. A three year in situ study of FRP laminates made from six different corrosion-resistant thermoset resins installed in chlorine dioxide bleaching towers revealed that a brominated Ep Nov vinyl ester resin, an Ep Nov vinyl ester resin, and a brominated Bis A epoxy vinyl ester resin provided the first, second and third best corrosion resistance, respectively [8]. A twelve month laboratory study utilizing an aggressive alkaline peroxide environment (see Table 6) was conducted on resin laminates made from the thermoset resin types listed below. Brominated Bis A epoxy vinyl ester resin Brominated Ep Nov vinyl ester resin Low styrene content Bis A epoxy vinyl ester resin Bis A epoxy vinyl ester resin

Table 5. Proposed Changes in Bleaching Sequences

CEHDED = Elemental Chlorine CEDED Containing (CD)(Eo)D E D D(Eop)D E D = Elemental Chlorine Free O D(Eop)D E D OPEPP = Total Chlorine Free OQZEPP
Whether, the proposed changes in the bleaching sequences occur as suggested or not, one fact is sure; the bleaching sequences will change. Changes may be brought about by government regulations, market requirements, and raw materials. An epoxy vinyl ester resin that will withstand the corrosive environment of a variety of bleaching process streams enables the pulp mill to easily re-route process streams to existing equipment without worry of equipment damage due to the corrosive nature of the streams. There seems to be an impetus to using the same process equipment with alternating bleaching environments in order to produce ECF and TCF pulp depending on market needs. The bleaching environments may change as often as every few weeks. For example, a mill recently needed a pipe leading into a chlorine dioxide upflow tube that could withstand the corrosive effects of both chlorine dioxide and alkaline peroxide bleaching environments. Since stainless steel and titanium could not withstand chlorine dioxide and hot (82 93C) hydrogen peroxide environments, respectively, an epoxy vinyl ester resin was sought that could withstand both environments [12]. The FRP equipment was made with a low styrene content Bis A epoxy vinyl ester resin and has been in service for over three years; experiencing both chlorine dioxide and alkaline peroxide process streams for

Table 6. Laboratory Alkaline Peroxide Environment Average 0.56 wt% 10.7 83.5C

H2O2 conc. pH Temperature

Each resin laminate was catalyzed with a benzoyl peroxide(BPO)/ N,N-dimethylaniline(DMA) catalyst system and subsequently post-cured. Another resin laminate made with a Bis A epoxy vinyl ester resin was catalyzed with a methyl ethyl ketone peroxide(MEKP)/ cobalt naphthenate(CoNap) catalyst system and subsequently postcured. All of the resin test laminates were fabricated with two layers of a synthetic veil. The studys results indicated that the test coupons catalyzed with the BPO/DMA catalyst system provided significantly better corrosion resistance than did the test coupons catalyzed with the MEKP/CoNap system. Figure 4 shows the weight change of the resin test laminates after twelve months of exposure.

Fig. 4. Weight Change of Epoxy Vinyl Ester Resin Test Laminates - Laboratory Corrosion Study
4 2 % Wt. change 0 -2 -4 -6 -8 30 90 180 365 Exposure (days)
Br Bis-A Br Ep Nov LS Bis-A Bis-A Bis-A/CN

Table 7. Ozone Corrosion Rate on FRP Clear Castings and Laminates (mm/yr)
Clear Casting or Laminate Corrosion Rate in Aqueous Phase(1) -----0.1 -----0.1 Corrosion Rate in Gas Phase No. 1(2) 0.3 0.4 0.2 0.3 Corrosion Rate in Gas Phase No. 2(3) -----0.8 -----0.8

Bis A EVER Bis A EVER laminate Ep Nov VER Ep Nov VER laminate

Fig. 4.

(1) The concentration of ozone in aqueous environments varies from 0 - 80 ppm depending on the temperature and partial pressure of ozone. (2) Gas Mixture No. 1 - 0.3 - 1.0% ozone at 45 - 50C. (3) Gas Mixture No. 2 - Ozone up to 6% at 40C.

The brominated Ep Nov and brominated Bis A epoxy vinyl ester resins with BPO/DMA catalyst system provided the best corrosion resistance to the alkaline peroxide bleaching environment. It is known that cobalt can cause the decomposition of hydrogen peroxide to oxygen and water [14], which may have an effect on the corrosion resistance of FRP laminates. However, the same resin type test coupons catalyzed with MEKP/CoNap tested in situ in a mills alkaline peroxide bleaching stream at 65C with only a trace of hydrogen peroxide at a pH of 10.5 indicated little, if any, corrosive attack after thirteen months of exposure. The data from the mill trial and laboratory study indicate that the negative effect of cobalt on the corrosion resistance of the resins tested is linked to increasing peroxide concentrations. The reader should note that the brominated Ep Nov and brominated Bis A epoxy vinyl ester resins provided a high degree of corrosion resistance to both, chlorine dioxide and alkaline peroxide bleaching environments. This is indicative that both resins types, like the low styrene Bis A epoxy vinyl ester resin, should provide satisfactory service in the alternating bleaching environments of chlorine dioxide and alkaline peroxide. A study by Petersson and Bergman reported the corrosion rate of three ozone environments on the clear castings and laminates of some Bis A epoxy and Ep Nov vinyl ester resins. The results are shown in Table 7.

Not surprisingly, the data indicates that as the ozone concentration increases, so does the corrosive attack. Petersson stated that FRP equipment could be used with good results between the ozone gas separator and the pulp washer, and in equipment for the filtrate of ozone bleaching stage. Usually, there is little, if any, ozone in the process areas just mentioned [15]. Table 8 lists the recommended epoxy vinyl ester resin types for FRP applications in a bleach plant and Figure 5 shows a diagram of a typical bleach plant of about five to ten years ago. The reader can substitute bleaching environments to develop the required bleaching sequences for the future.

Pollution Control Mercaptans, organic sulfides and non-condensable gases from the pulping recovery process are burned in the recovery boiler, scrubbed or precipitated, and vented. Ep Nov and brominated Ep Nov vinyl ester resins have been shown to provide satisfactory resistance to the hot, corrosive gases produced in recovery and power furnaces. Table 9 compares the corrosion resistance of an Ep Nov vinyl ester resin laminate and common metal alloys to some chemical environments found down-stream from recovery furnaces [16]. A vessel or holding chamber made with a Bis A epoxy vinyl ester resin was used to de-odorize mercaptans and hydrogen sulfide. The mercaptans and hydrogen sulfide vapors were mixed with about 2% ozone gas before being vented to the

atmosphere. The operating temperature was reported as ambient, but initial temperature requirements were from ambient to 43C. The vessel was put into service in March 1974 and taken out of service in 1994, still in good condition, because of a process change [3]. Chlorine and chlorine dioxide from the bleach plant are scrubbed with caustic resulting in chloride salts, such as, sodium hypochlorite. Epoxy vinyl ester resin laminates with a BPO/DMA catalyst system, a double synthetic veil and that are post-cured should be used in the fabrication of caustic scrubbing towers for chlorine. A BPO/DMA catalyst system is recommended over the much used MEKP/CoNap catalyst system because the cobalt ion reacts with the hypochlorite, both in caustic and acid solutions, to form the chloride ion and oxygen. The presence of cobalt as a resin catalyzation promoter in a cured resin laminate has proven to be very deleterious to the corrosion-resistant properties of cured resin composite laminates in sodium hypochlorite solutions [3,17]. The pH of a caustic-sodium hypochlorite solution should be maintained about 10.5 for the least corrosive environment. Properly catalyzed, fabricated, and cured brominated Bis A and Bis A epoxy vinyl ester resins have been found to provide the best resistance to caustic-sodium hypochlorite environments. A chlorine/chlorine dioxide scrubber fabricated in the manner recommended previously has been in-service at a southeastern paper mill since early 1985 [18]. For hypochlorite solutions of 10-15%, some prefer a dual laminate system. A recommended inner liner for a dual laminate is polyvinyl chloride(PVC) or chlorinated polyvinyl chloride(CPVC) with an epoxy vinyl ester resin laminate making up the structural wall. FRP piping can be used for the wide array of effluent and sewer lines found throughout a pulp mill because of epoxy vinyl ester resins ability to withstand a variety of chemical environments. There are FRP pipe products available today that not only provide the corrosion resistance required but can be installed so that there is minimal disruption at the mill site because there is no burying of new pipe. One trenchless technology is called cured-in-place-pipe (CIPP), which consists of installing a flexible tube impregnated with resin into an existing opening of the sewer or effluent line to be rehabilitated, inflating the tube so that it presses against the inside wall of the line, and then curing the resin in place with heat. Since the resin impregnated tube is flexible prior to resin cure, it can accommodate a multitude of oddly shaped sewers. CIPP has a smooth, jointless liner, which improves the structural integrity of the line and also improves flow characteristics. With the appropriate epoxy vinyl ester resins, CIPP can provide high-temperature performance up to 107C [19]. For the rehabilitation of

sewer and effluent lines that experience high pressure and require a high degree of structural strength, a centrifugally cast FRP pipe capable of being sliplined into an existing line is available. The pipe has an inner resin rich corrosion-liner, a structural wall consisting of sand and resin for strength, followed by an outside layer of fiberglass and resin [20]. Table 10 gives the recommended epoxy vinyl ester resin types for FRP applications in pollution control areas. Figure 6 shows some pollution control areas where epoxy vinyl ester resins can be used.

External Corrosion The external corrosion in a pulp and paper mill can be severe. Not only does metal undergo corrosive attack but many of the chemical process streams are corrosive to concrete as well. Leaks from piping and drips from flanges and valves onto concrete flooring can rapidly corrode the concrete to the point where the uneven surface can become a safety hazard. The concrete bases that support pumps undergo the same type of corrosive attack when a pump develops a leak. Polymer concrete made with epoxy vinyl ester resins can withstand the corrosive attack of may incidental spills and leaks [21]. In fact, polymer concrete is used to refurbish existing open concrete trenches that experience corrosive environments continuously. Polymer concrete is used for pre-fabricated open trenches in new construction sites. An Ep Nov vinyl ester resin is best for acidic and solvent process streams. A Bis A epoxy vinyl ester resin is best for caustic process streams. Metal grating, cable trays, and duct work are rapidly attacked by spills and the corrosive nature of the atmosphere, respectively. FRP grating and cable trays made with epoxy vinyl ester resins resist the attack of the most corrosive acidic and caustic process stream leaks. Brominated epoxy vinyl ester resins are the most frequently used resins for duct work fabrication because of the resins fire retardant property. Table 11 gives a list of suggested epoxy vinyl ester resins for various external corrosion FRP applications.

CONCLUSIONS FRP equipment fabricated with epoxy vinyl ester resins is a viable, cost effective means of successfully fighting corrosion throughout pulp and paper mills. Stand-alone

FRP tanks and stacks, linings for tanks and stacks, piping, duct work, grating and polymer concrete have all given satisfactory service in the varied corrosive environments of a pulp and paper mill. As noted with sodium hypochlorite and alkaline hydrogen peroxide environments, it is essential that FRP equipment be fabricated in such a manner as to insure the longest service life. This includes the correct laminate lay-up sequence and veil type, catalyst system, design, and fabrication techniques. If you dont know much about FRP equipment and thermoset resins, get to know resin suppliers and develop a relationship with one who offers technical service expertise in pulp and paper applications..

9. Patrick, K. L., J. E. Young, Pulp & Paper, Union Camp Expands Ozone Pilot Plant with Q, P, MC-Z NonChlorine Options, November, 1993, pp. 59-68. 10. Young, J., Pulp & Paper, Enzone Bleaching, Enzynk Deinking Advance to Pilot Plant Trials, November, 1994, pp. 81-82. 11. Harrison, A. Pulp & Paper, O2 Delig Matures into Key Process Segment at Modern N. A. Fiberlines, November, 1994. 12. Clarke, S. J., D. L. Singbeil, Pulp & Paper Canada, Corrosion of Titanium in Alkaline Peroxide Bleaching Media, (95)10:70(1994). 13. Thompson, M. J., T. W. Cowley, TAPPI Engineering Conference, 1995, Corrosion-Resistant Fiberglass Reinforced Plastic Composites for Alkaline Peroxide Environments. 14. Armstrong, A. D., The Pulping of Wood, 2nd ed., McGraw-Hill Book Company, New York, 1969, Vol. 1, p. 195. 15. Petersson, K., G. Bergman, The Eighth Annual Symposium on Corrosion in the Pulp and Paper Industry, 1995, Resistance of Polymeric Materials in Bleach Plants Producing Total Chlorine Free (TCF) Pulp. 16. Cowley, T. W., D. Kelley, TAPPI Engineering Conference, 1995, Improvements in Fiberglass Reinforced Plastic Equipment for Power and Recovery Furnaces Emission Controls. 17. Cowley, T. W., M. A. Robertson, The NACE Annual Conference, Corrosion 91, The Effect of pH and Temperatures on Fiberglass Reinforced Composites in Sodium Hypochlorite Solutions, March 11-15, 1991. 18. Caldwell-MacKay Co., Inc., private communication. 19. DERAKANE* Epoxy Vinyl Ester Resins for Cured-InPlace-Pipe, The Dow Chemical Company, (1995). 20. Large Diameter Centrifugally Cast Fiberglass Pipes Product Brochure, Hobas Pipe USA, Inc., (1995).

NOTICE The information in this publication is presented in good faith, but no warranty is given, nor is freedom from any patent to be inferred.

REFERENCES 1. Brown, G., R. L. McCreedy, and D. S. Blevins, Pulp, Paper and Dow, Pulp & Paper Resource Centre, Seminar, Dow Chemical of Canada, Limited, 1981. 2. Lora, J. H., E. K. Pye, Pulp & Paper, Solvent Pulping Opens Door to Viable Chlorine-Free, Effluent-Free Options, (1995). 3. Internal Dow Chemical Company report. 4. Is Something Eating You?, One Metal You Can Make With Our Resin, Dow Chemical Company, (1989). 5. Fiberglass Pipe Handbook, 2nd ed., Society of the Plastics Inc., New York, 1992, pp. 43-49. 6. Hinsey, N. W., TAPPI Journal, EPAs proposed cluster rule: The end of end-of-pipe, Vol. 77, pp. 65-74. 7. DERAKANE* Epoxy Vinyl Ester Resins, Chemical Resistance and Engineering Guide, The Dow Chemical Company, (1995). 8. Bishop, T., T. W. Cowley, TAPPI Engineering Conference, 1994, Corrosion-Resistant Fiberglass Reinforced Plastic Composites for Chlorine Dioxide Environments - Third Report.

*Trademark of The Dow Chemical Company.

21. Van Anglen, E., Pulp & Paper, Concrete Floor Coatings Needed for Protection in Harsh Mill Areas, February, 1996. 22. Alvarado, B., The Dow Chemical Company, private communication.

Table 1. Pulping Process Applications Recommended Epoxy Vinyl Ester Resin Types - Bisphenol A(Bis A), optimized Bis A, Brominated(Br) Bis A

- Caustic, white and black liquor feed piping and storage tanks - Caustic pulp stock chest - Washer compartments for pulp - Washer screens for collecting brown stock pulp - Lightweight, low friction chip chutes - Abrasion and corrosion resistant linings for caustic pulp slurry - Fan and ventilation duct work volatile organic compounds and non-condensable gases - Wash hoods, vapor condensing and recovery duct work equipment for caustic splash, steam, chlorine, chlorine dioxide, bleach and volatile organic vapors

- Flexibilized Bis A, Bis A

- Bis A, Br Bis A, epoxy novolac(Ep Nov) Br Ep Nov

Table 2. Cost Comparison for Installed Straight Run Piping Systems 10 cm dia. Pipe Installed Cost Cost per 100 ft. Ratio $ 2,552 1.00 15 cm dia. Pipe Installed Cost Cost per 100 ft. Ratio $ 3,407 1.00

Pipe Material

Carbon Steel, Sch 40 FRP made with epoxy vinyl ester resin, 150 psi @ 93C 316 Stainless Steel, Sch 10 Monel, Sch 10 Hastelloy C-276, Sch 10

$ 2,687

1.05

$ 3,704

1.09

$ 3,180 $ 8,860

1.25 3.47

$ 4,607 $ 12,123

1.35 3.56

$ 12,835

5.03

$ 20,761

6.09

Table 4. Reclamation Process Applications Recommended Epoxy Vinyl Ester Resin Types - Bis A

- Storage tanks and piping for caustic green liquor, and caustic or acidic/sulfite white liquor and recycled black liquor - Cyclone evaporators and parts for black liquor recovery - Venturi and packed scrubbers for removing aqueous soluble gases, H2S, SO2, CO2 - Storage tanks and piping for (1) calcium or sodium hydroxide and sodium sulfide for the preparation of white liquor for Kraft digestion and (2) sodium bisulfite and sulfurous acid for sulfite digestion - Piping for acidic and caustic effluent transfer - Fans and duct work for steam, non-condensable gases and sulfur containing compounds from combustion of concentrated black liquor - Self-supporting stacks and stack linings for steam, unscrubbed acidic and noncondensable gases from combustion of concentrated black liquor

- Bis A, Br Bis A

- Bis A, Br Bis A, Ep Nov, Br Ep Nov

Table 8. Bleaching Process

Applications Recommended Epoxy Vinyl Ester Resin Types - Bis A

- Wash water piping for transferring caustic and acidic used wash water from washer areas after bleaching towers - Washer hoods, drums and screens for collecting bleached pulp that exits C, E, H, P, and D towers - Seal tanks for washers after C, E, H, P, and D bleach towers - Hypochlorite storage and piping for subsequent bleaching of pulp and transferring bleached pulp - Caustic dilution storage and piping prior to and for transfer to paper plant - Chlorine and chlorine dioxide scrubbers from C and D bleaching towers - Polymer mortar for the installation of tile in bleaching towers and coatings - Fan, duct work and stacks for steam, caustic splash, chlorine, chlorine dioxide, and hypochlorite vapors from C, D, H, and E bleach towers - Chlorine, chlorine dioxide, caustic extraction and hypochlorite retention towers for bleaching pulp - Chlorine dioxide storage tank, chlorine dioxide generator dump tank, upflow tube and piping for chlorine dioxide generation, and pulp bleaching - Chlorine water make-up storage tanks and piping for bleaching in C towers

- Bis A, Br Bis A

- Bis A, Ep Nov, Br Bis A, Br Ep Nov

- Bis A and Br Bis A for caustic and acid streams, Ep Nov for highly acidic streams

- Bis A and Br Bis A, Ep Nov and Br Ep Nov for highly acidic streams and high temperature, acidic streams

- Bis A, Br Bis A, and Ep Nov

Table 9. Chemical Resistance of FRP Based on Epoxy Novolac Vinyl Ester Resin vs. Competitive Materials

Materials

Sulfuric Acid 25C Below 5% 95C to 30%

Hydrochloric Acid Not Recommended 82C to 5%

Acid Chloride Salts Not Recommended 65C to 20M ppm at low pH 100C All concentrations

317L Stainless [22] Alloy C-276 [22]

FRP made with epoxy novolac vinyl ester resin [7]

95C to 30%

82C to 37%

Table 10. Pollution Control Applications Recommended Epoxy Vinyl Ester Resin Types - Bis A, Br Bis A

- Piping and scrubber towers for chlorine and chlorine dioxide vapors from washer areas after C and D bleaching towers - Piping for caustic and acidic effluents from chlorine and chlorine dioxide scrubbers - Mixing, dilution, holding, and settling tanks (CaCO3) for waste water and reclaimed water, such as, white water - Vents and duct work for flammable vapors from the digestion tower in the pulping process - Exhaust stacks for fumes from black liquor reclamation furnace and chlorine and chlorine dioxide scrubbers

- Br Ep Nov, Br Bis A

- Bis A, Br Bis A, Ep Nov, Br Ep Nov

Table 11. External Corrosion Applications Recommended Epoxy Vinyl Ester Resin Types - Bis A, Ep Nov

- Liquor troughs, catch basins sumps, trenches and weirs for collecting caustic and acidic process streams and for nonpipe transfers/polymer concrete or FRP laminate overlays - Grating for acidic and caustic solution splash areas - Handrails, ladders, cable trays, equipment guards, and housing for electronics in corrosive fume areas and high acidic and caustic splash areas - Concrete surfaces in high caustic and acidic stream splash areas or concrete surfaces that receive high abrasive and impact treatment/polymer concrete

- Bis A, Br Bis A, Ep Nov

- Bis A, Ep Nov, flexibilized Bis A