Hydrogen Absorption of Titanium Heat Exchanger Tubes in MSF Desalination Plants-Shiri-Sato
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HYDROGEN ABSORPTION OF TITANIUM HEAT EXCHANGER TUBES IN MSF DESALINATIONiPLANTS Shiro Sato, Koji Nagata and Shigenori Yamauchi Technical Research Laboratories Sumitomo Light Metal Industries, Ltd. Nagoya, Japan l Introduction 1 Because of its excellent corrosion resistance, titanium has been exten sively used as heat exchanger tubes in various kinds of plants including MSF \ desalination plants. Regarding the service experiences of titanium tubes in I MSF plants, two different experiences have been reported. In one. case, two ! 1.5 MGD plants installed with titanium heat exchanger tubes on St. Croix in the Virgin Islands have been in successful operation since 1965 and 1972 [l]. On the other hand, in MITI's test plants, some of the titanium tubes used 1 in the brine heaters and the heat recovery evaporators have revealed the hy drogen absorption [2]. The data of hydrogen absorption are plotted in ·Fig. 1 in connection with the temperature of brine. As shown in Fig. 1, hydrogen I 1600 Test plant Position in tubes ~ 1400 0 Middle part ~ ii • A Tube ends .. ·- unknown ( ~ 1200 - <D I E a. t;. Middle part <D a. - I ... B Tub• ends - .. 1000 ~ I unknown ~ "' c I Mid~~~~-~---- .!! .._,,--- Tube ends BOO ~ c ~ :I e ·-'-r ------a> o•• ~ .L 11Edoe of expansion "'0 \1 ~JI ~ 600 ..e • ~ ·~ :1 :r (~ 400 -- <D I ' I 0 ' I I 200 "' 0 ~ • 0 ,;,Q 6> : ..... ~ tl \ 0 20 \ 40 60 BO 100 120 Tempuature ("CJ Fig. 1 Relation between hydrogen absorption rate and temperature in MITI's test plants. 398 S. Sato et al. absorption occurred remarkably at the temperature above 100°C. It was also noted that hydrogen absorption rate was widely scattering at the temperature higher than l00°C, suggesting the existence of some additional factors affect ing the hydrogen absorption other than brine temperature. In order to eluci date the phenomenon of hydrogen absorption under the condition of MSF plants, some experimental investigations have been made but the results were unsatis factory [2]. More recently, Togano [3],one leading member in MITI's project, pointed out the possibility of hydrogen absorption by the decomposition of ferrous' hydroxide, known as Schikorr reaction [4], 3Fe(OH)2 = Fe30• + Hz + 2H20. (1) This idea by Togano has attracted much attention as the deposition of iron corrosion products onto the heat exchanger tubes has been the common experi ences. Present work was undertaken to investigate the condition of hydrogen ab sorption in the solution containing Fe(OH)2 precipitates. In the experimental studies, effects of various factors such as temperature, surface condition of titanium, coupling with other metals and roller-expansion were studied in the brine containing different concentration of Fe(OH) 2. ·In addition, behaviour of Ti-Pd alloy tubes was also investigated. Experimental Procedure The specimens were prepared from welded titanium tube (Grade 2) and weld ed Ti-0.15 Pd tube. Hydrogen content of these specimens were 18-31 ppm. Surface conditions of the specimens were varied in three ways; as manufactur ed, as pickled in 7%HNOJ -3%HF solution, and as contaminated by iron after pickling. Contamination by iron was made by rubbing the titanium specimen with iron powder and iron rod. Some specimens were coupled with steel or copper sheet; ratio of surface area (Ti/other metal) was about 4. Some other specimens were roller-expanded into tube sheets; tube sheet materials were c.p. titanium, naval brass, or steel. The solution containing Fe(OH) 2 precipitates was made by neutralizing 20% (~ lM) FeCl24H20 solution by addition of 20%NaOH solution. The solution form ed greenish-white precipitates after neutralizing (pH= 6.7), and the precip itates varied its colour from greenish-white to white in a short time. In some tests, other soulutions were used to investigate the effect of Fe (OH)2 concentration;6%NaCl solution deaerated by N2gas bubbling for 24 hours, 6%NaCl solution to which O.lM or O.OlM Fe(OH)2 precipitates were added after deaera tion by N2 gas bubbling. All solutions were made with reagent chemicals and di sti 11 ed water. One liter glass beaker, which contained the specimens and the solution, was put into an autoclave. After evacuation by vacuum-pump, autoclave was heated to the desired temperature. Temperature was 80-150°C. The solution was renewed every 750hrs. Results l. Effects of temperature, surfaci condition and coupling with other metals Results of 1500hr test and 3000hr test in lM Fe(OH) 2 are shown in Figs.2 and 3, respectively. It was noted that hydrogen absorption occurred remark ably at the temperature higher than l00°C, though hydrogen content increased in some conditions even at 80°C. These results coincided very well with the results by MITI (Fig. 1). As can be seen in Fig. 2, hydrogen absorption of HYDROGEN ABSORPTION OF TITANIUM 399 --------________, Tube surface Coupling as manufactured 100 120 140 160 Temperature (°C) Fig. 2 Relation between hydrogen absorption of titanium tube and temperature (lMFe(OH)i, 1500hr). 100 80 . Ea. a. 60 E E"' e c 40 "'co .,,2... :c 20 0 80 100 120 140 160 Temperature ( •c) Fig. 3 Relation between hydrogen absorption of titanium tube and temperature (lMFe(OH)z, 3000hr). Specimens were tested without coupling with other metals. 400 S. Sato et al. titanium tube was extremely accelerated by coupling with steel sheet. On the other hand, acid pickling suppressed hydrogen absorption almost perfectly. 2. Effect of Fe(OH)2 concentration Hydrogen absorption in deaerated NaCl solutions with various concentration of Fe (OH) 2 is shown in Fig. 4. Hydrogen absorption was hardly observed in6% NaCl solution without Fe(OH}i, though two specimens showed a 1ittle increase in hydrogen content. This results corresponded to the results by otherworkers [2] [5]. In the solutions with 0.01 - lM Fe(OH)2 , on the other hand, titanium specimens as manufactured showed marked increase in hydrogen. From above results, it was obvious that Fe(OH)2 precipitates gave rise to hydrogen absorp tion of titanium tube. At each concentration of Fe(OH)2 , it can be seen that coupling with steel accelerated hydrogen absorption and pickling suppressed it as mentioned above. 160 140 120 E 100 .. / c !. -- --- c 80 3 ..c 0 e 60 ~ :c 40 20 0 001 01 Fe (OH) 2 concentration ( MI I ) Fig. 4 Relation between hydrogen absorption of titanium tube and Fe(OH)~ concentration in deaerated NaCl solutions (120°C, 1500hrJ. 3. Effect of contamination by iron In order to clarify the effect of contamination as pointed out by Cotton et al [6] who have investigated the hydrogen absorption of titanium in hydrogen gas at high temperature, titanium specimens contaminated by iron powder and rod after acid pickling were submitted to the test in lM Fe(OH) 2. Results obtained are shown in Table 1. It was apparent that contamination by iron made the pickled titanium susceptible to hydrogen absorption again. This may be HYDROGEN ABSORPTION OF TITANIUM 401 because iron contamination on tube surface presents the·convenient site for hydrogen absorption also in the present environment, or because iron contamina tion catalyzes the Schikorr reaction [4]. Table l Effect of surface condition on hydrogen absorption of titanium tube (lM Fe(OH) 2, 120°C, 1500hr). Surface condition Coupling Hydrogen content ( ppm ) none 43, 80 As manufactured with steel 91. 141 none 32, 33 As pickled with steel 3 I , 33 As contaminated by none 60, 73 iron after pickling with steel 11 2, 117 4. Effect of roller-expansion Results on roller-expanded specimens in lM Fe(OH)2 are shown in Table 2. Whichever material was used as a tube sheet, roller-expansion accelerated hy drogen absorption appreciably. These results suggested that iron contamina tion by expanding tool accelerated hydrogen absorption. It was noted in Table 2 that ·roller-expansion into steel tube sheet sensitized the pickled titanium again. In this case, tight coupling with steel, which may catalyze the Schikorr reaction or accept hydrogen easily, as well as contamination by expanding tool seemed to cause hydrogen absorption of titanium tube. Table 2 Hydrogen content (ppm) of roller-expanded specimens (lM Fe(OH)2, 120°C, 1500hr). Tube surface Tube sheet material As manufactured As pickled None ( not expanded ) 43 32 Titanium 66 23 Naval brass 63 24 Mild steel 78 110 5. Hydrogen absorption of Ti-Pd alloy Fig. 5 shows·hydrogen absorption of Ti-0.15 Pd alloy tube in lM Fe(OH)z. This alloy tube as manufactured showed extremely much gain in hydrogen, and even the specimens as pickled absorbed considerable amount of hydrogen. Above results demonstrated that Ti-Pd alloy was much more 1i kely to suffer hydrogen 402 S. Sato et al. absorption in the environment in question than c.p. titanium, Tube Tube surface r---2..- C. P. Ti as manufactured 400-f-6-+-------+-a_•~P_ic_kl_ed__ _, / E ~ Ti·O.l5 Pd as manufactured / Q. / <> • as pickled / / / __/. _,_ ~ 3001---------·-------- - _______ E / 3 / / c / .. / "' ~... 200 :r I OOt------,~- - ---------r-,-,..~,....-----_;-t)-- ,,,,,,"Ar' ~~~ - - - - - -- --- 0 1000 2000 3000 Time (hr) Fig. 5 Hydrogen absorption of Ti-0.15Pd alloy tube (lM Fe(OH) 2 , l 20°C ). 6. Microstructure of hydride and change of precipitates Fig. 6 shows cross section of a specimen after the experiment. Hydride needles were observed all over the wall thickness, which indicated that hy drogen absorbed at the surface had diffused into tube wall. Fig. 6 Hydride formed in titanium coupled with steel sheet (lM Fe(OH) 2 , 120°C, 3000hr). Hydrogen content was 269 ppm. In autoclaves containing Fe(OH) 2 precipitates and titanium specimens, ap preciable amount of hydrogen gas had been evolved even without metallic steel.