Corrosion

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
i

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.

Experimental
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.

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~ii!!iiiii!

Corrosion
i

1. Example of caustic corrosion around tube openings

2. Example of caustic deposits dripping from around a tube opening

Chemistry of test coupon materials Material C. steel 304L 310 Alloy 625 Alloy 825 Weld* 309L 312 625 600 C 0.11 0.01 0.06 0,01 0.02 Cr NR 18.20 24.87 22.10 23.34 Cu NR NR 0.11 NR 1.76 Fe BAL BAL BAL 3.08 30.41 Mn 0.36 1.82 1.94 0.05 0.41 Mo NR NR 0.16 8.81 2.74 Ni NR 8.11 19.72 61.97 40.22 P 0.01 0.031 0.024 0.005 NR S 0.015 0.011 0.001 0.001 0.001 Si NR 0,48 0.68 0.09 0.17

0.02 0.08 0.008 0.010

23.5 30.0 22.0 16.0

0.40 0,40 2.0 0,03

BAL BAL 19.5 7,50

1.5 1.5 0,20 0.10

0.30 0.30 7.0 NR

13.0 9.5 BAL 74,0

0.015 0,015 0.015 NR

0.010 0,010 0.010 0.005

0.40 0.50 0.30 0.10

* Nominal compositions of weld wire, NR = not reported. BAL = balance of alloy.

7~ August1993TappiJournal

3. Schematic of test system for materials screening test

Temperature recorder

.=s

Specimens Retort

Furnace Air inlet Air ouUet

weight loss of the coupons during this exposure period. The wrought coupons were 2.54 m m x 12.7 mm x 1.60 mm (1 in. x 0.5 in. x 0.063 in.), except the carbon steel, which was 3.18 mm (0.125 in.) thick. 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 carbon steel starting blanks were 25.4 mmx 19.05 mmx 4.78 mm (1 in. x 0.75 in. x 0.188 in.) with about 15.2 mm (0.060 in.) of weld metal build-up on all surfaces. The material chemistries are summarized in Table I. Because the weld metal will be diluted with the base carbon steel, the composition of the weld on the coupon will be lower in alloy elements than those reported in Table I. The chemistry of the welds was not analyzed. The test apparatus is shown schematicallyin Fig. 3. All coupons or weld overlayswere placed in 25.4-mm x 50.8mm (1 in. x 2 in.) high form alumina crucibles and covered with the hydroxide salt mixture. The crucibles were placed in support racks inside a test retort. The retort was heated using a vertical furnace. Air was scrubbed of residual CO~ using sodium hydrate-

asbestos and then metered into the test retort throughout the test. The test temperature was maintained at 343C + 5.5C (650F _+10F) for the entire test. Salt mixtures were added to crucibles containing the weight loss coupons. The various salt mixtures used are given in Table II. After one week at test temperatures, the retort was opened, and the salt mixtures were replenished as needed. Some loss of salts was seen due to evaporation and wicking up and out of the crucibles; however, all crucibles still had significant deposits after the first week. In addition, salts were still found in all of the crucibles at the end of the test, although some losses occurred.

(autoclave used as a heat source only). 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 0.0226-0.0283 m3/h (0.8-1.0 standard ft'/h). Care was taken to ensure that there was no metallic contact between the corrosion probes and the nickel container to prevent galvanic effects. Thermocouples immersed in the melt were sheathed in Alloy 600. The temperature compensation device on the carbon steel corrosion-resistant probes did not function as planned. Consequently, carbon steel corrosion rates required evaluation by cooling the probe down after each test. 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). Average corrosion rates were determined by measuring the ambient temperature probe readings at the start and again at the completion of each test. The difference in probe readings was converted into a corrosion rate.

RP~ults Materials screening test

The corrosion rates of the test materials in molten hydroxide salts at 343C (650F) are given in Fig. 4. All mixtures of hydroxide salts are more corrosive to Type 304 stainless steel than to carbon steel. The most corrosive mixture to stainless steels is NaOH + KOH. Moreover, all complex salts appear to be more corrosive than NaOH; NaC1 and NaeSO4 additions also increase corrosion rates above those seen in pure NaOH. At the end of the test, the NaOH + KOH mixture was found to be nearly totally depleted from the crucibles. This may be partly due to the rapid corrosion seen in this mixture, but salt also was lost due to evaporation and wicking of the salt out of the crucibles. Significant amounts of all of the other salt mixtures were found at the end of the test.

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 371C to 323C (700-613F). The NaOH was contained in a nickel 200 crucible covered by a lid. The crucible was heated by placing the container into a two-gallon autoclave

Vol. 76, No. 8 TappiJournal

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Corrosion
4. Corrosion rates of weight loss coupons exposed for 720 hours in molten salt mixtures at 650F with air cover gas (scrubbed of carbon dioxide) 5. Average corrosion rates of probes exposed to molten sodium hydroxide as a function of temperature. The boiler pressure corresponding to the metal temperature also is shown (assumes metal temperature is 50F above saturation temperature) BOILER PRESSURE, 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 2.4

2.2
2.0 1.8 1.6

0.8
0.6

0
1.4 1.2

,hi,,
L
320 330 340 350 360 370

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TEMPERATURE,C

The corrosion rate of Type 304L staLrfless steel was generally higher than any of the other test materials. Type 310 stainless steel was nearly as bad as, and in some cases worse than, the Type 304L stainless steel. Both Alloy 625 and Alloy 825 wrought materials resisted corrosion by molten hydroxides. The Type 309L and 312 weld overlays performed better than the wrought stainless steels. This result is consistent with field observations, wherein Type 309L and 312 welds in the vicinity of corroded tube openings experience wastage at a significantly slower rate than the 304Lclad layer. The Alloy 625 weld overlay showed marginal resistance to corrosion. The Alloy 600 weld overlay was the only weld material that consistently showed low corrosion rates in molten hydroxide salts.

Temperature limits for use of Type 304L stainless steel Pure NaOH has a melting temperature of 318C (604F), but the probes were completely frozen in place at the 324C (615F) test condition. Figure 5 is a plot of average corrosion rate versus temperature. 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. The corrosion rates decrease as the temperature decreases, and the carbon steel corrosion essentially stops at the freezing point. The power of the on-line method of measuring corrosion is demonstrated by the data presented in Fig. 6. At 370C (698F), the corrosion rate for 304L stainless steel is observed to increase with time; this would not have been apparent in a conventional weight loss experiment. Conversely, the 324C (616F) data for the frozen salt conditions shows a corrosion rate that decreases with time and becomes zero, implying that some corrosive species is being consumed (oxygen?) with time. Diffusion of species in a solid are orders of magnitude slower in a solid (frozen salt) than in a liquid (molten salt); this is likely causing the steady drop of corrosion rates with time at the 324C (616F) test temperature. At 356C (673F), there is a variable corrosion behavior with time, which we do not understand.

Discussion
NaOH corrodes Type 304L stainless steel, and therefore 304L may not be the optimum material for tube openings, particularly in higher-pressure boilers where highly caustic conditions prevail. The high corrosion rates of Type 304L seen in the field have been duplicated in the laboratory, making this test a reasonable bas~s for alterhate material selection. Furthermore, the hydroxide salts are more corrosive to the stainless steels than to carbon steel. The higher corrosion rates of stainless steel duplicate the field conditions. From this study, 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. Because the corrosion reaction in molten hydroxide salts involves chromium, higher chromium levels in the alloy are detrimental. Higher nickel

i 6'

Corrosion rates of 304L stainless steel corrosion probes as a function of time at selected test temperatures

7. Corrosion rates of various materials as a function of their Ni/Cr ratio. All of the resistant materials have Ni/Cr ratios over 1.5

356C

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z=
~= N

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z

2.8 2.6 2.4 4 2 1

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=_._.----

ffl 3 0 n,, 0 o

Z2 ~'.0

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t-Q: Z 324C
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1 2 3 4 Ni/Cr RATIO OF METAL

II. 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. Because of the benefit of nickel and the detriment of chromium, it is reasonable to expect a relationship between corrosion rates and a parameter such as a nickel-tochromium ratio (Ni/Cr). Figure 7 shows the corrosion rates of the various test materials plotted as a function of their Ni/Cr ratios. All of the resistant materials have Ni/Cr ratios above 1.5. However, when considering replacement materials additional considerations should be included, such as resistance to sulfidation and oxidation. Therefore, a material with adequate chromium levels also is recommended. Because KOH mixtures are more corrosive, we believe that dosed mills or high-potassium mills may see more

severe corrosion. Likewise, sodium chloride appears to accelerate corrosion of Type 304L in molten hydroxides. However, rapid corrosion of Type 304L stainless steel is seen even when no potassium is present. The temperature effect on corrosion of Type 304L stainless steel suggests that boilers operating at 8.375 MPa (1200 psi) and above may be more prone to attack by molten hydroxides. There may be some mixtures of hydroxides that may be molten at lower temperatures, but many constituents also could reduce the corrosivity or raise the melting temperature.

Alternate materials should be considered on all units operating above 8.375 MPa (1200 psi). []

Literature cited
1. Odelstam, T., Tran, H. N., Barham, D., et ~ , TAPPI 1987 Engineering Conference Proceedings,TAPPI PRESS, Atlanta, p. 585. 2. Barna, J. L. and Rogan, J. B., TAPPI 1986 Engineering Conference Proceedings, TAPPI PRESS, Atlanta, p. 1296. 3. Barna, J. L., Rogan, J. B., Mattie, R. J., et al., TAPP11989 Kraft Recovery Boiler Operations Seminar Notes, TAPPI PRESS, Atlanta, p. 1350. 4. McGurn, J. F., TAPPI 1988 Engineering Conference Proceedings, TAPPI PRESS, Atlanta, p. 147. 5. Metals Handbook, Vol. 13, Corrosion in the Pulp and Paper Industry (A. Garner, ed.), ASM International, Metals Park, OH, 1987, pp. 1187-1220. 6. Wensley, D. A., TAPPI 1986 Kraft Recovery Boiler Operations Seminar Notes, TAPPI PRESS, Atlanta, p. 231. 7. Tran, H. N, Barham, D., and Hupa, M., CORROSION/88 Proceedings, NACE, Houston, Paper 437, 1988. 8. Tran, H. N., Barbara, D., and Hupa, M., Materials Performance 27(7): 40-45(1988). 9. Tran, H. N., Barham, D., and Hupa, M., TAPP11989 Kraft Recovery Boiler Operations Seminar Notes, TAPPI PRESS, Atlanta, p. 283. Receivedfor review July 1,1992. Accepted Nov. 16, 1992. Presented at the TAPPI 1992 Engineering Conference. Vol. 76, No. 8 Tappi Journal

Conclusions and recommendations

Based on this study, we came to the following conclusions: Type 304L is rapidly corroded by molten hydroxide mixtures. High nickel, low chromium alloys are the best replacements for Type 304L stainless steel. Alloys 825 and 625 bimetallic tubing and Alloys 600 and 625 weld overlays have been demonstrated to resist corrosion.

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