26 stainless seat eH aendon at g,fube fom © inde eens ra opese up 8 & Figure 4-—typicel_corrvon information gathered ome sabettory sercennp, fest Ce Se" own fan egane aiden “HSsie for pubzon Apel 14 1959. A paper resented ae "Rantal Conterenes Res Boast Aactlaies of onounn Engines March 1635, 1888; Chicago, I Selection of Alloys For Refinery Processing Equipment* By A. J. FREEDMAN, G. F. TISINAI and E. S. TROSCINSKI Introduction EFINING CONDITIONS ia the Present push for higher octane gaso- line ate becoming more and more severe New and valuable. petrochemical proc: esses will demand process condition d fering’ considerably. from ‘those in the fefining industry today. For these. reac Sons, plus the ever-present need fo select the most economical materials of cone struction, careful selection of alloys Becoming increasingly important. Precone Ceived ideas concerning wee of particular alloys under certain conditions and teat- ‘ent of these alloys during construction Should be discarded in favor of care- iully planned and. executed. evaluation program. This program should consider Al possible variables whieh might influ: thot allay performance during construc- tion and normal operating cycles, inlud= ing both oncstream and shutdown periods fects of Process Variables A. dramatic example of the effect of Eommon alloys is the problem of high temperature sulidic corrosion in reform ers Tow chromiumemolybdenumstels fave been ‘sed for many years in fur- nace tubes on etude units, thermal erack- ing ‘unite ‘and hydroforming units. proc. sing sour stocks. When the newer Catalye reforming units were first de- Signed, it appeared so logial to specify these same alloys for high temperature furnace’ tes that Tle. acenton was id to posible new corzosion problems. Problems hg rom use of aera om the other hand, were seca ‘and Studied ‘thoroughly with the result that problems have been practically: non- Chen i) operating” uit But these carly unite were plagued by plugged cat: alyst_ beds, "poor conversion. an other troubles resulting from the accumblation af large quandiues of loose, brite scale. Only “when the magnitade and. impor- tance of this problem became cleat were Mudie made" to. understand. the corro- sion problems of these reforming proc- esses. Careful control of H.S/He ratios fd oof propery Roatsratcd 108 Stainless steel Or properly aluminized low Alloy steel furnace’ tubes have almost lintinated cotrsion and sealing problems jn catalytic. reformers. This experience, throughout the industey, has avvakened most refiners to the dangers of basing Alloy selections only on. past experience developed When alloys are selected for a new unit oF proces, all conditions to be’ ex- pected. during ‘aormat operating. cycles must be considered. For example, a mod. ten pipe atl had several forced. shut: dlowas in quick succession when the nie 107 Abstract Discusses variables im a refiery which af; Feet telecon of alloy tates 0 be weal fn‘ construction of uals Gives examplet of aures caused by"Tack of evabaton of toe in new proecies before Tabreation icietd reasons Iaboestory and 4 uid Be esabished “and information on, efeete of meric "concentration, and” tne ‘kp “discuss ‘metallurgical comideratons sles ‘oui be made I section af alle Et ec etait ten nd fa SES Grito’, alge a tthe’ need ‘to maintain. effective records of {est"chemical comporion and eat teat pent ‘hitory\ of each "specimen- Brey Hedin tect Ge snout lay salutes by"corrosoa monitoring in" proces equ: ment oo was new. ‘These shutdowns were caused by leaky. relief valves om the primary tower. Type 316 stainless steel valves ‘were installed during inital construction of this unit. Normally, this alloy. would be entirely” satisfactory inthe’ process fluids found in this unit. However: small amounts of sour naphtha and hydro- thlorie acid collected in narrow crevices Around the valve seats and rapidly ine This phenomenon, known a6 crevice corrosion, occurs when circulation oF df= to maintain the normal steam composi tiom at these points. Valve seats or the relief valves corroded rapidly, andthe Walves ‘could “not be closed properly. Figure 1 shows the corroded face of one af these valve seats, Solving this problem, once it was siscovered. and understood, was nat too difficult. Hastelloy B alloy Facings, resistant to acid atacks, were subsctted for the ‘Type. 316. steel on Walve seats and iss, and the problem disappeared Another specific operating variable which has caused. considerable dificulty Jn refinery unite is impingement attack. Gna pettocherical unt, for instance, = boiter tubes which were struck by a High velocity, "high temperature stream of corrosive fuids corroded severely Figure 2 shows the characteristic grooved appearance of tubes removed from this ute Tin this casey laboratory texts indie Cad hay ater than sine more Berslved more economically by modify. ing the process stream. Addition of ox dation iahibtors to prevent formation of Corrosive “components effectively elie nated impingement attack, Tn addition to conditions during nor- Nironments existing during shutdowns Ble must be considered when selecting fluid hydroformer were constructed. from 198108 Freedman datas gaye Rettas Senior Pre certain the "Soma a He eecied’¢ PRD degree from New York Univesty'n 4846. Pri fo joining Standard BIE ea enc ar at fhe Mane Schott Laborgtory ond the University of Rew wie ” Gi TISINAL is price supervisor in the BenceingReeatchDoportmentsStondard oi ei ‘ Engineee: tng Research Be. ie Standord Trscinak ‘Type 304 stainless steel, ‘This is a stand- aed imaterial for ths application, and no Corrosion. was expected. However, Teake fceurred in thee furnace tubes after only a few montht’ operation, ‘These leaks were found only near buttwelded joins Sections of the tubes, with cracks which appeared upon bending inthe laboratory, ate shown ia Bigure 3. > New welded tubes were found to be metallographially sound although some Circumferential. sbrinkage of the tubes had occurred near welded joints, This shrinkage was noted during fonstruction af the unit but was not considered serious. No ready explanation could be found for the failure of these tubes. lowever, laboratory corrosion tests wing solution’ similar co those in the tubes ding shute downs indicated the answer: intergram lar’ stress corrosion cracking caused. By aqueous condensates containing HS and 80, These gases react in the presence of water to form polythionic acids. These Acids are known to. stress erack 1-8 Mainless steels intergranular, once the eels have become sensitized by heating the proper range of temperatures Normal Fabrication procedures. provided the sizes, normal operating temperatures provided the sensitization, and normal Shutdown Procedures provided. the cor- 20t CORROSION—NATIONAL ASSOCIATION OF CORROSION ENGINEERS rodant. The result was a troublesome Tallure which was not detected until the unit was back’ on steam. Tn any ease. of corrosion failure, re- sistant alloys can be selected to. Bt the process, or the process can be modified fo accommodate available materials. Th the ‘ease of the uid hydroformer, the economical solution wat to change the Shutdown procedure to keep the furnace tubes free of condensate. Many other ine stances of corrosion. during downtime Have been recognized in. recent” years. The importance of controlling corrosive environments during. sbutdowns cannot be. overemphasized) especially when ex: pensive alloys and riical ‘heat. treat. ments were used during intial construc- tion of a unit. External and internal operating eondi- tions ‘must be ‘consdered in selecting Alloys. For example, in plants near salt ‘water, normal condénsavon occutring in the evening after a warm day may con tain appreciable amounts of salty even Salty tov the taste. During: warm days, this condeusate tends to dfy up, leaving salt behind, During the evaporation proce ess, conditions are ideal for transgramc lar stress corrosion cracking of austenitic stainlest steels The danger of strestcor- fosion cracking can be minimized. oaly by such means as proper heat treatment ater cald forming operations of powbly iy use of protective coatings or cathodic Similar favorable conditions for srese conrosion cracking say atte from use of Sale or brackish water in exchangers con iaining stainles stel of from having any of several different types of insulation in Contact with stainless steel. There seems to be enough residual chlorides in many inaslations to cause slanles tel to sess Corrosion ctack from moisture picked wp during normal condensation, It is ox tray ele to ea sch inlaon Completely against the entrance of water Vapor, if’ not liquid’ water, ‘The mere fact that stress corrosion has not ap- peared in older units is not a. postive Evarantee that ft will not appear in new Unite if conditions otherwise seem to be favorable. Not enough is known about this type failure to make aswarances. of its occurrence oF ‘nonoccurrence under any circumstances Laboratory and Pilot Plant Gorresion Testing A poor choice of metals for new unit constfuction can lead to costly and Sometimes hazardous failures in critical arts Also, preliminary corrosion experi- nce’ may have a vital influence onthe economic. decision to. construct a com mercial process. “That is, 2 new unit which. is" technically attractive may be economically ‘unsound because of “high material cost needed to contain the proc- Because of is importance, a corrosion- testing program for anew process ot unie should: begin as soon a8 feasibility of the process has been established, This program in. general. should consist of {wo parts Firs, preliminary laboratory study should be made to screen posible materials for construction of @ pilot Vol. 15 plant. Second, a combined laboratory and pilot plant program should. be planned. to. study, from the chemical, process and metallurgical viewpoints, all Corrosion problems expected in the com mercial unit Preliminary Work Because it is impossible to duplicate an entire refinery or chemical process unit in the laboratory or even in a pilot Plant, any corrosion testing program Should begin with a careful study of the process, Flow’ sheets should be’ exam- Ined for critical locations from a cor- rosion viewpoint. Laboratory tests, then tan be devised 0 reproduce, as closely fs practicable, all operating. conditions at these locations, ‘This is essential. Omis- sion of one variable such as impinge ment or peevence of crevices, for eX ample, can lead to a false estimate of alloy bchavior at the location Ince laboratory equipment is avail gpl matrneto by ete ae ected f corrosive components in the process steam ae known, the eoroson litera: ture may provide’ valuable clues. Pub- Tished information cannot always be used as final authority; small changes operating variables such as stream con- centration or temperature can affect pro- foundly the corrosivity of the fluids. If xno. past experience is available, metals Fanging from carbon. steel to. the so- called superalloys must be considered. Jadicious metal selection for intial testing can save time in later evaluations. ‘Any metals examined must be capable of ‘withstanding the physical stresses, of hhormal service, must be readily available fat a reasonable cost and must be amen- able to fabrication by standard methods Te would be foolish, for example, to evaluate an alloy available only in cast formas a possible material for tubing rom a relatively few laboratory tet, much information ean be obtained. Types Of alloys requited in the construction of the pilot plant equipment can be deter- mined readily. Tigure 4 shows. typical Corrosion information which can be gat ered in laboratory screening tests. These data were obtained from a single corro- sion tes in an organie acid solution con- taining process impurities at 108 F by means. of laboratory corvosion probes Corrosion probes have been described in earlier publications * rom the graph, it can be agen hat carbon tee, corroding at 0.275. inches per year, would be totaly unsuitable for te in this service. Even Type SOE stain. tess steel, with a corrosion Fate of 0.064 inches pet year, does not appear to have any merit. Type 316 stainless see, with 4 Corrosion rate of 0.021 inches per year, iooks promising and probably is a good construction material for the pilot plant equipment. This. alloy seems’ especially ercouragings the corrosion appears to be ccreasing fo 4 negligible value after ap- proximately 20 hours. ‘This effect can be Exuaed by protective lm formation or possibly by" depletion of the corrosive hgent in the solution, Such beneficial cflects may not always be realized ina Actual process, especially under high ve- Tocity conditions or in a'continuots proc.8 Es EXTRAPOLATED CORROSION RATE ‘Mics PER YEAR ure Safeco tem Sct of temperate om eeain rats ihoniaeeguston cst in which the depletion effects are negligible. The last alloy shoven, Hastel- loy G, ‘corroding at 0.007. inches per year, should be telied on for excellent Torrosion protection if subsequent. work proved Type 316 stainless steel to. be Snsuitable ‘When alloys are chosen for a pilot plant i fs important to remember that the lane pron wil provide product Eimples having high pusity for consumer fraluations. A considerable amount of time "and money may be. requized (0 pany product the mater edo pilot” plant equipment are. not selected Exrefully to prevent contamination by Corrosion products, Corrosion Testing During Process Development In the combined laboratory and pilot plant work following” the initial labor tory. tents, a judicious corrosion eval- tation. program is required. Here, all possible! variables auch as temperature, Stream composition, alloy microstructure, fabrication procedares. and. possible ‘oc. carrence of various types of corrosion ‘hould be evaluated thoroughly, both in the pilot plant equipment and also under mulated procest conditions in the labo- fatory. Similarly, external conditions at the proposed plant location should. be Conder. Far example, amonere pollutants and the type cooling ‘water Evallable canbe limiting factors in the hoice of certain constriction ‘materials Temperature Effects In many cases, final operating temperatures of com: nercil proce are tot determined on heat the end of the pilot plant study. Hence, it is important’ that constriction alloy corrosion rates be determined over the entre range of posible temperatures In many cases, temperature. effects on corrosion rates can be predicted from the then equation “Ifthe Atmhenius Equation is vali a plot of the corrosion rate logarithm against the absolute tent. perature reciprocal should. result in Feraight line, as shown in Figure 5, This type information is useful in. predicting corrosion rates. Knowing that & particus Ke=@ RF + Ache Equation: Corroron Rate where Ln Corrosion Rate = “+ Constant SELECTION OF ALLOYS FOR REFINERY PROCESSING EQUIPMENT 5 lar type of corrosive environment be- haves in this manner enables one to interpolate or extrapolate corrosion rates over a wide temperature range, ‘Temperature has another important effect on corrosion rates, Metals of alloys an corrode by one or more mechanisms, depending upon temperature of the cor rosive medium, Corrosion rates can d crease with exposure time, remain constant with time, increase with time for combine all three effects. The corro- sion mechanism is important when the results of short term corrosion tests are extrapolated toa yearly basis. As an example, the effect of distillation residue temperature on the corrosion rate of ‘Type 316 stainless steel is shown in Fig- ure 6. The conditions shown in this graph are typical of those found in a distlla- tion column where a wide range of tem- perature is normal. In this application, ‘Type 316 stainless probably would be a suitable construction material at temper- atures to about 350 F. In this tempera- ture range, the protective oxide films on the surface of the stainless steel appear to be maintained; at higher temperatures, the films break down and accelerated Concentration Effects. Stream concen trations can have important effects on corrosion rates, Unfortunately, corrosion rates seldom are linear with ‘concentra tion over wide ranges. In equipment such as concentratars, reactors and distillation columns, concentration changes occur continuously, making prediction of cor- rosion rates difficult. ‘The effects of boil- ing acid at different concentrations on the corrosion rates of several alloys are shown in Figure ?, In this application, the concentration of acid did not appear to influence the corrosion rate of Hastel- loy C. Corrosion rates of Types 316 and 317 stainless steels increased continuously with increasing acid concentration, Type 304 stainless showed an apparent. maxi- ‘mum at about 40 percent acid. At higher concentrations, the corrosion rate de creased to a substantially constant value, Time Effects. Metals or alloys ean cot rode by one or more mechanisms. In this situation, corrosion rates often are ex- pected to change with time. Figure 8 lustrates typical corrosion-time curves. ‘The rate of attack may (1) remain con- stant with time as shown in Figure 8A, (2) slow down at a rate inversely propor- 109 109) = TASTELLOY € EXTRAPOLATED CORROSION RATE MiLS PER YEAR 0-20-40 60-80 100 ACID CONCENTRATION % Figure 7—Eect of organic acid concentration on corarion rates of basing temperature onal 0 the ehickacs of the scale a8 shown in Figure. 8B or. (3). virtually Stop after a tapid inital atiack of lime ited magnitude as shown in Figure 8C. “The attack rate also may be more complex, For instance, the curve in Fig- tire BD has a range in which the corro- sion accelerates with time, and the curve in Figure 8E, consists of small parabolas, cach parabola corresponding "to. scale growth, and each break in the curve to f fracture of the scaley followed. by 2 healing of the breaks. Once the charac: teristic rate type is established, reason able extrapolations canbe made from Short tests to Tong time exposures. Also, possible ways ‘of controlling corrosion Tay be suggested by these data. Tt intergranular corrosion, stress cor- rosion cracking, hydrogen embrittlement or hydrogen blistering should occur, the time factor may be of litte. importance. It these types of corrosion ace observed in any application, the material generally is considered to be unsuitable, and other materials are selected or some other equally safe and positive corrective meas- tre if taken. The risk of a sudden, un- predictable. and. uncontrollable. failure Eaused by one of these mechanisms can- hot be taken in any commercial unit or pilot plant. Only in cases of uniform at. {ack and pitting are rates of propagation considered and corrosion allowances es- tablished. Velocity and Impingement Bilects Many laboratory text nd. plot plane operations may be conducted tinder cons altons somewhat lest severe than. dhose Which ill occur in the actual operating Unit, Stream velocities in particular may Be lower. This can be extremely impor: femed because many materials’ depend pom formation of protective surface film to” provide corrosion resistance. Tt this film’ removed. by exposure fo a high ‘velocity “medium. or By impinge ment of dispersed gases or similar dis Curbing elements upon the metal surface, the covrosion race“can be much higher than it would be if the Alm. were. per- mitted to form in its normal fashions Depending largely upon chemical com- postion somie alloys are stacepable to this type of fin formation andl others atVol. 15 other and are exposed to an electrically. solution, combinations of metals should be chosen that are as close together as possible in the galvanic series. Coupling two metals widely separated in this series generally will’ produce ac~ celerated attack on the more active metal Often, however, protective oxide films and other effects may reduce or eliminate galvanic corrosion. Final decision in each application should be made on the basis fof thorough laboratory and_pilot plant study of galvanic tendencies on’ the Eifects of Additives and Process Changes Corrosion rates often can be affected” greatly by minor amounts of compounds added “to process reams. Corrosion inhibitors, for’ exam= ple, have saved millions of dollars fn the Pettoleum industry by eliminating, the heed for. expensive alloy ‘construction Anti-oxidants added in small amounts to 110 CORROSION—NATIONAL ASSOCIATION OF CORROSION ENGINEERS STEEL IN ACID SCALING REACTIONS. ALIN AIR other and z 2 z 8 el 8 3 g g 2 Ez zg = 8 a 8 8 8 c nea nae Lggagitimic on LINEAR PARABOLIC Resrueverie STEELBRASS IN SULFUR tnetals Invelood 7 Cu IN HoS~ 3 3s 3 3 special § = 7 8 E— ° D TIME TIME MIGRO-GATAGLYSMIC SIGMOID Figure 8 Schematic crtsion-tine curves. Figure 9Veloity effects ne co Had eel Spel Wo" are not. For example, the corrosion re- Esance of Hastellay © docs not teem to depend at all upon film formation, where- a5 that of Tlastlloy B scems quite de- pendent ‘upon this effect Sensitvity to Nelocty of impingement effects can be Keudied adequately in the laboratory if the pilot plant does not provide suitable Conditions, but information must be avail able to cover the range of stream veloc ties expected in the final operating units Also, If'a realistic evaluation if to. be ‘ade; such tests must be conducted under actual operating conditions of tempera thre and presure and with actual process Components in plant streams, which can- 22t si Staines tel, Specimen @: Hasty 8 pstochomiea, process 5 shadimen 0" carn set. Toe iS nnot be introduced readily in synthetic laboratory solutions, may be the main culprits in causing ‘severe velocity cor- ‘An example of the effect of veloci or impingement on corrosion rates is shown in Figure 9. Samples shown were exposed! in a corrosive stream from a petrochemical plant. They were rotated at a peripheral speed of 1130 fpm. Typi- al velocity effects can be seen on the ‘Types 304 and 410 stainless steels, car- bon steel and Hastelloy B. Type 316 stainless steel was not affected. Galvanic Effects. When dissimilar metals are used in contact with each of corrorive organic peroxides and acids Nitrogen blanketing of storage tanks ac complishes a similar. purpose. In some cases addition of a. drying tower may climinate small” amounts “of corrsion producing ‘moistre.from_an otherwise fnnoctous steam. Alternatively, ia ether cases dilution of this corrosive’ moisture with relatively” large amounts of water may render less dangerous “These possbilies may produce large savings in capital investuent costs By Permitting use of carbon stel, for exam Ple, instead of expensive alloys. Careful Taboratory and pilot plant testing usually will indicate the value of these methods in a particular case. OF course the re= quired purity of the final products from Suchemleal plant may prevent use of ad- ditives Tor Corrosion-cantrol ‘Metallurgical Considerations General Selection Although a metal of a given type may be necessary (0 provide resistance to & corroding medium, the metal’s corrosion resistance may vary over a relatively wide range, depending upon its metal- lurgical structure, Properties of a metal or alloy may be either structure-sensitive for structure-insensitive, In general, cor rosion resistant metals are sold commer cially in the condition in which they have optimum corrosion resistance. Hence, the preliminary weeding-out tests, conducted at the bench scale stage, should be made using commercially as-received materials. These. tests will establish which basic type alloys (for example, nickel-rich, eop- per-rich, aluminum-rich, stainless. steels, etc.) should be considered for further study. Often this general information is known from data in the literature, Microstructural Effects Weld Metal Structure. Plant equip- ment is built mainly from wrought ma- terial, fabricated largely by welding, The welding operation can. introduce objec- tionable features which should be evalu- ated. Deposited weld metal has a struc- ture’similar to that of a casting although possibly not quite as coarse grained. Fig- lure 10 shows normal metallurgical strue-January, 1960 dite in sk dlc Sale a sGepeit; Cored tructre islets itfrenecs. in shading. ofthe fe ‘motries 123K Glycerin eth etch Section Bs Stossel el tures for typical stainles steels in the ae erie fora and lion teat fd) and the weld: deposited. (cat) con: ditions. ‘The ‘weld metal has a. cored Structure, consisting of miro-regions of Saryingthemicalcomposions, 8 result of solidification directly from the molten State. The cored structure may be nde: Sirable in severe corrosive media because fn interdendrtc corrosion anay”worm into’ the metal. However, this effect fot normaly met in most processing Imedia, Satistctory ‘homogenteation of the cored weld. structure may require heat treatments from four o eight Hours or sometimes even longer at rather high temperatures, Such heat treatments may or may not be practical. Grain Boundary Precipitation Effects in Stainless Steels: Welding also produces a heat affected zone in the base metal on tach side of the weld metal. This zone is that region in which. temperature. has foen enough to permit metallurgical re- actions to take place during welding. In Some metals such as stainless steels and high nickel base alloys, this can lead to 2 eontlition known as sensitization. Sensitization also can occur ina solu- tion-annealed. structure ifthe metal is held for a sufficient ime at temperatures between 800 and 1500 F. A typical sensi teed structure in stainless sal is shown in Figure 1A, A continuous precipitate actually chromium carbide in stainlest Heels, occurs in the grain boundaries, In iweldments this precipitation fs localized near the base metal which is adjacent to the weld. Accelerated attack can occur in these sensitized zones because of chromi- lum depletion in the metal. adjacent. to the grain boundaries resulting from this WN OF ALLOYS FOR REFINERY PROCESSING EQUIPMENT 1 Tipe 204 ‘Corbide network 125K, i ted’ eich ‘Section osinsed austenite ton: 25X, Ghearegio etch Shown of low moan precipitation or because of galvanic ef- ects induced ‘by it in conjuction. with the matrix. Th's may lead to aki edge attack in weldments in the heat af- fected. region, “Where the entire base metal has been sensitized by an appropri- ate heat treatment, there may bea gene cron in aderonce betwee the meta grains, This destroys the matetial's physic Gal properties. Figure 11B illustrates the mature of the corrosive attack in a sen- Sitized region of a stainless steel ‘Various ways have been found to elimi- nate’ sensitization in stainless steels. Be- Cause the principal rapid precipitant in Stainless stels is Enown to be a chromium tarbide, precipitation should not occur if'the carbon content of the material is decreased to. a low enough. value. ‘The present specification limit for so-called xtra low carbon (L of ELC) materials is 0.03 percent carbon, ‘This, unforunate- 1y, often is interpreted bythe mills to mean 0.035 percent carbon. Accurate Analyses are difficult to make for carbon in stainless steels. Also, there may be Some question as to carbon content/uni- formity. throughout a large heat of ma- terial. Consequently, carbon contents may vary widely" from’ the specified limi, and the actual advantage of the ELC srades for high corrosion resistance may fot always be obtained ‘Another method {0 avoid sensitization in stainless steels is. through chemical abilization, Addition of proper amounts of niobium’ (still called ‘columbium, by most American metallurgical companies) or iantam to he safes ede, foe lowed by appropriate heat treatment — preferably about’ 1600 F, will cause the Earbides to. precipitate “throughout the metal structure as disrete niobium or tanium carbides, rather than preferen- tially at grain boundaries as continuous clhromium carbides. Consequentyy the Corrosion resistance’ is not affected ad- Wersely so. far as. sensitization dusing welding is concerned, If weldments are held for” short. periods at temperatures neat 1200°F without prior 1600" treat. ment to precipitate the carbides, the heat fected "zones may become. sensitized ven in the presence of niobium or “Another method of avoiding senstizn- tion in stainlese steels 'y called thermal Stabilization. ‘This method is based upon the principle that the grain. boundary precipitate of chromium carbides is least Rrarmfl in the form of discrete particles which do. not have such’ partce-to- Particle contact. ‘The precipitate can be cparated in this way by use of special heat treatments before the metal fp into service. For stainless ate a mini sum of four hours at 1600 25°F is Fequired. However, as in the chemically Nabillzed steely it is not wise t0 hold weldments of such a heat treated steel at temporatres near 1200 F vies the sted ie"again heat ‘treated at'1000 Falter welding Th service temperatures fall, between 200 and 1500 Fan intermetallic phase called the sigma’ phase may form slowly in most stainless steels Formation of signa, phase drastically reduces the lin pact dactilityand in some cases the cor- Fin estan of sates so. Sh Fiat offects of chemical ‘and therial stabilization in these alloys Grain Boundary Precipitation Effects in Other Alloys. Other alloys also de- Be112 velop sensitized microstructures which make them susceptible to intergranular desived medium before being applied Attack in appropriate media. For example, copper base alloys tend to be susceptible even though no obvious sensitization ef- fects can be noted in their microstructures. This is especially true in ammonia. con- taining media, Recently, there have been some feports that a modified type of alu- minum bronze may be immune to many of the media that normally attack copper hase alloys intergranalarly. Although the reports seem promising, any such alloy should be tested in the desired medium before being applied extensively. Effects of microstructure upon cor- rosion rate may be important even with the most highly corrosion resistant super alloys. For example, Hastelloys B and C have alloy contents so high that, for most applications, chemical composition alon provides adequate corrosion resistance Metallurgical structure in such cases is of litle importance. However in_some respects, the Hastelloys are similat to the ainless steels. The alloys’ optimum cor- rosion resistance is produced by a sola- tam anneaing eat rete hich re 5 4 rapid cool from the annealing temperature: Figure 12A shows. a. good solution annealed structure in Hastelloy- G. However, if this annealing treatment is not carvied out properly, the sensitized structure shown in Figure 12B may result with a continuous grain boundary pre- Sipitate In severely corrosive media, sensitized Hastelloys Band C may corrode inter: sgranularly. Heat affected zones adjacent {to welds on these alloys are. subject to this attack even though the base ‘metal is" solution-anmealed, Also, ascast weld metal may corrode faster’ than solution annealed base alloy Problems in Clad Vessels "The effect of heat treatment upon cor- rosion Fsisance of meals becomes in treasingly important when other possible fabrication variables are introduced. For example, corrosion resistant. metals fre- quently ‘ate used in'a clad form rather than in a solid form to reduce capital in vestment There are four cladding methods in general use today. In one,'2 sandwich is fade. of the corrosion resistant ‘metal dnd carbon steel, sealed around the edges by welding and hot rolled to effect a pressure weld between the plates. The Banding is almost 100. percent Tn another method, the metal is brazed te eal tacking pat: The sheets fe ently are available only in relatively finall Sizes and. must be welded to. pro- dluce the larger plates needed. The nature of these welds mutt be considered because they can be possible points where cor tosion might occu. Tn a third process, a loose liner is fasiened (oa carbon sel shell by elec: trical resistance ‘welds spaced on ap- propriate centers, usually 1/4 to 2 inches part. The fourth process i the so-called tip liner process in which a Toose liner is installed in sheets or strips of various sizes by welding 24t CORROSION—NATIONAL ASSOCIATION OF CORROSION ENGINEERS In all four processes, the desired micro- structure in the corrosion resistant metal is often difficult to obtain without dam- aging the carbon steel backing or the joint of metal to carbon stecl. Therefore, microstructures obtained must be evalu- ated from a corrosion viewpoint. IE metallurgical structures produced by these types of clad liners are not ade~ quate to give the corrosion resistance ex- pected, a loose heat-treatable liner may be necessary. Because the liner can never fit the carbon steel shell exactly, the use of internal pressure, necessitated by proc ess conditions, can result in cy‘ pansion and contraction of the & degree depending upon the nature of the process, Even if the process is a con stant pressure type, the liner will be subjected to cyclic operation every time the unit shuts down and starts Plastic strains introduced by these cyclic conditions can ead to various types of mechanical or corrosion fatigue failures or to stress corrosion cracking. Laboratory equipment designed to test metal endurance under accelerated cyclic conditions cannot reproduce plant opera- tions exactly. However, any failures pro- duced in laboratory equipment should be ‘a warning of possible ouble ahead in the process unit, Stress Corrosion Cracking in Various Alte “The problem of stress corrosion erack- ing of metals is becoming increasingly Sctious, Stress corrosion cracking can Oc. Gar across the grains of the material and long grain boundaries, at -diseused aoe , : Figure 13 shows typical einsgranular sires "corrosion cracks produced. in Stainless steel by attack of aqueous chlo- Fie solutions, At present, eh phenome. fon “is pooily | Understood. Although Gbloves Bre epeciay ave aug this cracking other corrosive agent alse may be important. For example, Monel, High resistant co such cracking’ im pres tnve of chlorides, may be prone 0 (rank. franolar cracking in prestnce of hydro: fen fluoride ‘No method is known which can con- twol tranggranular cracking under all eon titions Ta any process, thorough labora: tory and pilot plant testing is required wth sresed specimens and acta proc: ts fluids to evaluate’ possible dangers from this «ype stack. Effects of Hydrogen on Alloys Other types of serous metallurgical failares can occur during operation of & tit, Possibility of these Tatures often is besioked beeause they are not ticly Caused by corrosion, The action of hydro- gen upon stccly is an example, At suit She elevated temperatures and presses iydeogen will rene with carbon at the steel surface, removing the carbon and Gecarburieing the steel Tt nothing ele, this tends to reduce the stec's strength properties and to decrease. the salety Ector indesign. Also, under" suitable conditions, hydrogen wil dissociate. at the metal surface’ and’ difuse into the eel in nascent form. This diswolved hy- drogen may react with carbon insie the Vol. 16 steel to produce methane, which accumu Iates in"grain boundaries until its pres sure cats grin buna ring hie tffect is known. as hydrogen atta ftearbursed, Rauredsrugure shown in Figure 1d, The fssired. material has loat mich of its mechasiea! srength ‘This type attack. is well understood and can be prevented by use of appropii- ae Tow alloy steels, depending upon op- trating tempersture and hydrogen partial pressure. Often these resistant alloys can Bevsed. at no additional cost breause at the higher design sreses allowed for the alloy’ material in comparison, with plain carbon stel Hydrogen attack can occur in carbon stools under what might appear to. be mild conditions, For example, refractory Tiners often are depended upon to Keep a veswel wall ata temperature low enough to avoid hydrogen attack, Failure of the Tining material or bypasting of process fide ehind ie can Pee te nei wal temperature to a point where hydrogen itatk can occur, Bailures of important fperating units in the refinery industry Have occurred for this rea. Hydrogen also cat actin another man- ner to destroy. metals even though 10 Corrosion loss can be noted. For example, iP tantalum is held in certain mediay it may become charged with dissolved ‘hy- drogen. "This hydrogen dost not react permanent with the tan or th ny ‘impurity in the tantalum). at in the case af carbon steel Rather, it mere the ductility of tantalum to a negligible figure, thus making the metal susceptible tora brite failure even at extremely low Strains. Therefore, i hydrogen charging of metals is at all possible, physical tests of samples after corrosion testing should be made. Records of Materials and Serice Conditions One important point which can easly be orrlake when evaluating silos for new process equipment is the necessity of maintaining records of the chemical Composition and heat treatment history of each, corrosion specimen and of all fabrication procedures used in construct ing’ oth pilot plants and commercial ts, Its embarrassing to Bind one spec ten of an alloy with: unusual corrosion fesistance and be table to. determine which events in the sample's history con. Iributed to its success. Also, constriction Gf a unit based on test raul with ale loys having ‘nonctypical compositions “or heat treatments can lead to eatasteophic failures in plant equipment. With good records at and plus the reslls of tare: fat corrosion test, exact alloy composi- tions, heat. tfeatments and’ fabrication procedures can be specified for optimum Eorresion resistance inthe finished plant ‘An alloy used for. plant construction may" tend. to change’ its metallurgical Srictute. with ‘dime, under” the process Conditions to which it i subjected. This Factor is frequently overlooked in litera- tire'data and in much Taboratory work Tn mott cases, these. structural changes Fesistance at the actual operation. tem:January, 1960 perature is concerned, but they ean lead to serious corrosion during down times. In all cases involving special heat treat- ments, itis advisable to work closely with metal or alloy producers. To be of any value, the heat treatment recommended must be completely practical and easily conducted in the field under adequate ‘control but without special precautions ‘oF equipment, Metal producers know the industry and can be of great value in her of not any given technique is practical. Corrosion Mo Equipment Plant operating conditions can differ markedly from those uted in the labora: tory and pilot plant. ‘Thus, coreasion valuations should not end with construc- tion of a new plant or unit. Provisions Should be ‘made during construction. to install corrosion monitoring ‘devices at sensitive locations throughout the plant. ‘This is particularly important in chemi- cal plants manvlacturing products of High ‘purity in which small amounts. of Coron rads cae prot wallty” problems. Based. upon accurmu iEted monitoring data in the plant, vad cus methods can be used (0 control any Corrosion which appears. Process modi tations sometimes are possible and may tliminate the problem. Corrosion inhibi tors, anGvoxidants or other additives may ber elective. As a fast resort, it may be necessary t0 replace existing equipment with more. resistant and. usually much tore expensive alloys. Corrosion monitor- ing daca, combined with the pilot plant craluations, are estenal to & wit des sion on this subject. Corrosion monitoring in process equip- ment has been discussed in Several easier Publications" In general, wo methods fre available for monitoring purposes Corrosion coupons and. electrical. reist- ance corrosion probes, Understanding the felationship which these techniques bear to one anather i important. Probes and coupons can be installed at almost any point in a process; both ‘will measure Kecurately. te actual coreosion rate on the metal specimen at’ the installation point However, probes and coupons are best suited for obtaining different types of information, and. any comprehensive Corrosion monitoring program should take use of both techniques Corrosion probes are especially useful for direct tn? stu measurements of cot rosion “rates in operating. plant equip. ment. Corrosion and. fouling products formed ona probe usually” have. low tlectrieal conduttivities compared to the etal specimen. Therefore, the probe tan be ‘elt in place and. read. reguladly and without interfering with normal unit operations, Sudden changes in corrosion rate caused by changes in stream compo- sition or operating conditions can be de- tected almost immediately, before. any appreciable damage is done to the unit Corrective measures, such as the use of inhibitors, can be evaluated quickly and ccurately without expensive shutdowns heeded 10 handle cortosion coupons 1g in Process SELECTION OF ALLOYS FOR REFINERY PROCESSING EQUIPMENT Retractable coupons, which ean be ine serted and removed thfough a gate valve, are available for these same uses, Be- Cause of the navaldable errors intro- duced ‘in cleaning and’ welghing_ small Coupons, longer times are needed. for Corrosion rate determinations, Rapid changes are difficult or imposible to de- tect by this method Corrosion “coupons, most useful for sion rates, ean be enclosed within a unit for inspection during. shutdowns. With proper weight ‘lose ‘measurements and sual. inspection, all effects of the cor- tluding general corrosion, pitting, inter granular attack, ete, Many alloys can be Studied simultaneously, with heat treat ments and fabrication procedures com parable to those practical for the unit in {uestion. Hence, all of the corrosion cx. Perience’ accumulated. in the laboratory Sind pilot plant can be. checked. under follscale operating. conditions. Tf serious corrosion should develop in new unit, 2 indicated by probe data and it changes bles cannot correct the ilfieulty, com plete coupon data. will be available on Which to base selection of a more. re- sistant alloy for corrosion control Summary Selection of alloys for new process equipment is a complex procedure, Be- satuse of the many different effects thac operating variables can have upon cor= rosion te, laboratory and pilot plant corrosion evaluation programs should be designed carefully to cover all. posible phases of plant operations, A ‘careful metallurgical study" should. be made 10 determine the most desirable alloy com. penitions, heat treatments and fabrication Procedures for the. process. Finally, be- fase: Taboratory sand. pilot plant tests never duplicate plant operation, exactly, Should be monitored continuously so that Belore structural "of" produce-quality problem develops References L.A, Degwnies and C,H Shem Soe ts, 188 Cin AT. Freedman, ES. Ty haa: AS*Hetist Rea foston Moniaring ia Kefnary Equipments Gor: Fosion, M1 (1988) Apr S.A. Deavgicky and A. J. Fecedman. Petroleum Regnery Si No.7, Tir assy Tule: HA. Dravnicks and HA. Catala. Tndutriat Applestons ot t'Methed or Alesina ‘Retount af Coogan’ Without Remora fenton" Broducts: Cortonon 10, 80 HB. Jot man, A, Deavnieks, W. B, irc rs RS Money Siction of et Iniubiert ag" Meee Sertice Requirements. Cor Fontan 13, Be UBh) Feb 6.0 J. Freedman and A. Deaeniehs, Evaluation ton fihibicrs: Corronem, 1, ‘Method ot Cor. oss ae Be TA. Ja Freudman and RG, Canagary. Covro- Ndinod" OFM Ctlada® 1 NEES, 5° CBS) Aug 2 aeleied DISCUSSIONS Question by Robert W. Manuel, Socony Mobil Oil Co., New York Cit In the case of steel exposed to hydrogen at high temperature, it should be noted 13 [SE cel shang eh iste 5x!" ciyecregie teh, sisleter one reo hich ee Sox Niet teh fre Bins en by hyaragen ‘ie grain Boundoric that permanent loss of ductility can occur before the advanced decarburization and microfissuring shown in the figure is ob- served—in fact before any damage is observable under the microscope. Cone cerning the example of intergranular precipitate in Hastelloy, T should like to ask which type Hastelloy this is and what corrosive medium can produce. inter- granular corrosion in Hastelloy Reply by E. S. Troscinski: ‘The alloy type is Hastelloy C. The corrosive medium in which intergranular corrosion of Hastelloy C may aceur is impure acetic acid containing halides Question by Donald L. Burns, Gulf Oil ‘Corp, Port Arthur, ‘Texas: ‘The solutions of corrosion problems are complex and of course the complete evaluation of alloy materials is very im- portant as you have shown. However, the economics of various methods must be considered. Does your company evaluate the use of corrosion inhibitors vs the use of these alloy materials for new units? Reply by E. $. Troscinskis If the problem of contamination by an inhibitor is unimportant, then it is con- sidered as well as alloy materials, For the most part, economics govern the final choice, However, contingencies which sometimes atise with the use of inhibitors also must be considered, 25¢