Corrosion Control on Amine Plants

Comparison between corrosion rate of DEA and MDEA
A case study in sour gas refinery (SGPC- !angiran" R.Mesgarian and M.H. Firoozbakht

#ntroduction : Shahid Hasheminejad Gas Processing Company (SGPC-Khangiran) has five similar gas treating units and it has experienced using !" #$%&' as a s(eetening solvent in gas trains for more than )* years+ ,or the last decade(ith increasing gas demand- the possi.ility of capacity increasing for the s(eetening units (ere focused on replacing of / !" instead of !" + &rying to achieve this aim- after many revie(s and studies- it (as decided to change the s(eetening solvent from !" #$%&' to / !" $0%&' in )**$ 1+ &herefore using second and third amine types (ere experienced for sour gas treating in Shahid Hasheminejad gas processing company+ Corrosion su.ject in al2anolamine gas treatment plants has a special importance+ Plant economics are negatively affected .y the loss of revenue- due to the unplanned outagescaused .y corrosion damages- and the cost for their repair + /any of the causes of amine plant corrosions have .een identified- and reported earlier- 3ased on this experience)- #- $- 0+ &he design and operating practices of these gas treating units (ere constantly updated and upgraded+ "mong those factors identified- are the choice of amine type- acid gas- acid gas ratio- contaminants- and operating conditions+ 3y regarding the experience of second and third type in SGPC- 4n this article it has .een tried to investigate comparative results of corrosion rate for lines and e5uipments in amine paths+ "lso the amount of heat sta.le salt formation and amine degradation products (ere compared for !" #$%t' and / !" $0%t '+ ,urthermore methods used to control and reduce corrosivity of solvents(ill .e offered in part 44 of this paper+ Materials and met!ods: ,igure (1) sho(s main areas of an amine unit- that the rate of corrosion must .e measured .y different corrosion monitoring methods + 4n SGPC- coupon corrosion testing system- has .een a normal practice- during previous years+ &he rate of corrosion in the main e5uipment includes6 7e.oilers- lean8rich heat exchangers- pumps- contactors- regenerators and amine circulation paths- (hich (ere measured and analy9ed- for more than one hundred points- for .oth !" and / !" solutions- at the similar operating conditions+

lems+ &he heat Shahid Hasheminejad gas processing company (the results (ill come in part 44)+ .(ith contaminants such as oxygen (.than hydrogen sulfide (H)S).amine loading.le salts.y undergoing the chemical reactions.)) +&a.samples of amine (ith different life times (ere analy9ed.Figure 1: Main corrosion areas in a schematic amine process flow diagram "s (e 2no(.< HSS shouldn=t exceed 1*' of the amine concentration>+ 3y nature.le salts are non-regenera.).e entered.or generated (ithin the units .le amount of HS"S in amine solution+ "s a rule of thum.and inade5uate design (too high flo( rates) have influenced the corrosion in amine +plants : Heat sta.ent throughout the plant+ 4n this research.rate of oxygen that can .an amine purification pac2age (ere designed and .uilt.)).le salts are essentially the reaction products of al2anolamines and the acids (ith a higher degree of acidity.and the amount of contaminants for !" and / !" solutions (ere measuredthen the effects of contaminants (ere evaluated on corrosion+ .temperature.and sulfur dioxide ( remain and accumulate in the a.2ey factors including6 type and concentration of amine .the heat-sta.))+ &hese acids are usually introduced to the amine units (ith ma2eup (ater and feed gas streams.and car.le under solvent regeneration condition+ "s such.on dioxide (C.inally for reducing impurities.sor.on monoxide ( a major role in corrosion pro.and degradation products.contaminants .le 1 sho(s0 common sources of anions and it is a guideline for maximum tolera.

oilers and lean8rich exchangers have higher corrosion rate than the other e5uipments+ Table 2: Location of coupon in gas treating units .after )$ months of operation period .8component in gas "cid in the feed gas8.ormate8oxalate "cetate &hiocyanate Phosphate Source /a2eup (ater8.# @ )H).itors8phosphoric acid activated car.lash drum .Table1: Heat stable salts.Coupon ?o Docation 1 Contactor 2.) A S).rine (ith inlet gas /a2eup (ater8corrosion inhi.ilter E 7eflux 1* .6 "mine cooler 7 7egenerator F D+"+ .oiler 4 D87 !xchanger 5.3 7e.corrosion rate for amine pipe lines and e5uipments (ere measured for three similar gas treating units ( G&BC1-#-0) -for .on 3ased on scheduled program.oth !" #$(t' and / !" $0(t' at the same operating conditions+ Measurement of DEA and MDEA corrosion Docations of coupons in gas treating units (ere sho(n in ta.including6 re.e divided in t(o areas (high corrosion 9one and lo( corrosion 9one) for !" solution+ High corrosion 9one.le). common sources for the anion Anion Chloride ?itrate8?itrite Sulfate8sulfite &hiosulfate .and the results of corrosion rate of coupons (ere illustrated in figure )+ 3ased on the results+ Corrosion in amine pipe lines and e5uipments can .itors Sulfur species oxidation products )H)S @ .) degradation thermal degradation 7eaction product of H)S and C? Corrosion inhi.

oilers and lean8rich exchangers. "Tu# $esults and discussion &he results also sho( that corrosion rate of e5uipments for / !" are less than !" (especially for high corrosion 9one)+ &emperature is one of the most important parameters that affects the corrosion rate+ Process fluid temperature in higher than the other parts in amine circulation path+ "s it (as sho(n in the figure).Figure2: Corrosion rate for MD ! and D ! in "tu1 .le #>-F+ .le salts (ere sho(n in ta.ove+ Heat sta.le amine salts (HS"S) and amine degradation products play an important role in corrosivity of al2anolamine.all of the points in high corrosion 9one are related to e5uipments that mentioned it is necessary to control them in amine solutions+ 7ecommended limit of individual species of heat sta.

2> / !" .heat sta..2> 1. (5 5*.4> ---- 3y reaction .5> amine molecules and other components in the feed gas (..ormatchloride. +). 75 )7.+ 3 ---5.le salts such as6 sulfate.four samples (ith different life time (ere analy9ed for !" #$(t ' and / !" $0(t' .4.. &... )+.the amount of neutrali9ed HS"S for !" solution (after one and half year operation) is 0E' more than / !"+ /oreover.oth / !" and !" during operation+ 3ased on the results. 7. 5...) 75..le salts (ill form in ... ). ). 47. +.& 4.)). &. 7.the amount of HSS and degradation products (ere indicated+ 7esults are sho(n in the titration and gas chromatography (G+C+) for !" is 0 times more than / !"+ "lso "nalysis results of amine solutions clarifies that heat sta.ragments amine and other component..ormamides (%t' Solution !" 1.)* .(ill form+ Da. ---). +5.contaminants (ill form more in !" than / !" solution during processing of sour gas+ &he amount of main degradation product of !" solution (&H!! ) is much more than / !" for the analy9ed samples+ . )7.le salts and amine degradation products are accumulated for . 75 -..oxalate etc.degradation product (ill form+ &H!! (&ris-hydroxyethyl ethylene amine) and 3icine are the 2no(n sample degradation products of second and third amine type+ 4n this study. &.acetate.(especially C.oratory result sho(ed heat sta.& .) 7+5 (.Table #: $ecommended limit of H%!% and degradation products in D ! and MD ! solution (HS"S(%t' Solution (&H!! (%t' Solution (3icine (%t' Solution (.<alate (ppmw (Acetate (ppmw (=utyrate (ppmw MDEA after )( mont! MDEA after * mont! DEA after * mont! DEA after )( mont! %imit&'( ..oth / !" and !" solutions+ "mine degradation products are high molecular (eight compounds+ 3y reaction .le ($)+ Table &: samples anal'sis for amine solutions SAMP%E (2 GC / 0itr (1t (2 06EED (1t (6SAS (ppmw 8eutrali9ed (:ormate (ppmw (Glycolate (ppmw (Sulfate (ppmw (.)-Cl and etc except H)S and C. )5. 5. &5.5> 1> 3> / !" 1.. )7.5 +. .) 3 +.7 &.) 3 +. ---- &he results indicate that the difference .results sho(.& (.)). 7).

3allaguet-H+P+."pril 1EE> .Corrosion rate for amine circulation e5uipments and pipe lines are more sever in !" #$(t' compared (ith / !" $0(t' solution(particularly for high corrosion 9one)+ -Heat sta.G critica! !ook at amines" a practica! review of corrosion e#perience over four decadesG-F#rd annual GP" convention ()**$)+ #+ 3ich-?+?+.a2ht /+H-GConverting to a tertiary amine ups +1 +sweetening capacity at an Iranian gas refinery G.ility and reducing the corrosive nature of the solvents.and Schu.$Corrosion in a!kano!amine p!ants" causes and +$ +(minimization$-Corrosion)*** ()*** uPart /+ S+./esgarian 7+ and firoo9.3acon &+ 7+ and !d(ards + H+.e controlled and minimi9ed .on processing-Han+-)**F )+3onis-/+7+.7ichard..ert-7+.1EE> +: Sheilan /+H+.Ian horn !+-G mine treating and sour water +> +stripperG.ifth !dition.e seen from the results.4t can .urification.oth HSS and degeradation products are of concern in !"+ $eferences: "miri S+..ifth !dition.+as ."rthur and ?ielsen.and 7igaill-C+.&+ 7+ 3acon and uPart /+S+.the amount of HSS and degradation product in the gas treating plants must .or our gas treating units= relia.&ffect of .$Corrosion in M%& sour gas treating p!ants" corre!ation between !aboratory testing and fie!d e#perienceG-CorrosionE: (1EE:)+ 7ooney-P+C+ and uPart-/+S+.Street +!+.)**F 7ooney-P+C ."pr-/ay +1EE# +Kohl./arch1EE:.y proper amine type selection+ .Hydrocar.e monitored and controlled during operation+ .G'nderstanding corrosion in +0 a!kano!amine gas treating p!ants part()* G.Hydrocar.Spooner 3+?+.on processing.on processing.&he major degradation product of the second and third amine type is &H!! and its accumulation in !" is much more than / !"+ .-.that the amount of HS"S in / !" after 1F month exceed the allo(a.+..Corrosion in al2anoleamine gas treating units can .le salts and amine degradation products increase the corrosive nature of the solvent and formation of them in !" are more than / !"+ .Iacha-.Hydrocar.4n / !" the control of HSS is important..le limits+ Conclusion: .on M%& so!ution +F +corrossivity$ .(hile .