Corrosion-resistant tube materials for extended life of openings in recovery boilers
Larry D. Paul, Joan L. Barna, Michael J. Danielson, and Sharon L. Harper

ABSTRACT." The corrosiveconditions causing rapid corrosion of

Type304L stainlesssteel in tube openings have been duplicated in the laboratory. Alternate materials a/so have been testea~and some show improved corrosion resistanceover Type304L. Alloy 825 and Alloy 625 composite tubing and Alloy 600 and Alloy 625 weld overlay materials all showpromise as a replacementfor Type304L in tube openings. All recoveryboilersdesignedor operatedat 8.375 MPa (1200psi) ,and above should considerusing these replacement materialsfor tube openings. KEYWORDS: Allo~ alloy stee~ corrosionresistance,fused salts, hydroxides, inorganic compounds, openings, recoveryfurnaces, replacement, stainlessstee~ substitutes, temperature, tubes.
irecess recovery boilers burn sulfurrich fuel (black liquor) that results in highly corrosive conditions in the furnace. To reduce corrosion to acceptable rates, the furnace wall tubes are commonly clad with Type 304L stainless steel. While this approach helps protect the lower furnace from accelerated corrosion by sulfidation, localized regions in the furnace have other corrosion concerns. Type 304L stainless steel cladding can be corroded in small patches around boiler tube openings (1-9). Figure 1 shows an example of wastage around a tube opening. Tube openings


that can be affected include all elevations of air ports, liquor gun and burner ports, and observation ports. The rates of corrosion vary widely and have ranged from 0 to 0.762 ram/year. The cause of this corrosion has been attributed to molten hydroxide salts that condense when the combustion gas is contacted by the relatively cool air from around the casing of the tubes (4-5, 7-9). Figure 2 shows caustic deposits dripping from around a tube opening. Sodium hydroxide at air port openings can exist only under very specialized conditions (1, 7-9). The CO 2

content of the air (about 330 ppm) is sufficient to convert sodium hydroxide to sodium carbonate (1). However, the reaction times are a function of CO2 concentration and temperature; at boiler tube metal temperatures, the reactions can take several hours to complete (1). Thus, sodium hydroxide can exist only near tube openings, and rapid corrosion of stainless steel only occurs at boiler openings. One approach to avoiding this localized corrosion is a substitution of the materials used for the tube openings. While we know that pure nickel can resist hydroxide corrosion, other concerns, such as sulfidation, also need to be considered. Test materials were selected from those known to resist corrosion in the sulfur-rich combustion gases that exist in the recovery boiler furnace. Only those materials that could be obtained in the form of a composite tube were considered in this study. Weld overlays also were evaluated as a means to repair existing corrosion sites. However, since corrosion tends to predominate on the casing side and does not rapidly attack the underlaying carbon steel, weld repair may be unnecessary.

Materials screeningtest
Coupons of selected materials and weld overlays were exposed to molten hydroxide mixtures for 720 hours. Corrosion rates were determined from the
Vol. 76, No. 8 TappiJournal

Paul, Danielson, and Harper work for Babcock & Wilcox Co., Research & Development Division, 1562 Beeson St., Alliance, OH 44601. Barna works for Babcock & Wilcox's Fossil Power Division, Box 351, Barberton, OH 44203-0351.


010 0.41 Mn 0. NR = not reported.01 0.20 24.0 NR 13.5 1.5 30.031 0.22 P 0. BAL = balance of alloy. 7~ August1993TappiJournal .30 7.10 23.01 0.08 0.0 0.008 0.34 Cu NR NR 0. Example of caustic corrosion around tube openings 2.97 40.~ii!!iiiii! Corrosion i 1.87 22.5 BAL 74.5 7.50 1.001 Si NR 0.015 0.82 1.01 0.5 0.02 0.11 0.05 0.005 0.005 NR S 0.50 0.40 0.76 Fe BAL BAL BAL 3.011 0.40 2.0 0.72 61.03 BAL BAL 19.81 2.0 0.20 0.0 9.17 0.11 NR 1.09 0.16 8.30 0.94 0.015 0.001 0.0 16. steel 304L 310 Alloy 625 Alloy 825 Weld* 309L 312 625 600 C 0.015 NR 0.40 0.41 Mo NR NR 0.74 Ni NR 8.30 0.0 22.68 0.36 1.015 0.024 0.08 30.010 0.11 19.010 0.010 23.02 Cr NR 18.10 0.10 * Nominal compositions of weld wire.48 0.06 0. Example of caustic deposits dripping from around a tube opening Chemistry of test coupon materials Material C.001 0.

and the salt mixtures were replenished as needed. all complex salts appear to be more corrosive than NaOH. The material chemistries are summarized in Table I. NaC1 and NaeSO4 additions also increase corrosion rates above those seen in pure NaOH.188 in. The 304L stainless steel probe worked as designed and could be used to give on-line corrosion rates (in real time at the test temperature). All coupons or weld overlayswere placed in 25. Salt mixtures were added to crucibles containing the weight loss coupons.3.) high form alumina crucibles and covered with the hydroxide salt mixture. The various salt mixtures used are given in Table II.5 in.) with about 15. Temperature limits for use of Type 304L stainless steel The corrosion rate of 1020 carbon steel and 304L stainless steel were determined using specially designed resistance-type corrosion probes in molten and frozen NaOH in a temperature range of 371°C to 323°C (700-613°F). Moreover. x 0. Average corrosion rates were determined by measuring the ambient temperature probe readings at the start and again at the completion of each test. Air was scrubbed of residual CO~ using sodium hydrate- asbestos and then metered into the test retort throughout the test. The chemistry of the welds was not analyzed.). the retort was opened. The retort was heated using a vertical furnace. but salt also was lost due to evaporation and wicking of the salt out of the crucibles. the NaOH + KOH mixture was found to be nearly totally depleted from the crucibles. salts were still found in all of the crucibles at the end of the test.8-1.18 mm (0. RP~ults Materials screening test The corrosion rates of the test materials in molten hydroxide salts at 343°C (650°F) are given in Fig. the composition of the weld on the coupon will be lower in alloy elements than those reported in Table I. which was 3. Care was taken to ensure that there was no metallic contact between the corrosion probes and the nickel container to prevent galvanic effects. Consequently. No.060 in. Thermocouples immersed in the melt were sheathed in Alloy 600.0283 m3/h (0. The crucibles were placed in support racks inside a test retort.8mm (1 in.60 mm (1 in.) thick.7 mm x 1. Because the weld metal will be diluted with the base carbon steel.4 mmx 19. The most corrosive mixture to stainless steels is NaOH + KOH. although some losses occurred. 8 TappiJournal 75 . Schematic of test system for materials screening test Temperature recorder . After one week at test temperatures.54 m m x 12.) of weld metal build-up on all surfaces. however. The temperature compensation device on the carbon steel corrosion-resistant probes did not function as planned.063 in. The test temperature was maintained at 343°C + 5. x 0. 4. At the end of the test. carbon steel corrosion rates required evaluation by cooling the probe down after each test.75 in.5°C (650°F _+10°F) for the entire test. This may be partly due to the rapid corrosion seen in this mixture. Significant amounts of all of the other salt mixtures were found at the end of the test.05 mmx 4. x 0. x 2 in. The NaOH was sparged continuously with air (air passed through sodium hydrate-asbestos to remove carbon dioxide) at the bottom of the melt at a flow rate of 0.=s Specimens Retort Furnace Air inlet Air ouUet I weight loss of the coupons during this exposure period. The crucible was heated by placing the container into a two-gallon autoclave Vol. Some loss of salts was seen due to evaporation and wicking up and out of the crucibles. 76.78 mm (1 in.4-mm x 50.125 in. (autoclave used as a heat source only).2 mm (0. except the carbon steel. The difference in probe readings was converted into a corrosion rate. 3. The carbon steel starting blanks were 25. The NaOH was contained in a nickel 200 crucible covered by a lid. The wrought coupons were 2.0226-0.0 standard ft'/h). all crucibles still had significant deposits after the first week. x 0. In addition. All mixtures of hydroxide salts are more corrosive to Type 304 stainless steel than to carbon steel. The weld overlays were prepared using a gas metal arc weld process to lay down the various weld materials over 1018 carbon steel coupons. The test apparatus is shown schematicallyin Fig.

which we do not understand. this is likely causing the steady drop of corrosion rates with time at the 324°C (616°F) test temperature.°C The corrosion rate of Type 304L staLrfless steel was generally higher than any of the other test materials. .6 0. Figure 5 is a plot of average corrosion rate versus temperature. The higher corrosion rates of stainless steel duplicate the field conditions.4 2.2 2. Because the corrosion reaction in molten hydroxide salts involves chromium. the hydroxide salts are more corrosive to the stainless steels than to carbon steel. The Alloy 600 weld overlay was the only weld material that consistently showed low corrosion rates in molten hydroxide salts. making this test a reasonable bas~s for alterhate material selection.8 0. the Type 304L stainless steel. L 320 330 340 350 360 370 .8 1. and the carbon steel corrosion essentially stops at the freezing point.o . The power of the on-line method of measuring corrosion is demonstrated by the data presented in Fig. This result is consistent with field observations. Average corrosion rates of probes exposed to molten sodium hydroxide as a function of temperature. and therefore 304L may not be the optimum material for tube openings. The plotted data show that the corrosion rate for 304L 76 Aunt 1993 TappiJournal stainless steel is greater than that of carbon steel by a factor of almost 10. this would not have been apparent in a conventional weight loss experiment. the corrosion rate for 304L stainless steel is observed to increase with time. but the probes were completely frozen in place at the 324°C (615°F) test condition. The Alloy 625 weld overlay showed marginal resistance to corrosion. particularly in higher-pressure boilers where highly caustic conditions prevail. mPa mm 100% NaOH r-~ 75% NaOH + 25% KOH mm 90% NaOH ÷ 10% Na2SO4 95% NaOH + 5% NaCl c:~ Repeat of Test deposit #1 2..6 2. Conversely. higher chromium levels in the alloy are detrimental. The boiler pressure corresponding to the metal temperature also is shown (assumes metal temperature is 50°F above saturation temperature) BOILER PRESSURE. and in some cases worse than. there is a variable corrosion behavior with time. The high corrosion rates of Type 304L seen in the field have been duplicated in the laboratory.4 1. The corrosion rates decrease as the temperature decreases. wherein Type 309L and 312 welds in the vicinity of corroded tube openings experience wastage at a significantly slower rate than the 304Lclad layer.6 0 1. Corrosion rates of weight loss coupons exposed for 720 hours in molten salt mixtures at 650°F with air cover gas (scrubbed of carbon dioxide) 5. The Type 309L and 312 weld overlays performed better than the wrought stainless steels. Type 310 stainless steel was nearly as bad as. implying that some corrosive species is being consumed (oxygen?) with time. Temperature limits for use of Type 304L stainless steel Pure NaOH has a melting temperature of 318°C (604°F). Furthermore. the 324°C (616°F) data for the frozen salt conditions shows a corrosion rate that decreases with time and becomes zero. Higher nickel . ° w°'' TEMPERATURE.2 . Diffusion of species in a solid are orders of magnitude slower in a solid (frozen salt) than in a liquid (molten salt).Corrosion 4. 6.0 1.hi. Both Alloy 625 and Alloy 825 wrought materials resisted corrosion by molten hydroxides. two replacement materials and two weld overlays for the purpose of repairs emerge as the most resistant to molten hydroxide corrosion: • Alloy 625 bimetallic tubing • Alloy 825 bimetallic tubing • Alloy 600 weld overlays • Alloy 625 weld overlays. At 370°C (698°F). Discussion NaOH corrodes Type 304L stainless steel. From this study. At 356°C (673°F).

j . Therefore. B. and Hupa. . 1988..5 356°C z =¢ . N.. 9. we came to the following conclusions: • Type 304L is rapidly corroded by molten hydroxide mixtures. Atlanta. TAPPI 1987 Engineering Conference Proceedings. T. TAPPI 1988 Engineering Conference Proceedings. Corrosion rates of various materials as a function of their Ni/Cr ratio.. Barham. 5. B. A. Mattie. H. TAPPI PRESS.. TAPPI PRESS. Wensley. 16.. 1296.0 0. Barham. J. 147.. Y ._. All of the resistant materials have Ni/Cr ratios over 1. M. However. . Figure 7 shows the corrosion rates of the various test materials plotted as a function of their Ni/Cr ratios. J. 77 . 1987.. H.. N. All of the resistant materials have Ni/Cr ratios above 1. 76. N. • High nickel. McGurn. 8 Tappi Journal Conclusions and recommendations Based on this study. D. j z ~ z= ~= N ! z 2. 13. OH. Barna. M. D. L.. Tran. Metals Handbook. 1992. L. J. ed... Paper 437.TAPPI PRESS. Garner.8 2. Barna. NACE. p. .2 0 .375 MPa (1200 psi).6 0. Because of the benefit of nickel and the detriment of chromium. F. p. Atlanta.8 0. I 332°C =_. Barbara. 7. 8. _- . J. Atlanta.. Accepted Nov. 0 o W Z2 ~'.4 1. sodium chloride appears to accelerate corrosion of Type 304L in molten hydroxides.5. Tran. low chromium alloys are the best replacements for Type 304L stainless steel.0 i I v Weld metal a Wroughtmetal t-Q: Z 324°C O 0 0 0 20 40 TIME. Atlanta. h 60 80 O O 1. TAPP11989 Kraft Recovery Boiler Operations Seminar Notes. Metals Park. H.2 1. D. The temperature effect on corrosion of Type 304L stainless steel suggests that boilers operating at 8. TAPP11989 Kraft Recovery Boiler Operations Seminar Notes. Tran. and Rogan. Salt mixtures used for weight loss corrosion retort test Weight % NaOH KOH Na2SO NaCl 4 Deposit I Deposit 2 Deposit 3 Deposit 4 100 75 90 95 0 25 0 0 0 0 10 0 0 0 0 5 levels in the material seem to be beneficial due to the formation of a protective nickel oxide.. Odelstam. it is reasonable to expect a relationship between corrosion rates and a parameter such as a nickel-tochromium ratio (Ni/Cr). TAPPI PRESS. such as resistance to sulfidation and oxidation. Barham. H. Rogan.. p. D. Corrosion in the Pulp and Paper Industry (A. Atlanta. Tran. J. .). ASM International. Presented at the TAPPI 1992 Engineering Conference. 3. Receivedfor review July 1.i 6' i i • Corrosion rates of 304L stainless steel corrosion probes as a function of time at selected test temperatures 7.1992. TAPPI PRESS..8 1. Houston. Because KOH mixtures are more corrosive. Materials Performance 27(7): 40-45(1988). [] Literature cited 1. when considering replacement materials additional considerations should be included.6 1. p. Vol. Likewise. but many constituents also could reduce the corrosivity or raise the melting temperature. p. TAPPI PRESS. Alternate materials should be considered on all units operating above 8.6 2. et al. and Hupa. Atlanta. No. et ~ . a material with adequate chromium levels also is recommended. TAPPI 1986 Kraft Recovery Boiler Operations Seminar Notes. 1350. . M.. R. 283. pp. N. and Hupa. Vol. we believe that dosed mills or high-potassium mills may see more severe corrosion.. Alloys 825 and 625 bimetallic tubing and Alloys 600 and 625 weld overlays have been demonstrated to resist corrosion. 4. 2.375 MPa (1200 psi) and above may be more prone to attack by molten hydroxides.. CORROSION/88 Proceedings. D. . J. However. p. 6.4 4 2 1 I "~1 I I I I.4 0. There may be some mixtures of hydroxides that may be molten at lower temperatures. 585. rapid corrosion of Type 304L stainless steel is seen even when no potassium is present. TAPPI 1986 Engineering Conference Proceedings.. 231.---- ffl 3 0 n. 1187-1220.l r 1 2 3 4 Ni/Cr RATIO OF METAL II.

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