Materials of Construction for Sulfuric Acid ABSTRACT Corrosion resistance of metals und normetals connonly used in gulfurie acsd service 15. suritae rized. "The eurcosson protection of aatala 3 explained in the context of electrochemical benay= tor, The effect of velocity, terperature, anauri- ties ond oxidants 1s discussed, Materials af con struction fur specific equipment are inetudod. :NTRODUCT LON Sulfurie acid is the largest. volue inurgamie acid iss use Lovay, und 5 ganarally considered the fnost importent industrial chonical. Sulfuric abid tis made by the contact process. Elenontal sulfur or waste which contains sulfur is burned to Form sulfur Sioxde. Sulfur dioxide is converted to sulfur tri- oxide by contact with » vanadium catglyst. The sul= fur trioxide is obsorbed in oleun and sul Furic acid in 9 series af towers. With anereaged environ rental concerns, sources nf mulfur sie as. anelter for power plant stack gases axa now being converted to sulfuric acie. The corrosiveness of sulfuric acid varies con- siderably and depends on many tactors, toremost of which are temperature and concentration. strong, hot conditions present the greatest prublass, and TVUIGINT As the term used to describe Fursng sul- furie seid. “Dieu 15 2 solution of sulfur trioxide dissolved in 100% sulfuric eid (which is often referred to ue monohydrate, one molecule af sulfur Lrioxide conbinea with one molecule of water). Thus 2% oleun contains 20 pacts sulfur trivtide dis- Solved in 80 parts of 100 culfurie acic Process Industries Corrosion $. K. Brubaker E, |, du Pont de Nemours & Co,, Inc. Wilmington, Delaware ew materials except platinum, tantolum, Fluor cachon plastic, and seid byick-lined steel will Fesist 60-98% sulfuric acid above 120°C. Honever, ‘other variables also influence tha resastunce uh materials ta sulfuric acid. the presence of oxidiz— ing of reducing contaminants, velocity effects, solids in suspension and galvanic affects can sitet the serviceability of 2 perticular materiel of construction. tk in unwise to select materiale af construct ion For equipment that will handle sulfuric seid solely on the basis of published corrosion data unless the wunnliliuns uwulved ure adequately and epecifically covered by the reference data. Seeuiryly minor c3 Ferences in impurities or envirormentel cori! ions wmay sigmficantly affect the actual ‘service corto. sion rates. Impurities such a9 halides generally increase corrosion. eratson or the presnee OF oxidizing egents generally accelerates currasion of honferrous materiale and reduces coreusion of stains Jose alluyn, but the extent nf these effacts dependa fon specific’ conditions. liot wall effects are. tres quently overlonked, and heating coils nade oF the sane material as the containing vessel ran corrode Fepidly while the condition of ‘thn vessel atsel ? Fenaand catisfactory. It ie, therefore, advisable to consider all general corrosion deta’ unly as a andieatur of rela Eave resistance and a guide oy which tho Linsting conditions of materiale may be further reviews) Final selection of materiale for specafic equipment depends, of course, on such Factors ee allowable corrosion rate, desired mechanical and physical Proportieg, fabricetion requirarents, availability, Bnd cost. 243,[CORDS LON MECHANISM The corrosion of metals an oulfuris acid 19 cum. plex nd en understanding uf electrochemical. theory is useful. the electrochasical benavior of nest metols felis into tnree categories which ran be Classified es active, passive, or act iverpougive behavior. Sew Figure 1. For sctive behavior (Case 1), the corrosion potential is 1p the active cogion, end a wide ange Of corcosien rates 13 posaible. for pseaive bono tor (Case T11), the anodic and cathodic currant Curves intersect in the most stable passive regions these alloys generally passivate spontaneously ond exhabit low corrosion rates. For active-passive behavior (Cese 11}, the cathodic curve intersects the anodic curve at three potentials: one in the active ragion and two in the passive tegion. Since the middle region is not stable, the intersections indicate the possibility of unpredictable end stare ic corrosion rates depending on the environment. Slight changes in the envaranment. way calse 8 ane to setive behavior. In tact, @ regular vacillstcon between aetive snd paseive behvior la aftoy observed. Thus Case IT corrosion is difficult to Study and presents the most risk for materials selection. ‘Sestingly adontieal snvizonment al cond, txons fron one Ixb to another, trom one plant ta another, and from one day to another can give rise to widely varying results. Stainless steels and tekoi-bese alloys frequently exnibit Case {1 behov= or phen Deigg spyshed to their Linity in sul urse MEASURED & * A c Tog current & “Toa current Case | Tog current THEORETICAL a. “Tog current Case potential FIGURE 1 ~ Conparison of measured end theoret ical ‘anodis polarization curves, for active, passive, and solive-pagsive behavior. "(4 = anodic’ currenty C Cathodic current). Source - Siebert, Ret 2 244, CARBON Steet Goneral Resistance Steel has long been used in handling concen trated sulfuric acid at aeblent temperatures. under static and ‘low velocity conditions, less than 0.5 m/e. A soft, sulfate film forms which is, highly protective untess physically disturbed. The actual gocrosion rate of steel 18 etrangly dependent on tonperature, acid concentration, iron content, and Flow because these parsneters determine the issol ur tion rate of the protective eulfate film. Faure 2 depicts the corrosion resistance of stvo! as 9 Tunic tion of Lenperature for nontlosing conditinns. at concentratzons above 65%. In tne concantratign Fenge of §5-100% steel is applicable for enbient Lenperature storage tenke and piping at low veloc ties, ithin the 10-101% range, steel emibite fotentiaily catastrophic increases in coreasion Fates op the tenperature moves sbove 25°C and is nat Peconnended except where low tenperatures and veloe~ aties can be asgured. Steel 15 voed in cleus ver vice sbove 101% “seid concentration st anbient. and Moderate taaperatures. LLovali zea attacse Even st Flow velucities within the prescribed Linits, localizes ‘corcusion can occur. "Disco nurties such as short=cadhused elbows, execsoiv penetration of welds, pipe misnetch, ete, may ca sufficient downstream turbulence to dist protective sulfate fain, the sulting in hagh cuctosion Fetes. It is important thot welanents be tharwughly Anspectes to assure that they contain no slag, sure Face porosity, laps, excocsiva penetration, os ol welding defects which might’ initiate. scelaca! Eereosions in addition, steel vessels and. piping should be free of mill-stsie, or sersous pitting us non-uniform corrosion may uccur Hysragen Grooving Hydrogen grooving is another focn of tecalized attack that occurs on vertinal ar anelined suefoces exposed to the liquid phases, During the carton of stool by sulfuric avid, hydrogen ia evolved, If produced in sufficient quantities, tlie lyerngon come ines to form stall bubbles which stron salons Seo ferred paths on vertical and inclined austaces Ge Fupting the soft protective iron. sulfate rig: Over 200 mp} € f a fe ig? fn iG Ean Lb Fas = fa " = © 8 me 15 ww ww wo Wes vo % Sut Beis FIGURE 2 - Corrosion of steot py sulfuric ecid as» Function ef temperature and conwenteation. (First BubLished in Industrial and Engineering. Chemistry and later in Corrosiua ~ & canpilation by M. Gy Fontana, Auerican Creaical Society, Hashangio, OC! Process Industries Corrosionaia FIGURE 3 ~ Hydrogen grooving currosion of Elbow was sectioned and view of top steel elbow: 160° 13 shown, Channels and eventually deep graves may be Foomed Grooving 1s conmanly abserved in tne fop9 of hori~ zontal manuays ov the side oF starage tanks and on the top 180" ‘oF morizontal pipe runs, See Figure 3. In piping, stagnant conditions combined with solar heating promotes graoving, thus # minimum velocity of 0.3 m/s 15 often cwcamended. Grooving combined with eraaien-corresion alse ‘occurs un the sidewalls of tanks,” Sea Figure. &: Location of the liquid inlet in the roof near the shell has, an at least two cages, resulted in combined erosion-cortasion end fydragen grooving causing estastrophie ruptuee of large storage tenis. Vopor Phase Attack Tiger claws is 2 tena used to dencrihn predomi rately vertical grouving which is sometines observed in tho vaporo ypace uF Luiers ar rail cots TL us, due to condensed dilute avid deippings. Liquid level groaving nes occurred in tanks were water aks oc candensation Nave tun down walls snd com tactad the concentrated acid. Jnfluewce of Copper Copper additions to steels for improved resis: tance fo sulfuric ,acid ig © controversial subject WiLlions and Kowp® coportes that steels containing 9.02% Cu had rates 16 tines higher that steels cond taining 0.10% Cu in 42 we% sulfuric acid. the associated electre-chesical study snowed that the effects of additionai copper dissolved in steel Fedueed the exchange current of the cathodis reac tion tneredy decreasing the corrosion rate. A study by Endo and Morioka” confirse the beneficial effect OF .1=.5% Cu in weak ulfurie acid aolutions up to about 535. Mowever, in concentrated sulfuric echd Solutions ‘above S0% ‘the corrosion mechanion appears to differ “and the beneficial affect was, nul observed. Many companies nelieve the advantages, 3 any, oF the use of copper-bearing steals for Nand Ling strong sulfurie acid are not suffacient to ‘ant the extce expense. Process Industries Corrosion FIGURE 4 - Hydragen grooving corrosion on sidewall of sulfurie acid storage tant Anodic Protection Anadie protection hss been used to lower corron sion tates tn steel twaage storing 93-39% eulfur seid. the intent is to prolong Lark Jife. ard. min mize irun pisiap: Typieaily, corrosion rates can be lowered 50-80%. In this prucess the steel ts lets trocherieatly driven fran the getive te the passive region by the application oF an applied potent tal betmion 2 cathode anc the steel. If proper pavsive sty o_achleygg, gthe corrosion’ cate ‘dropa fo. less than 0.1 nny 218 At anbient temperatures the vur- fant required to'nointaln passivity 1s very lowe AL elevated tenperetures oF with lowe concenttst one, Current. drains ace high. The use of stainless steel and Alloy 200-5" (\NS"NaD20). an Lanka. boing prow tected mist be carefully anelyzed av. the pase protection jotential for steel” nay ‘overlap active Fegiona for ‘these stloys With impcovenents in the sulfueie seid produc tion peacass, purer acid with lower iron content 13 hevag pradu This acid 18 more corcasive to steel than the high iron acid.” Thus the use of aeodie protection will become incteasingly inpare fant. Muclnisn oF Corroaten Pratect kor Carbon steel corres! ictave state at al concentrations up to TOE sulfurie scad. the reece: tun is the classical exidation of iron atone al surface by hydrogen redial Fost, + Hy At concentrations below 50% the iran sulfate corrosion product reasily goes into sslutiun and corrosion rates ore high. Ab higher vanmunt rat tome the initial corrosion raly is hugh but it is quickly Fecveed by the accumulation of irog silfete corsa Sion product. flligen and Sehwoal’ have shown tine cissolution and diffusion of the farrous. sul fate famey fron the surface is the rate limiting step. Dean and Grab have nodeled the effect of velocity, concentration 4yd temperature an the corrasson pro” cess in piping! and storage tanks." AE concentra Lions From 65-1008 at enbuent temperatures the sul Fate layer di¥fuses into solution sufficient ty slow For the use of steel as a material of construt!ions Fe + 4,50, WUT year 0.008 inches/year = 4 mils/yea 245Corrosion rates are typically 0.15 to 1.0 m/y. In the oleun range above 101% eulfurse acid concentra tion (W% Free sulfur trioxide), steel cortedes in the passive region duo ta the ‘oxidizing effect of sulfur trioxide. Corresion rates are typicelly 0.1 fn/y at ambient’ temperature. In the 1OU-101% con centration cange the steel goes through an active passive travsition state and mescuted corcasion rates are erratic and excessive at temperatures above 25°C. cast saons Gray Cost tron Gray cast iron nas been used for piping and ccaotang guifurie.acsd since: ucad:plosta were riset Sonlte” Gast iron ts at lenst 20 cestatant ao steal In the 65-1008 concentration range at ambient ten perature, This is dup to the tron sulfate protec Hon mechanssn. The haghec carbon and orlicon tan tort ‘oF eeat irons leads. to conditions favoring Superior ‘rosistener at mgt: welociticy ond eles Voted Lonperdtures, nt lense in the. concentration ranges of 90-1008." Gray east tron 16 lesy.senattive to Velocity then steel and is frequently used up to U7 wip in larger dienster piping. Fontana ond Green'® speculated the weperion resistance of cost ton’ ap due to interference af the granite, flake Netware with the reaction petwoen the acid and the allie matrix. “tiaann'S soygeste the geepnite sees set 26 cethogie areas and shift the cotsouion potential to w more favorable region Gray cast iron should not de used in the oleun Fenge due te @ tendency tonard vaolent cracking. It As theorized that free sulfur trioxide attacks the Qraphite-matsix boundary Forming corrusien products which strain the structure via volunetrie expansion. Cracking of gray east iron has algo occurred in con: centrated sulfuric acid service where it was at tech ed to stainless steel coolers protected by anodic protection. It is thecrized the anodic current "Fouls" Une cast iron into behaving es thnigh it ts to minim service. Thiy prublen was solved by placing a ten foot ductile iran pipe shoal het meen the ‘covler and the gray eact iran piper Ouctile feast iron ig not subject to the sane phenomena 3s the grapnite 18 19 the farm of ig0lated modules and the metal matrix 1s subetant tally etrongor, Gray cast zon is deittie and frequontty cup tuces catastrophically. Care must ve taken tu properly support cast ion pipe and to replace it before it thins excessively ‘due to corrusion. For Feplacenent ar new piping, ductile cast ion, stainless steels with and withaut anodic protection, and plastie-lined pipe see now favored. Ductile tat Iron Generally, ductile cast iron is nearly 28 corco- sion resistant as gray cnnt tran to concentrated sulfurae acid secvice. "Laboratory testing coaparing the materiels has been inconclusive, probably because cheaical compositions vary conaidersé ly. Actual plant experiences with piping tend ta indi cate 0-50% higher corrosion rates for ductile cast Aton versus gray cast iron but this 12 usually com Pensated for by the sdditional corrosion ollowsnce fon ductile cast’ iron, 246 Recently 9 mod:fied ductile cast irun, Honea? was inteaduzed which reportedly has twice’ the corre Sion resistance of conventional ductil® cast atone This alloy has about 3.5% silicon vera the 1.62 2.8% for standaré ductile iron, Silicon Cast. Iron Another material that hes long bem used for handling sulfuric acid i magn ailicen iron (UNS Fe7003). Iron with 14.5% silicon content nas excep- {onal resistance to sulfuric acid an all concentro= Exons to 100% up to the atmaspneric boiling posatas Corrosion rates are normally less than 5 my (0.17 fia/y) a3 shown in Figure 5, 0 fn eset fe = sw = 1 ew Po a 10 Faia swe an ow mm wo © wm ww te Sutra FIGURE 5 - Corrosion of high silicon iron by sul Furic acid asa function of temperature and concentration. (Fixst published in Incustcial and Engineering Chenistry and later in Corzosion - A compilation by M. G. Fontana, Americen Chemical Society, Wasrington, 5c) Nye resistance of high silicon iron stems feon the he Formation uf a strong, sulicumeciehy abrasion-recictant film. Even the most. sovetely abrasave Slutties cus be little. The high silicon azans ace available only in the eeet form. [0 addituut, Liwy havo low tensile strength and victuolly no’ ductility. High ‘silicon 3Fons are susceptible to thermal and machanical shock. Sharp hammer blows and rapid. temperatura Fluctuations have failed the material. High silicon Aone are rapidly attacked In olew’ or sthec wef vives containing free culfur trioxide, Only sul lor trioxide, sulfur dioxide and luvrind contosinants are known to drsstically alter the corrusion eos Fence of high silicon sron to sulfuric acid. AUSTENLTIC STAINLESS Sree Tho resistance of austonitic stainless sleets to sulfuric acid 18 complex due to the active-passive ature of the alloys. fi excellent ‘sunmary, gneled- ing corrosion-rate dsta exists cleaners! The Following discussion highlights this topic. ‘WVeRaT— Woncanto ductile iron = a ductile tron developed by Monsanto. Process Industties Corrosion rebar naceHechanian of Protection Stainless steels depend on electrochemical pas- sivity ~ Case IIT behavior - for resistence to cor Fosion in sulfurie sesd solutions. Stable passivaty is achieved at anbient temperatures in the very low fang very high concentrations and in oloun. The pro tective film is believed to be an oxide; Nowever, at higher concentrations and in the oleun range, sul~ Fate deposits and/or corrosion products are belzeved to be @ factor in passivation, especially if ele- vated tonperatures are Involved, In margins) conditions oscillation betwaen active and passive behavior often accure at regulat antetvals. “Frequently stainiess steels have useful corrosion resistence despite these oscailations. Such 1s the case wien osly a saall Fraction of the. tine 13 spent an the active state. However, care mast be taken as upward changes an velocity and/or temperature can sharply ancrease rates. Anode peo tection 1 userul an these marginal situation t hold the corrasten patential in the paseive ceguon, Corrosion Resistance At onbient temperatures, austenitic stainless steels (eg, Type 304 ~ ONS 3304008) exhibit. stable Case 11L passivity in sulfuric acid above 93% cone centration end are Teequentiy used For piping and tonkage where product purity 19 desirable, The corrosion retes are essentially nil compared with 0.15-1.0 ma/y for steel. Holybdenun stretenes the passive ragion maieing Type 316 (UNS $3160) and Type 517 (UNS. 331700) accoptabie sdove 90% concentration at ambient tonperature. The upper tenperature Linit For otable passavaty Tor Type 304 and Type 316 in 95% sulfuric acid t= believed to be around 40°C. For 98.5% sulfuric acid, the upper, stable pessive inst is believes ta be above 70°C." Ae concentea tion increases above 99% corcosivity drops rapidly allowing the use of stainless steels in exces uf ‘00°C. In dilute acid nly the wolybdenun grades such 63 Type 316 or 317 are Useful, althovgy Type 304 nay be used wnea only a trace of acid is present. Fiqyre 6 ahows corrosion data developed by Abo, all, ror these alloys in as-mixed ond refluxed (aerated) sulfuric acid solutions. Staintess steals have poor resistance to deasroted dluke uolul sure. Type M0 ctasntece oteel with 25% chrentim and no antontaonally added wolyodeius 18 axe resistant than the molybdenuo-deaeing grades when oxidizing agents are present. This is attcinuted to the higher chromiun content of the Type 310, Effect of Valocaty Af a stoinless steel is solidly in Case [11 pase sive behavior, velocity sppeury to have Little effect. Laboratory tests of Type 30a (NS $30403) wath yatocitias up'to'é m/s in 93% sulfuric acid ot anbient tgmpecature have shown Case IL passive behavior’? “However, once the allay drops to Case II (active-passive) type behavior, usually due to increasing Lemperature, velocity has @ major effect Under abrasive conditiana cast stainless steels have show Case 1] ‘active-passive behavior gn 968 sul- Furic acid even at ambient Lenperatures. Process Industries Corrosion a] fens ron | TTT 1 FIGURE 6 - Jaocoreasion chart For Type 304, Type 516 tnd Type 317L in refluxed (aecated) eulfurte aead up ta S08 cancentration. Reprinted Fron INC CER-1 bulletin, Ref T4. Original source ~ Abs, ot al, Rer %6. Effect of Revulau uid Oxidante Nighly aerated solutions wre much are suitable or tnese alloys than airaftan nae. Isknwiae, Ene presence uf uxidizing impurities stabilizes the’ pac- five film, and Liese resistance to sulfuric acie becomes aarkedly belter. Cations that are sasily roiribley auch wa ferric, euptic, atannie nt ceric, are oxidizing agents that oan inhibit the attack of stainless steels in sulfurse acid solu tone. “Streicher found that 0.19 grams of Ferrie on per Liter was sufficient to cause pevslvity and low ‘corrosion Taran io hniling ils sulfuric eeidy but O15 ggans ferric inn pine liter did not give Anhibition. Kiefer and Renshan!® showed that other oxidizing agents such as chronie and nitric acid,yere effec~ tive in reducing corrosion rates. Auld?) hae chow thet nitric acid concentrations as low es Te5t Anhabit the corrosion of stainless steel over o wide range of sulfuric acié concentrat ions at ayfient. and elevated teaperatures. Anderson, et al", docue rnented how oxidants in sufficient uentatiee will also reduce the corrosivity of sulfuric acid on steel by shifting tha corrosion potentiel from an active to @ passive state. 247Erect oF Sulfur te soxcide Most storniess steels and nickel-base slloye have SEpaLC reductions in Gartpgton rates uh athens sulfuric acid above ote oF and in oleum. The. increased resistaice 1s bolieved to Ge deentg ie ncroase, sn the oxidizing nature of the aces, “aythe the 98.3% sutrurie acta azeutrope the te, oete pressure and the cutrosion resistence Rik heres Fopsdly with ineceaing concent fatiee This sheep Gromaft in eorrasion has been cheered fay anne Of atloys in sulfuric acid plant abanngt icy tee environments. “Table 1 shows corcecien ete cee yarious alloys tested in. an absorstiont nee ewaroment., The molybdenun containing atfoye me disticctly anterior unless the cheangee ate Wigh a6 a5 tha cage with Eoarite Decne, agin absorption tower, 98-99% sulfuric ecid flows (erorerd over @ ceramic bed wnile the gas stroce TEL antains sulfur trioxide pasans upward tnrougn The packing pronates contact such that the ‘Sulfur trioxide is absorbed into the salturee fasily reached. | Brick-Lined steol and cust seen ore neg, typical eaterrais of constcuction: homwer’ Tam careful control “oF “the seid envirereect” Ponstruction with stainless steel may be rose Extreme care must be taken when using stelnlose Feeeseattn sth, 28-1008 concentration tango at. hah Eswperstures as velocity conditions, ‘echet iene ay sreiaeeeertcatton or changes in oxidant Levels ay anitiate “high corrosion wath Figure 7 and the data in lable t” Sooge fteintess steets ‘are tree trom the coneeee Shout @inor concentration variations and’ coe Festotance is extended walt in exeeos of 100% Table 1 CORROSION RATES IN ABSORPILON TOWER ENVIRONMENT WITH 99% SULFURIC Aci at t00-120°C Corrosion Composition & Alloy fate (mwv/y) Dea staat og Cast tren ont Ductile iron 125 Type 30a, ong 1% oo 2 Type 3160 V.06 we als Alloy 904, ong. am aS Alloy 20 Gb-3 0.08 me 2S Alloy C-278 oss 135 574g Alloy 6-2 23 05 70 2 Beat Aca 6 By E-rate® 26-1 alot % 0 4 QEDIES ie a regictered trademark of AL Legheny Ladiun’'Steat “orp. 248 20 200 Teupenarune °c kee 20 97 915 98 985 95 958 100 00s by WEIGHT % H2so8 camer ade cSRErOsiON chart OF Type 204 an highly srreegerated sulfuric acid. “Source HeaListen yay al, Ree 22, ble 2 CORROSION TEST tN FLOWING 98.7% SULFURIC aciD aT tanec Source ~ Renner, wt at, Ret, 26 Corrosion Alloy Rate Cin’) Type 308 os Type 516 sat Alloy 90a, 23 Audic Protection Anudin protection io a piwLical netned of ctending the us Sarge for stainless steels in sulfuric sein, Ginn ‘anodic protection @ cosponent {anode 29 held in tno passive = cove TIL cornnent, by on anpressed current ‘trom a vathese. Fortunately sulfuric acid is @ geod cuniuctor of Eleetrietty and thecorore has. good tntouiee tambler, Shell sides oF ‘stainiess stocl sel ey Stainless. stee! may Se ores fected jn 99% sulfuric acid up to 70°C amin sue Corrosion rates can be reduced to 00%” Soap RPtONMAL ely “200 anedieatly’ procee reg Teglere Mave ‘been installed an seig cocifeai te Twops in sulfuric-acid ptents throughout tae weciae Process Industries Corrosion I } iSSE RARE CRIS FIGURE ® - Isocorrosion chart for east ACI CO-WHCu an-sulfurse cic. Source ~ INDO CFB-1, Ref 14, Silicon Stainiess Stools Aystenitic stainless steels cantaining 5-6% Silicon have interesting carrosion characteristics An concentraled sulfuric acid service, Both cast land wrought versions are available, ihe cost ver= sion, Durcomct 5, made by the Duriran Cope tow a typical conpusiton of 5% Si, 21% Cr, 16% Ni, 8-028 0, bal Fe.2?” Ino wrought version of this alloy, A-611, is made by YEW? In austria. Ihe typical composition ig 5.3% Sa, 18% Cr, 18% Nis 0.02% C, bal. Fe. the A-617 alloy has useful corco™ sion resistance in 99% sulfurie acid to 120°C with out snudic protection. Corrosion protectin is obtained via the formation of a tenacious, stlicun= Fich film formed on tne gurface during the initial days of corcosion. Corrosion Tevistance of the vast alloy 18 similar. Piping, disteabutors. and. pump tanks handling hot 99-99% Sulfurie acid heve bech mage Fram the A-G11 alloy. Dao! SIALNLESS STEELS Coot sininless steels have voventivlly the sane corrosion resistance to sulfuric acid ws Lei ‘wrought counterparts. Because the ‘cast versions Contain second phase’ ferrite for castability, care ust be taken that proper heat treatment. and micro: stcucture hotogenization 18 perferned” for naxinun corrosion resistance. Sone investigators have show that preferential corrosion as the recuit of the duplex structure can be a problem. However, proper ly eqjf and heat treated duplex materials perform well, One cont alloy that does not have 9 clase wrought. counterpart’ as ACL CO-dMey (UNS 393570). This’ alloy has the dame alloying elements. es, ACI [I-74 (UNS 395150). but. genera ly “in Tower, omunts Corcosion vaaistanee Liee betwen ALloy 206) wr) ype 316. Figure B te the isococrosion chart. for Unis elicy. “Corrosion resistance of cb-tiCy extends avez ‘their entire concentration range. ot. anbient Seaporatures ond the olloy is suitable in excess oF WORE" in oleun services” TSWVereinigte tdelstahlwecke aktiengese! Lschart Process Industries Corrosion FIGURE 9 - Isgcorrosion chart for Hestelloy Alley H-532 in sulfuric acid. Souree = INCO CEa-1y Ref 1a, sents fob FIGHE 10 - Isecarrasion chert for ALloy 904 in sulfuric acid. Souree ~ INCO CEB~7, Ref 14, HIGHER AUSTENITIC STAINLESS S1eELS Lake the austenttic stainless steels the earro- sion resistance of the higner austemtic stainless Stons 15 also complex. However, the range of ‘jaa suvaty and corrusion resistance "1s extended due to Une hugher ulloy contort. Lake Une staunlusy strolay Cane T= active ani Page 11 art iveenagaur cyclic behaviue are the aades of corrosion. Revise tance 18 achieved in the Cove LIL = pagmive ovate, An excellegksumary including corrosion data exists elsewhere." “The ‘Tollowing chsevseion highlights this topic. Fe-Base Ni-Cr-Mo Alloys This class of alloys contains approxinately 25% Sa = 20% Cr - 4.5% Ho, sonotanes copper and wane tines titaniun or columbiun stabilizing elesents. Alloys in this catagory not containing ‘copper are GareFally sore corrosion resistant han Type 316 stainless steel and incluse Hastotloy” alley H-532 and Jessop alloy J8-700 (UNS NO8320).. Figure 9 shows an iwvurtusion chuck of Altay HeSIZ. Tne. tenpereture and concentration ange of Ems allay hus been extended beyond that for Type 316 a the result of te increased alloy content. The copper-besring alloys in this class ace nore Fesistent an sulfuric acid than the capper-froe alloys. figure 10 19 on isacorrosion chart for a 25% Nu = 20% Ce = 4.5% Mo = 1.9% Cy alloy such as Alloy 904 (UNS N0G908), The Copper additions, rake the alloy suitable for the entire cancentrat ion range at anbiont. toaperuture, TUBETETIGY a8 registered trademark of the Cabot ‘rp 249FAGURE 14 ~ Tsocorrosion chart for cast ACL CN-7M in sulfuric acid. Source ~ INCO CEB-1, Ref 14. ‘erftase Ni-Cr-Ho (20 Type) Alloys The "20 Type" alloys are usually the Firat com sidered when @ sulfuric acid environment 48 tao ear rasive for the uso of steel, 300 series stainless steels, or cast iron. This group of alloys contains both wrought and cast allays which are raughly equivalent in resistence to aulfurle sete ‘east ACL OWI. Figure 11 shows an isocoerse sion chart Far-cast ACL eu-IM {UNS 395150). Ths Alloy generatly ‘te. suitable to 80°C at concentras Lions €6°50%,. For nighae concentat ‘ons good’ Eur ae sion is expected to 65°C. Sove af’ the alloys con fonwing to this specification acqyetter_krown by their” teode names auch as Ouriaet™? 520) anc Aloyee oy 20. A typical composition is 29g \M1 = 208 cr 238 Cu ~ 2.54 Ho, bal Fe: Wortnite™ ts anotnoe east, alloy with a ‘composition closer to 9040 then ohn nt ALLoy 2000-3. The wrought counterpart to colt MET TE wae aevotoyen sod Ser ease known as Carpenter 20. In 1948, colurbius we added to this alloy for stabilization against sensitize tion and antergranuisr ultack. In 1963 the nickel teouleuil ws rulued to 33-39% fo give greater recie~ tance to chloride strews-currosion “cracking and improve resistance to boiling aulFurie acid under heat trensfer conditions. Minor changes were subse quently made to give greater resistance to inter granular corragion. This wllay is nay known as Cat penter 20co-5" (uns Nou020). A typical ‘conposi~ Lion is 348 Ni ~ 208 Cr = 3.5% Cu - 2.5% Ho bole Fe. Corrosion resistance of Alloy 20Ch-3 13 similar bo ONIN, An isucorrasion ohare is shown an Figure 2 TburiMel is a registersd trademark of Quriran Co., Ino. (B)Worthite is a registered trademark of Hortnington Pum ine. (#)Corpenter 20Cb-3 is a registered tradesark of Carpenter Technology Corp. 250 3 es 12 = Isocorrosion chart for Carpenter ALloy b-3 an sulfuric acid. Source - INCD CéB=1, oa, i ro “| Tismmy o fee FIGURE 13 - Ieccorrosion chert for Incoloy Alloy 825 an guifurie acid. Source = INCO CEB-T, Ret Td. NICKEL ASE ALLOYS Ihe nickel-bese austenite alloys have superior sesistance to corrosion in sulfuric acid an the 835% concenteation range due ta thei high wliay content. Frequeatiy, low coreanion rates teva Lh botn te actave and passive corcosion sratecy thus, Teliable corrosion benovi0r is echieved over wide Fange of concentration. Lewporavures and ipuy levels. Extonaiye sgigguosion,. data. and ceterunces exist elsewere. iS BF A haghlight of the resis~ tines oF the nickel-base ai lays Valtows. Ni-Base Fuctr-Hu-tu Al tuys Atloy 825 (UNS 108825) has excellent. resistence to sulfuric acid up to 40% cancent ration and in con centrated acid, a3 shown in the isocorcosion that an Figure 13." The higher nickel content. uf tis alloy varsus ‘the "Zu lype" alloys offers atigntly Improved curcasion rasistenre at high tonpera ures 19 low and hegh concantretiens oF sulfurse ais. Alloy G and 6-5 (UNS ND6007 and NOMS) aco mod afications of the now absolete Haatetloy® Alloy Fy Atypical conpositinn 19 GS% Ni = 228 Cr 6.58 Mo ~ 2% Cu." Alloy G-> 22 8 modified version of Allay & with the sane general corcasion resistanca, It tos Modified to resist forsation of grain boundary precipitates during prolonged heating such 02 stress relief, "hese alloys are pronitad for their resis. Lance to halide contaminated, eulfuric-acid ev scone ments. See isocorrasion charts in Figures dard Be Process Industries CorrosionBeppe I id eae 30853098 sao FIGURE 14 ~ Isocorrasion chart for Hastelloy Alloy an sulfurie seid. Source ~ INCD CEB-1, Ref 14. FIGURE 16 - Isocorrosion chart far C-276 in sulfuric eld, Source = INCO CEH-1, Ref Id. sata FIGURE 15 - Isocorrusion onart for Hastelloy G an. sulfuric acid solutions (contarinated with chlaride ons). Souree = INCO CEB-1, Ref 14 Niscu Alloys Alloy ‘100 (UNS NOM400) 19 used For handling sul- furke acid under reducing conditions. thusy, this alloy offers an alternative to stainless steels and thet alloys exlubiting aetive-pustive behavior when eulfurie acid solulivwe ace nwt oxidizing, such ao Wewerated dilute acid. Alloy 40) exhabsts reason ably low corrosion rates in gir-free sulfuric aetd \p to 85% concentration at 30°C, and up to SUH con Centration ut 95°C. Ni-Base Mo-Cr-Fe Alloys Thege nickel-base alloys, containing about 16% Moy 16% Cr and 3-54 Fe, are available in both wrougnt (Alloy 6-276 aud Cad = UNS WIOZ76 and NOES) and cust Torn (ASTM AUS Grades CA-T2MW anid Fw-7K). “The corrosion resistance in general. 1s excellent. See Figures 16 and 17, At toon tea perature ‘the corrosion rate for ali concent rations 415 less than 0.1 mivy. Secauge of the higher ches Mun content, ‘these alloys are nore resistant, to sulfuric acid containing oxidizing contavinates (eq, cupric or Ferric ions), than materials ouch as Alloy 400 or Alloy 8-2 (UNS WiD665)s Another material in this group is Alloy &25 (UNS N06625). The isocorrosion chart ts chow? in Figure 18, Process Industries Corrosion bn SS. . FIGURE 17 + Isocorrosion chart for ALLoy C-27%6 in gulfurse acig and aylfurie acid plus chloride Source ~ INCG CEB-1, Ref “14 2 4st mma | + 9 amy . “sulla Reid, wi FAGURE 18 - Isocorrasion chart for Alloy 625 in sulfuric acid. Soures ~ Ref 27. Niece Ho ALLoys: These nickel-base alloys, containing about 30% Noy 3-68 Fe and 1% Cr, are available in the cast and wrought forms. The ‘corrasion resistance of these Alloys re excellent in pure sulfurie seid over a mide range of tenperatures and concentrations HOW ever, oxidizing contaminants such os fertie ona considerably increase corrosion rates snd nave ‘caused premature failure. Chlorides gl90 increase corrosien rates. 251FIGURE 19 - Laocorrosion chert for Alloy 8-2 in sulfurie acid. Source ~ INCO CCB-1, Ref 1h, Alloy 8-2 18 the weought material in this alloy group. "See the isocorrasion chart aa Figure 19. the cast version with similar corrosion recistunce tg AST AQvA Grade N=12H¥. Cast alloy ASTH 8498 Grade N-7H,. pager koawn by rade ppp ceszgnstiuns as Chloranst\™” alloy 2 or ili !F gilcy m2, alse falls into this geners) grouping. Nistiage CreFe-Co-Si Alloys These are proprietary alloys developad specifi- colly for hat concentrated cgyjfurie acid pump and SoLi8 SppuacationesLowaoe ™® itoy 95 16 1 cast lloy. "hr Ssocurrosion ehart is shown in Fagure 20, Figute. 21" ahowa the effect of temperature in 985 sulfuric seid as detemined. by Laboratory tests Lewmel® alloy 65 20 0 eustile cast alloy that can aio be sade’ in the rough form, Gath forms hove nt corcosion cesiatance in the 0-60% and #0 ie huh parFormance te erratic In the €0-f03 Panyer Soe Figinm 22, Nusiaga Ce-Mo-Cu ALLoys: These are propcietary alloys designed ta resist: sulfuric acid concentrations up to 988 up to 100°C. Tiliex® 98 is 2 weldable, sachinaule cast alloy. Tiliun® 8, also 2 cast alloy, 18 # version of Iiliun® 98° modified ‘for enhanced ‘corrosion Te038- Lance. I1lun® 1s not easily welded, hovever. Tha asocoreasion chart for [liui® 8 is shown an Figura 23. ‘TOVUHTorimet is a registered trademark of the Duriron €a.5 tne. (I ILLiun is a registered trademark of Stainless Foundry & Enginosring Ine. (12iLewmet is 9 registered trademark of Charles S. Lewis & Co. 252 z [of 7 : § 100 212 E E a a te F FIGURE 20 - Leocarrasion curves far Lewtet Altoy 99 in solfurie acid. Souree ~ INCD CEB-1, Ref 14. FIGURE 21 - Corroaien of Lenmet Alloy 5> an 98% sulfurie acid. Source ~ ING CEB-1, Ref” 1, F 008} jw0 d j i FIGURE 22 - Corrosion rates of Levmet Alloy 6&6 in fsulfurac acid golutigna at 100°C (212°F). Sauree ~ INCO CEB-1, Ref 14. 9 ~ FIGURE 25 - Leecortasion chart For Ilium ALloy 8 an sulfuric aead. Source ~ INCO CHAI, Ref 14, Process Industries Corrosion220 E140 g B too i © 3 ag CONCENTRATION [ieeight Perce) FIGURE 24 - Corrosion of zirconium (UNS 860702) by sulfurse acid asa function of temperature end concentration. Source ~ Wobster & Yau, Ret 28 zaRcontint The Largest applications for zirconium (UNS 60702) in" the chemical industsy have been in hot sulfuric ‘cid. “Zirconiun nas excellent resistance to sulfurie acig up to 308 concentrat ign at tempera tures. to boiling and. above, "In the 50-65% concen Ustion range resistance ia generally. excellent at levates temperstures but the passive film io @ lees Effective barrier. Experience nad shawn that. weld ng ond oxidizing apecies in 2508 sulfuric aeid cm encourage selective attack, In. concentrated eul~ furte acid ‘hove 70% the corcosion rate of zircon Inetenann. Fapidly with inerraniog roncentent ion, Since welds are Koow 0 be slightly less resistent than Uhe purent neta, eiveomue a9 seldos used ove 60-438 concentration in the welded condition Unless it has been heat treates to mexamize corro~ Slon resistance, Ine cosruppopyresistance OF enreo- naun is shown in Figure 2489 The corrosion resistence of ziccomtun in sul- Furic acid 13 dependent on the Fornstion of & pas sive film. The protective fis consists of predomi rately cubic 250) whick ts highly ordered and corro- Sion ‘resistant. ? Elocteachaeieal neasurenent show the! corrosion ‘potentisl af zirconium in sulfuris acid to be located solidly in the pasaive region when IP as resisting corrusion. However, oe tensor” ature and/or concentration incceases, the. teanapas- sive (Hrestaomn) potential decreases and there jo 1099 tolerance four oxidizing agents such au (Fey cu, M03).""at high tamporetures an concentrat iond reater Yhan 50%, "oxidizing agents in’ sufficient Quantities delete’ the passive region causing eir= coniun to carrode set ively. Tirconiun has no resistance to Fluorides unless they have been complexed using inhibitors auch as silica, phosphorous pentoxide, or zirceniur sponge. Process Industries Corrosion ‘team 15% 805) “CORROSION RATE Imm/¥ Oe to B58 “TEMPERATURE IC) FIGURE 25 ~ Coreoston rates of tantalum an 98% sulfuric acid and oleun. Source - Corrosion Data Survey on Tentalun, 1972, Faneteel Ine. ‘aNTALUM Tantalus (UNS 805200) has resistance over the entire cange of concentration ane tesperature except For very strong. and exceptzonsliy not conditions. Figuce 25 shows the corrosion rates of Lantalur in 90% acid and oleur. A common use 16 fOr rebosters fand concentrators oF sulfurae Reid an the TOS con centration range, aTaNiUM Sha cuprie ions 2S Leap Lead 19 resistant to eulfurte acid, but the pro tective sulfate file i¢ increasingly solubilized above 90% concentration. the Film 16 oasily dansged by erosion or abrasion at even low velocities with the rate of attack increasing rapidly with concen tration. Lead is useful az @ pan eaterial to catch cid drippings. It is olso used as a membrane bee hhing prick in culfurac-acid concenteating units and in sulfurie-acid scrubbing units. The poor physical properties of lesd (it creeps under its own weight) the! virtual disappearance af skilled ersfearen (lead burners), and the increasing use of normetals have greatly reduced the use of Lead in the chemical Andustey. 253(COPPER AND COPPER ALLOYS Conper and copper-bage alloys are not widely used in relatively pure sulfuric acid because of the fdrastic effect uf oxidizing conditions. The resu!- tant coprie ione aleo cause autocatalytic corrosion, Gruss 16 not often used because of the potential for Gerincification, Bronzes have the greatest applica bility, wath the aarmal coppertin bronzes shawang acceptable service belo# 60 concentration at 79°C. The silicon bronzes evtend the suitable range to bout, 70% congentration. The aluminun broness have Resistance sppraaching ALLoy 400, however, destumi= fifteation can bee problem, ' particylarly ath DMloys conteaazng more than 8% olunanun. NONMETALS Nonnetal lic materials of cunstruction have wide application in sulfuric ecid. Yost of these mate fialg have good corrosion resistance to the pure acid, perticularly sn dilute concentrations, ond ore primarily reste tcted by the wachanical pcoperties at Remerature. Mey are reletavely unaffected by most Inorganic. contaminants, except for strongly oxidiz~ Ing agents such as nittie acid, peroxides ond ucheonat es. Brick Linings: Brick linings have been used for the most severe sulfurie acid conditions. Under most conditions, acid-resistant fire clay brick can be used. For extrone conditions silica brick is used. High Sluvsna refractories are inferior at high tempera tures and concentrations due to brick impurities. At concentrations balow 70% lead, plastic or elasto- erie corrosiorresistunt membranes are required Dehind the brick, The Brick serves 96 a thermal and abrasion barraer. At highet concentrations brick en be osed directly on steel althawgh TFE or mortar berriecs are often used. For maderata concentcom Lions and temperatures, plastic murtars such 3s furases. and ptienalics are ‘used. For nigh tenpecs- tures nd concentrations the silicate cenents are Fequiced, Sucsun silzeate cement has been the must Common type an spite af the Fact that. it slowly ean- verte to sodium sulfate, wich hydrates and bem Grades. Potassiun salicale is tm preferred uy ito Sulfate sali oes not hydrata. Mortara based on pure collaidel villea ace olgy wvailale for extra feonsit ions. | Polyvinyl Chinrade Polyvinyl ehtoride (eg, ASTH D-1789, PYE=1120) has excellonl cesistanes’ lu vulfuie acid to approximately 93% eoneentration at ambient temperature. Chlorinated polyvinyl chioride (eq, ASTM D-2886, CPVC-4120) is resistant to slightly Inighar concentrations and teaperatures. these hhaterialg have hoon vised For pipelines but srw vot Popular for longer runs since they have high coeffi Bienta of expansion and require essentislly contin. tious support. Many companies prohibit the use of solid plastic piping For safety considerations duc to the poteatiat for breskage. 254 Lined Pipe Polyvinylidene chloride {PVOC - eg) "Saran", polyptopy}qyg. (PP), polyvinylidene Ftuaride (PVDF, 5, Kynae\Vey]y and potyteteafluoroethylene (@IFE ~ ea, teflon’? “ee? piastaes all are used Tor Linings in pipe for handing sulfuric acid. the range of usefulness is shown in Table 3. Although polypropylene ig anown as resistant to 96% sulfurie Beid at ushient. temeratures, thece 13 considerabte Conteaversy on this. point. eines high concent rat ois fan cause chareing and stress-carcosion erscking. {Yo svoid this, the palyprosy one must either be kept an compression oF # copolymer used. Jebte 3 SULTABILETY OF PLASTEC-LINED PLPING SYSTEMS IN SULFURIC. ACID Mexia Concentration Ynteriod —onporature ("¢) Sulfuric Acad vor ve cee 2 308 Ni >60% ca 3 «ca 80 3 rf 96 30 35 vor 120 105 80 65 Wwe 260 0-108 ATeaperature may be further Limited by mechanics] conditions undee vacuun. Sourve: Dow Cheical Midland, Michigan. Polyethylene Potyathytens posuesses @ hich degree of resis~ tance £0 attack by gulfurie acid up to 98% concen Eeutaon oF amhiant tampecature. The high density resins shon vietuxlly no attack an 98% seul [onperutures to 80°C. "The woe oF palyethylene Cquiement. for handling sulfuric aci aust be Testricted to celavively Yow temperatures and Lox Toads unless continumusly supparted. Polyethylene ty widely used in laboratories Tor beakers, bottles, ttey wileh do not ceyuirc heating uver direct Flamake Tanks enostrucknd of molded, seaaless, high-deneity, erose-Linked potyathylena have been used to store relatively small volunes (eg, 1000 gal) of concentrated sulfuric acid up to 96% TW FRET Te 9 registered trademark of Lhe Ponwalt coro. (ayferton as = registered trademark of E. 1 du Punt de Nemours & Co. Process Industries CorrosionFluoroplastics Fully Fluorinated plastics such as PIFE, FEF, land PF are unattacked by sulfurse acid and oleus at B11 concentrations. Other Tuvreplastice, inelusing POOF, ECITE ard EIFE are cexistant to acid up to 90% concentration, but have lesser resistance to oleun snd sulfur thoxide. Temperature Limitations and polymer designations ere found in Table 4. Tople 4 SULTABLLETY OF LININGS. IN SULFURIC. ACI Faxanun Concentration Moteriel Tenperature (*¢) — Sulfurse Acid Pre 260 ora 260 FeP 205 Ecire 150 etre 150 Por 120 10s 0 65 PIFE ~ poly-teteaflucroethylene = 9, Ow Pont Tetloné-tFe PFA ~ perfluoroatkoxy = # modified TFE - e9, Ds" Poot.TeFlon®-Pra ECHFE = ethylgggyentorotrsfluarosthylene - 09, Molar’) FEE = Flussinated ethylene propytene copgtymer fesan wath IFE, ep, Du Pott Teflon® FP EIFE ~ modified ethylone-t¢bggflurcetny one = Soe bu Pont Yerzene Pie pely-vanylidene fluoride oa, Kynar® Fluncoplasties are hing sed more aod wore for sulfuric wc1d apprieataane euch ae Linings 1A pumps. and valves, Sheet linings of FCP, ECIFE, and. PVDF permit Fabrication of large cosponents such 23, tanks. Spaghett i-type CCP heat exchangers have dean used to cost concentrated sulfuric seid in contact plants for more then two decades. in Europe the hest recovered is often used for town heating These units cannot be used to coo) oloun as tne reaction pf Free sulfur trtoxide and water vapor permeating the FEP tubes causes excessive tenpera~ tures and destruction of the resin. Recently, PFA canstruction end design "odificstinns have inproved foxchanger tenparaturo and presoure capabilities. Dispersion oc poxder Linings of PVDF, ECTFE and PFAy with of without Tiber reinForcoxent, are applied ba a broad range of steel equipment, Equipment size is liwited only by eysilable ovens. USWalar is a registered trademark of the Allied Chaneal to. (16ytefzel 1s a registered trademark of E. 1. dy Pont de Nemours & Co. Process Industries Corrosion Polyester Resins Polyester and vinyi-ester resins, normally used to form 9 fibergless-reinforced Laminate,” show virtually no attack in dilute sulfuric acad ot 92°C and are used in pickling operations where 15-20% cid may bo encontared ot 80-90°C. AL 50% concen ration, the pulyesters can he safely used to 63°C and even find applications in special cases were the tanperature approaches 92°C. At 75% anid, tho Lomoerature ust be restricted to <65°C. At 90% fmost polyester and vinyl-ester rosin are rapidly degraded oven at anbisnt Leaperatat es Phenol-Formaldehyde and furfural Alcohol Resins These resins oro blended mith reinforcing glass or other Filler to make corrosion resistant. campos ite pipe and equipnenty ) Prenol-formoldehyde compos ites such as Haveg’'”) at NA (Cider filled) aad Haveg® pipe (with glass roving) have cesistunce to sulfuric seid at concentrations up to S08 at 190°C, to 70% at 100°C, and to 96% at. andient terperature Fucfural ateoto! cesins composites auch as in Haveg? Gt NA (Fiber Filled) have resistance to sulfuric eid at concentrations up te SO% at 90°C snd up to 30% at ondient. temperature, Cacbon and Impervious Graphite Impervious graphite has oxcellent corrosion resistance to all bul highly oxidizing concentra tions oF sulfurae acid. Impervious graphite coolers are ued in 93% sulfuric avid. Care must bo telcen that the anpeegnant is resistant ta the solvt io Polyester, furan and PIFE Inpregnante ace avai Lab Carbon is sunewnat superior ta graphite in the higher concentrations and is generally preferzed fur hat acid at eaneeatrat vans shave 0%. Carbon is less conductive and Tacks strength, and is, ther fore, unsuitable far cooler consteuct Longs Both Carton und graphite ace, of course, brittle 6:2 Loot seni ane Lanuon Heat-cured phenolic Linings on steel are often used to pravent’ iron contaminat inn in 93% sulfuric acid and have reasonable Life in 98% sulfurse ack at anbient tosperature, These thin-faln Linings Should nol be used Tor concentrations below 70% because of rapid corrosion of exposed steel sub- strate at pimoles. Butyl rubver snd Neoprene have good resistance to 50% sulfuric seid at modest temperatures and will resist (4g§% acid under anbient conditions. Hypaion'™87, a “sulfonated chlorinated. polyety enc elastower, ‘has been successfully used in plant applications involving dilute sulfuric seid, ay wel] 85 hoses handling 93% sulfuric acid, Glass awd ylass-lined equipment iy widely used in sulfuric acid service. For severe sulfuric. acid Applications, gless-lined steel i 8 popular rat. Fial oF constuction. TTWaveg Ts a registered trademark of Anetax, Ine (u}Hypaion 45 a registered trademark of E. 1, du Pont de Nemaurs & Co. 235,SPECIFIC CQULPWENT Unleas othermise mentioned, the Following diseuseion is Tur equipment handling’ sulfuric acid in the 30- 100% concentration range at ambient tenerature. Tanks: The basic material of construction for storage tanks handling sulfuric acid in the 70-10% range 1 carbon steel. Tanks should have a ‘ininun corrosion llownee ef 3m over the design thickness inacker corrosion allowances, eg) up to 6 nm, are Frequently spactfied iF the ‘conditions of tempera ture aod ‘concentration wareant. Under sone condi tans, corrosion rates have been reported to reach Van/y. The tank may have & controlled potential applaed (eg, through anodie protection) to minimize iron contamination and conteol corrosion. Gaked phenolic coatings have been applied to 93% (68 Beune) storage tarks to minimize iran pickup and corrosion, but Life is Linited in 98-99% service d to the highly oxidizing nature of the acid. (Cau- tions Suck coatings must never be exposed to alkam Line nouteaiszations, because alkali attacks baked pheaolie cuatings even an dilute concentrations.) The entrance nozzles and feed tubes should be physically located near the tank top center, and Girectes steaignt dom oc anay fron tho veasel wall, to mimmize the potential for Localized attack by Lusbulence affects: The discharge nozrles may be of staintess stest construction (ie, solid, Tined, clad or weld over~ Tay) to cage with the velocity increase at thet Location. Type 308. aay be used above 93% concen ration.” Type 316 may be used abave 90% concent rae tian. Fer loner concentrations Alloy 200%=3 may be Other desirable dosign Fastures include a high Liguid-level leew against overflos, a dessicat ing vent against absorption of ataowpherie moisture (unless the cLanate is arid}, and @ suitable cates nent of cunoff area in cose a releaac should occur: The vent should oe Located st the highest point on the lank Eo prevent hydrogen entrapment. Hysrogon evolved by corroRion can cause pranais buildup if blacked in piping, seab (repair) patches, oF vloued Caries axe nul uukgusbely vetlad Sie-ontoring nozzle are often alloned to protrude past the innar sueface of the tank et Least 2ocm on Une Lup 160°, This minimizes chances of hyétugen grooving up the sidewall. Many compenses use steiniess steel side nozzTe constructign (either Solid, Lined or weld overlay) ta prevent mydrogen Grooving problems That occur mith carbon steel. Tanks should ve made of steels resistant to brittle failure uch as ASTM ASIG. rattle failure 15 all too comon in sulfurie-seid tonkage due te high stresses in walls thinied by corcosion. For additional information athers®*83? nave summarized culfurie seid storage bank problems snd requirements Tor design and Fabrication. 256 Tank Cers and Road Tankers These ure mobile sterage tanks. Unless Lined there way be a tendency to accumulate on arom sulfate sludge which must be renaved periodicslly. To minimize “corrosion during this operation, the sludge should first be mechanscally or manually Fenoved, then the residue flushed with concentrated acid. Only then can a copious water wash and subse quent sudaeash weutralizetion be permitted. Not Bgain that neutealszation is incompatible mth baled phenolic Jinings, Unlined Eank cars are nghly sus- eptible tu hydragen grooving in Lhe top 100" Tank cars and road tankers should be matte of steels resistant to brittle fracture ouch ag ASTM A516. Tao many brittle Feilures of ASTH AZB> acic tank ears have been reparted. Papang The gaterials selection for strong sulfuric acid (7o-100%5" piping opends on @ murder af Factors, aut especially’ size, velacity and pumping schedule, Carbon steel piping may be used at ambient tan perature and low volacityy ie, 0.9 a/o maximus, oF here the punping schedule’ is brief (og, a Tew hours per dey). Good quality melds are essential and ymulti-pusé (3 passes asnznun) welds are suggested. Tf piping remains pressed ful, it wil see only static strong acid during the non-pumping hours, but 3U must be tenanbered thst hydragen pressure. ay Gevelup and hydrogen gruuving may accu, Khen Sirained, piping shauld be pigged free of acid oF placed tinder @ dey air ar anert gas pressure. Cast iron (gray or duct Lle) pipe has s samesmat ‘greater toleranes than staal for velocity, and nas been the preferred waterial up to 1.5 w/a 30 large sizes. Because gray cast iron 15 subject to mechan eal bresuage, duct ile Aron 12 row favored. fur small diameter piping, eq, under 100 nm, 300- Series stainless steel is preferred at_anbient tom perature and velocities up to 2 m/s. Type 30M nay he used far 93-100% acid. Type 316. may be used For G0-109% cid. The inside must bo chlorige free (preferably rinsed with 3 Low chloride ar chlcride- Free water and dried) bafore sogress of the acid 18 permitted. Abloy 20Cb-3 ar Lined pipe in afken ssn fur concentrations below 90%, Valves For imple shutoff valves in concentrations shove 90%, ol ybdenum-bearing slaintess steele are Used. Ihe industry standard is the cast version of Type 316 (CF-3M) with a cast UF=8 {Typo 304) oon aceestable alternate in concentrations above 93% Uaet Ub-aitu valves sie fhequently available ab Tittte edditiowal cost and offer ceuastance Lo dilute acid os well, Far throttling valves, where higher velocity turbulence snd/er temperatuces aze encountered, the CK-TH Least Alloy 20) 1s often used, Thea alloy as, Glso used for stock tank plug valves te prubect, against. inadvertent localized duiutiga effects 93 it wall withstand 8il concentrations at axbient tempur= ature, Process Industries CorrosionPups ENA centrefugal pumps are the endustry stan dard, althougs glass-lined ue inner purps are. alen suitable. Ine Lotter must be protected agains! mechanical damage. alloy £-276 (or tre east equiy~ alent) punps are sonetines employed, but usually ere neither necesssry or econumical fur urdinery hand- Ling ggg sturages Vertical 1nft punps with Process tran? casanga ‘ond Lewnet® arpellers are Frequent= Ay used for recirculation of acid in gulfurac-acid plants Caskets Solid (feltes) PIFE, glass-filled PTFE, or gtsintess stoel spiral-nound FIFE gaskets ace’ pre Ferrad, but envelope gaskets are satisfactory if the clastonerie or other coxprossisie material within am effectively shielded by 9 fluorinated” plastic envelope. Hoses Only fluorocarson-lined braided stainless oF suitaale elastonere hoses (eq, chlorusul Fenated polyathylene) can be emplayed’ in concentrated Sulfuric seid, coolers Fate ong teane Alloy 62276 coolers are used for uot ing Se IR sulfuris vid oneantration pty the Eeepepphure Limits of the atl plates anc tne vitor a gaskets, Cooling of 93 and 99% concentrated sulfurie acid 1s frequently done wath enodseally protected stein less steel coolers.” the ecid und the C-276 anodes are placed an the shell sido. Type 316 1a the usual tube neterial but 904. nas bees used where natersice (tubecids) conditions are severe, Cooling of oleun 1s Frequently done with carbon Steel spiral exchangers, Waterside cortosion prot Lees ace the greatest concern and baked phenolic Linings are used. Type 304 shell and tube coolers are also used with the water placed en the tube aise. ADKNOALEDGEMENT We author wishes to thank. b. Intnalt, 3. Ls Cooney, wT. Pollack, Bs J. Moniz, and Eo Ls Forty Tor their assistance in the preparstion oF this paper. TPFROCEEE ran mace by C. 5. Lewis & Cov, St. Louis, 15 3 modified cast iron cantaining & snail graphite Flake size. (20}¥aton is a registered tradonark of E. 1. du Pont de Nonoure & Co. Process Industries Corrosion REFERENCES, 1, Materials uf Construction far Mundling Sulfurse Aerd, NACE Publication 54151 = 1985 Revisions 2.0, Ne Stebert, "tarrelation of _Luboratury Electrecnesical’ Investigations with Fisid Apalication of Anocie Protect ion,* Mat. Pert P38, February 1931, 3. He 8. Tong, "Corrusion and Electruchenacel Behavior of" Fe-Cr-Ni Alloys in. Concentrated Sulfuric Acid Solutaons," pregented at Symposiun bn Progress in Electrochemical Carrosion Testing, ASIN, May 20-25, 1979. 4. RH. Kain and P. £. Mareis, *tnadae Protection of FecCr-Ni-Ho Alloys in Concentrated Sulfuric Bei," presented at Corrosian/76, NACE, Houston, Texas, Moreh 1976. 5. M. Tiivel and F. MeGlyna, "Avoiding Problems in Sulfuric Acid Storage,” prosented at Rearican institute of chowsal’ Engineers, New Urlesns Meeting, April 1985. 6 E. Willians and M. E. Koup, *Efrect af Copper Content of Carson Steel en Carrasion in Sur furie eid," Corcosion, Val 21, No 1y pp 9-14, denuary 1965. 7. My Endy ond §. Morivka, "Dissolution Phenonencn ‘of Copper-Cont ining Steels in Aqueous Sulfuric Seid "Solutions of "Vaesous Coneentewtions," presented at the Japanese MeLal Assaclat lun 3rd Symposiun in April 1938, tranelated frum Japanese by the Ralph HEELeoy, Custon Division, Bustin, Texas, 8.0, Fyfe, et al, "Corcosion in Sulfuric acid Storage Tanks," GEP, March 1977, 9, 8. 1. ELlagon and W. Re Sehmeat, "Corrosion of Steel in Concentrated Suifurte Acie,” Elec. Sees, Yol 125, p 524, 1978. 10.5. W. Bean, Jr. and 6. 0. Grad, "Coreasion of Carbon Steel by Concentrated Sulfurie Acie," NACE Corrosian/Ad, Papier No 147, 3984, TL. S.-M. Dean ond Gs D. Groby *Carracion of Carbon Steal “Tanks "in Concentrated | Sulfurae Acid Garvie! HACE Buevionioi/B5, Puper No 298, 12M. 6. Fontona and N. D, Green, Corrosion Engineoring, MeGraw H111 Bask Coy Now York, NY, 1967. 13. £. Maann, "Corrosion of Cant tron in Concentrated Sulfuric Acid Under Potentrostatic Conditions," brit. Corr. 3.4 Vol ty Novenber 1966. 14. Corrosion Engingering Bulletin 1, "ihe Corrasion Resistance of Nickei-Containing ALlays in Sulfucie Reid and Related — Compounds,” The International Mickel Company, 1983. 15. 2. E. Strutt, "Corrosion Resistance of Staintess Steels in 938 and 95.5% Sulfuric Acid,” 8 report to the Materials Technology Institute, Seat. 1985. 257uw 18. 1. 20. a. 2, 2. 2a, 2, 28. 258 H Abo, Me ted, ans 5 Resistance’ of Various Stwinless Steels to Sulfuric Acid Selct ion,” Bosholy Gjutso, ¥ 23, pp 341-346, 197%, an Japanese. Noguchi, “Corrosion P. PF. Wieser, ot al, "Resistance to Erosion Corrosion of’ Comercially fast Steals Watersals Protection and Performsnee, Val 12, No 7, 9p 34-38, duly 1973. H. A, Streicher, "Corrosion of Stainless Steels 2h Bailing Acids and Its Supcession By Ferric Salts," Corrosion, Vol 14, No Z, pp s9t-70t, Fob. 1958. 5. C. Kiefer and W. G, Ranshaw, "The Behavior of the Caromaun Nickel Stainless. Steels in Sulfuric Acid,” Corrasion, Vol 8, p 235, August 1950. 3. Re Auld "EFFect of Meat Treatment and Welding on Corrosion Resiarance of Austenitic Stainless Steele," Proceedings Second Internat tonal Conference on Metallic Corcosion, Nace. 1. MN. Anderson, et at, "Effect of Nitrogen Okades, Sul fur Dioxide, ‘ana Fercie Tons on the Corrosion Rearstance | of Mild Stee] in Concentrated SulTurie Reig," Metallurgical Trans. VoL LIA, August 1980. D. R. MeAlister, et al, “Heat Recovery From Concentrated Sulfuric Reid," United States Pats 4,576,813, March 1936, D. R. McAlister, et al, "A Major Breakthrough in Sulfuric Acid Heat Recovery,” pcesented at ALONE 1986 Annua! Meting, Now Urleana, LA, April 986, Me Renner, et al, "Corrosion Resistance of Stainless’ Steels’ and Nickel Alloys in Concentrated Sulfuric Acid," NACE Corrosiun/B6 paper 169, D. J. Oreonister and 1. f. Spance, "Influence of Higher “Silicon Levels un the Corrosion Resistance af modified CF-lypx Cust Stsintess els," Proceedings of the NACE Corrasion/85, Syepositn on Corrosion in Sulfurie AviMy p Pe A. Seidiur, —MMuchanases oF Corrosion $n Goneanteatind’ SF |e Acid," presented at Sulfur 2. 28. 2. 30. ah 32. 35. 3h 38. 36. 37. 185 Intornat 1385. inal Conference, Londen, 10-13 Nov. J. Re Crum and Me E. Adkins, "Correlation uf Alloy 625 Electrochemical “Sehaviue with the Sulfurie acid Isocorrasaon Ohart," Proceedings Of the NACE Corrosion/85 Symposium on Coceast an Sulfuric Acts, p 23s R. 1. Webster and Te L. Yau) "Zicconue in Sulfuric Acid Applications," proceedings of the NACE Corrosion/85 Symposiun” an Corrosion in Sulfurie seid, p 69. Ne Ay Maguire and Ty Le Yeu) "Cortusivn= Electrochenioal Properties” of Eirconsum un Mineral eids," Paper 265 Corcosion/B6, NACE Le Xe Glesinan, "Carroston of Tetaniur in Sulfuric “Acad ’ and Chlorine," — Carcosion, Septenber 1956. 2. 9. Gegner and W. L. Wilson, "Curresion Resistance af Tktaniua and Zirconius In Chenicel Plant Exposures," Corrosion, Yol 15, 1999. 2. P. Cotton, "Iatenaum For the Chemical Plant Glen! Engr. Prog., Yot 66, Ho 1D, Oct. 1970. Ne G. Feige, “Ine Industetal applications of Titanium inthe Chemcal Industey," presented at the Sympasiun on 1itamium-Ziseantus Fur the Chemical’ Process Industries, New Orleans, Nov v5. R. €, fatnall and D, . Kratzer, “ihe Use of Flurapiasties in Sulfurie eid service," Proceedings of the NACE Corcosiar/85 Synposiun fon Coerosion an sulfurse Aei8, p 85. 2. R. Schley, "Impervious Graphite for Process: Equipment =" Part 1," Chomieal Engineecing, Feb. 18, 1978, J. Re Schley, "Iapecvinus Graphite fer Prucess: Lquapment —" Part 2," Chemical Fagineer ing, Macen 18, 1974, C. Sheilds and W. 9. Nosserty exeniiy x Lesson fron a Sulfurie’ Aced Tank Failare," Pollan Enganaering, Dos. 1987. Process industries Corrosion0 dg, Ww. Ww Ww Ww. Toosds ax aN Ww | a WN WN ‘Lad OIL coup opt | OPH cape | SENOS v OR H/LON 7 : : = = = 50 oN PAS 7 v sidca__| teoe¥a_| _soewa soo | aotewm | soma _|_toie1a_| -esoncwa -o1010109 apaunor WSN | _NS'SMO NSSMS, NSSMO_|_NSSMO | _NSSMO_|"NSSMO [_NSSMO | WHSMO | WaSMO | Sig DoE Tupi IED Tats 2 avasa | Sve av. - ovia_| ov og SUE PECL ean é 3 ¥ t T ARAN GT = viet rea Ti ri Tie rea ay Eee Tia Spe was : ‘ttrd aay oev__| soreciey | msocamce-y | “tory | roresonv | rosszsiy | sicazew | coeas | aamssev | sow open ey roriciey | voeaciey | Wie ciey | oraziey | ire ciew | vara | sooty | aso eg SOO 7 asd ses sree seseeeaen [enna = GST | — apa | SoRRATSNG a HL ‘aNoo ‘NOD |__ows | onvars | vos | wars rosth_| _tost_| vost sang (oa c > * t = 1 aaRENTTAN INaWHOVILV uonsadsay pue sanpasoig SUpIPAA “TENGINEERING S' PT BADAK NATURAL GAS LIQUEFACTION STANDARD MEMO # 8 Project Warehouse Supervisor Date 2{s]o]s|o]}s n Facilities Engineering Section Head aes Subject Bill of Material Transmittal (Part No.: 1 / Rev. No.: 0) JopnuMBER |7| 5/4] 1]1 as, 4] if2 L| | | JOB TITLE L SPECIFICATION FOR REGENERATION SKIDS/ACID ALJZER UNIT ENGINEER - died GROUP HEAD: Posma Rajagukgfk For the above project, please find attached X_] Original Revised Additional Bill of Material (BOM), CE] consrctonmaertt LZ] consteton Tos EZ] consmabies [2] commioninn spares Note: Items for commissioning spares are indicated in t Use of Material he remarks collumn of the B.O.M. The material is used as the solution of upgrading valves material in the regeneration skids Please proceed with material procurement to meet the required schedule. By copy of this memo, Maintenance Planning / SCC & CP Section *) is requested to verify that a Work Order - referencing the above Project Number -has been prepared to accept charges. Please be advised that for this job: A Design Package is not required X] A Design Package has already been issued. + LY a SA di, Deded HendraNS * Fe Setontiead DISTRIBUTION : (_1_) number of copies ‘Amie dalled Design Package (Memo # Part Rev. ___} will be issued before _/_/ *) strikethrough as inapplicable Memo only to (1) Teetmnical Dept. Manager (2) Custodian’s Dept, Manager (1) Logistics Dept. Manager (1) Project Eng, Section Head / file (1) Process Eng. Section Head Memo Attachment to (1) Project Warehouse Supervisor (3) Maintenance Planning Section Head (1) Custodian : Utilities?/1ISection (1) Technical Library File, ICS (1) Facilities Engineering File PPG0305-01-08 Rev. 0- 15/11/00 Effective : O/01/01 ‘Approved by TDM/PDMWW eke PI Td z > va [az ry 1 pour ZALY aalasm04 0 danyoug| CTV AAPA YOOUD YALA C1 : va | oz 0 ON TAYE wUVWay NoManIOsaa aLITAWOD isanias_|_ssvio | uinn | ALO] “ON WIGAN NOLS Nowyoisi9gas AdnS"ONT'TVAOUdAY ‘DNA TOUd TVAONdAY Ad GIN VddUd ava aooz snp: aaInoay 34va aQNTWIITH suman s37y oweasusd>y 10) se wcyoceyo au TYNIDINO. TWIVW 10 Ta ANVdINOD NOILOWASNON SVD IWHNLVN XVGVE “LdMAC ARV2 Lined Check Valve ARV/SG Lined Sight Glass Combination Universal Application