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    Corrosion and Fauling in Alkylation Units PDF

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    CORROSION AND FOULING IN SULFURIC ACID ALKYLATION UNITS Presented By Jeff Caton, Staff Process Engineer Brian Racen, Staff Process Engineer Greg Troutman, Process Engineer DuPon(™ STRATCO® Clean Fuel Technology 11350 Tomahawk Creek Parkway Suite 200 Leawood, KS 66211 September 2008, os ee nl ‘Table of Contents Page Number INTRODUCTION REACTION SECTION = A. REACTOR CORROSION e 2 2 Figure 1- Zones where Wet Streams and Acidic Sireams are Mice. BL CONTACTORREACTOR TUBE BUNDLEFOULNG nc : [REFRIGERATION SECTION AND DEPROPANIZER A. REFRIGERATION SYM, BL Dernoranazen S¥STIMS.... eta igure 2- Wet Depropanizer Feed Treatment = C.— RerRioHRAWT REcycLE PUMPS... [NET EFFLUENT TREATING AND FRACTIONATION, : A. Aca WASH CoALESCER/ALKALINE Wactax WASIUWATER WASH COALISCER Figure 3 - Acid WasW/Alkaine Water Wash/Woter Wash Coalescer. 1B. BAUXTE TREATING : = Figure 4 Acid Wash Colescer/Bausite Treating : © Dasopuranzan ToweR. ACID BLOWDOWN SECTION, —— ‘igure 5 Acid Blowdown Drum and Blowdown Vapor Serubber. CONCLUSION. te : CCorosion and Fouling In Sulfur Acid Alkylation Unis Paget ‘CORROSION AND FOULING IN SULFURIC ACID ALKYLATION UNITS 1 mTRopucrion (Causes and contos for many ofthe potential comosion and fouling problems in 2 slic sci alkylation unit are reviewed in ths pape. Corsion and fling should not be serous problems ina plant hati well designed, operated and maintained. Process conditions tht [provide the best yield and product quality also tend fo minimize corasion and fouling However, probiems are et uncommon in plants operated a rates significantly above the design espacty or where maintenance and operating problems go uwesolved. ‘The Fundamentals of Corrosion and Fouling Control ‘Most corosion and fouling in uli acid alkylation unit canbe mininized by following ‘he common sense fndamecas sted belo: Mainzain good reaction conditions. “Avoid high velocity or temperature insur eld service. Donte acd sit stagnant ‘Mninize the amour of waerenering the process ‘Keep acidic steams dey and “wet” sreams neutral Use corrosion restant ‘materials where they mis ‘Manian good retin operations. ‘Be exra alert n wits pushed above design capacity, ‘Throughout the rest ofthis paper, these rule wil be reste o specific examples in each section ofthe alkylation unit Tl. REACTION SECTION A. Reactor Corotion ‘Maintain good reaction conditions. ‘The reaction conditions which produce the best quay aliylte at the lowest acid consumption alo tend to minimize corosion and fouling throughout the alkylation lit Low reac longer, low space veloc, high sbwane-olefin rao and high acd stengh all favor the allylation resction and tendo suppress Uudesible side reactions. In particular, the rate of corrosion and erosion in a STRATOO® Conictor™ reactor is minimize at low temperature and high acd strength (epecilly low water content). Contactor reactors in low acid strength Service tendto have he highest ates of eorosion Reactor operation also affects corrosion and fouling outside the reaction section. Good reactor operation can minimize the formation of SO, snd alkyl sults, which can overoad the depopanizer fed tweatment and net effluent treating stems, respectively. The formation of SO, increases a eaton temperature increas Corrosion and Fouling n Sulfrie Acid Allylaton Unis Page? Avoid high veloc temperature in sulfur acd service. 1m genera, the acid sueng nthe reaction section ofa sulfuric aid sylation plant shoud not be allowed to fll below about 89 wits, The overall corrosion rate of ‘abn se! is very low at this ald strength, 20 gene corosion ts usually not a roblem. However, some prsations ar necesay to preven localize erosion. Tron sulfite, a corosionprodet of carbon steel and sulfuric ci, forms a protective ‘mon the surface of testa. Ths coating bas low solubility in strong aid alow ‘empertue but is soft and can be sipped away i subjected to high Mid veloc Fortis reason, DuPont sizes sulfuric eid ines tha are to be in continuous service such that the velocity maintains between 1-3 feet per second (03-09 meters pet second) in new alkylation nits, Corosion and erosion accelerates dramatically if the ‘eosty exceed 35 fet per second (09-15 meters per second). This problem is ‘ot uncommon in older allyson units that ae being operated well beyond their CILESO, + 10 (CHyO-CH, + 21:80, -> 2CHLISO, + 10 Corrosion and Fouling ln Sulfuric Acid Alkylation Units Page 4 “Methanol and DME ar also hail because they increase the solubility of water in the hydrocarbon fed, rendering the alkylation unit fed coalesce les effective, The sddional water in the eefia Ted charge and that peedaced bythe above reactions ‘ours accelerated comoron in the Contactor reactor ming 2008. With good operation of the MBE plant water wash and methanol recovery colum, very litle methanol should be present nthe skylton pnt fod In contr, the ‘ater wash dos not remove DME, Tis conoentaton in the afin steam depends ‘08 MTBE reaction ze operation. DuPont recommends tht fines with MTBE oF "TAME units upstream oftheir lklation unit analyze their olf feed regulary for cxygeates. Bear in mind that the refinery Ibortoy gs chromatograph must be specially configured o fll detec all the DME preset MTBE rain. DnPont 7s found that refinery labs tend to underepr the acta amount of DME present. ‘Stops shouldbe taken to prevent conditions or upsets which increase oxygens in the aliylation ni fed. The us of molecular sieve dryer to remove oxygens and ‘water fom the MTBE raffintc may be very atactive depending upon the ‘concenrton of oxygenate in that steam the reactors are experiencing a high corosion rte due to oxygenate in the feed, cone posible remedy is to ineease the acid spending stength upto about 92 wis ‘This action will increase the sid rate hough the un and reduce the concentaton cof water in the spent acd Keep acidic sreams dry and "wet" sireams neutal, Use corrosion resistant ‘malerel where they mic, “Localized low acid concentration can occur in zone: where wet hydrocarbon and acidic steams are mixed, ven though the overall mixture may not bein the ‘orosive range. In this context, a hydrocarbon steam is considered wet if it ‘contains dissolved water Free water need not be pset. BY this definition, the ‘olefin fed and recycle isobutane in most plants ae considered wet steams Ta regions where wel and acidic steams are mixed, comosionsessant material is ‘sbsttted for earbon sel An examples shown belew in Figure 1 Corrosion and Fouling In Sulfuric Acid Alkylation Units Page 5 ‘igure 1 Zones where Wet Streams and Acile Streams are Mined To resist conosion inthe Contactor restor mixing zane, DuPont typically wet Tastelloy C forthe impeller and hydrocarbn feed nore. "The piping wherein the ‘olefin fed and efgeant recycle are combined ise pot at which a wet steam and ‘sn acdi team ae mixed. (In this case the regent recycle is the acidic stream because it contains small amount of SO,) DuPont speiis Alloy 20 piping from two feet (610 mm) upstream of the feedretigersnt reyele mix point 10 the Contactor eactr feed nazi. B. Contactor Reactor Tube Bundle Fouling ‘The tube side of the Contactor reactor be bundle sometimes becomes fouled, specially in pans that are operate at high acid spenling svengh andlor above NaHISOS 80; + 2NAOH > NasSOs + 1k0 ‘The mest important parameter in operation of he cautic wash are good, ‘mixing the rato of casi to hydrocarbon fed andthe use strength, Corrosion and Fouling In Sulfuric Acid Alkylation Units Page 8 re - Wet ry een tH = oy 20 Pipe ogee) t fe 31688 Pipe (ee oJ + —sED ‘A vairy of mixing devices inching eductors, mixing valves and sac ‘mixers hae been used 1 improve contacting betwen the depropnies Ted ‘and the emusic. DuPont specifies an Allo 20 Sulzer SMV fivosago sic ‘mixer for serve. The sta mixer ito be designed to produce 300- 400 micron elelated average droplet size atthe outlet ofthe mixer. Note that this dopet size is based om Sulze’s comeations and might not be applicable t© mixes provided by other venders. Apical ferential ‘resure fr a mixer of this ype is B15 pa (Q6-1.1 kpem’), The sate mixer presure drop should be monitored with 2 diferent presse indicator. An unexplained reduction in pressure drop i ily to indicate damage tothe sai mixer. In order to avoid corrosion inthe mixing zone, the piping fom four fet (1.2 meters) upstream of the eustictydrocarbon ‘mix point to the sac mince and the piping fom the sate mixer to the susie wash drum is made of Alloy 20. ‘The caustic ciculaon rte is mained in the range of 20-30% by volume of the depropanizer fod Fresh caus strengths above 15 w% should be avoided. Plugsing ofthe depropaiae feedeaisie’satic mixer and associated piping die 10 “precipiacen of caustic sls has boon known to oeur when the concentration ‘of the fesh nut is too high, Fresh caustic strength is nomally inthe 10- Te wiverage ‘Carosion and Foaling in Sulfrie Aci Alkylation Units Page In btch systems, the caustic shouldbe replaced ata minimum stength of 3 tas measured by tration. The caus solution wil lose water ovr tine tothe diy depropanizer fed seam Concentated caustic solutions tend 12 ‘enulsiy and cary over, s0 makeup water shouldbe added to replice the ‘water that i ost The simplest way t do this 10 add process waters eccisary fo hold a constant interface level inthe caustic wash rum. 1s imporant to use water, NOT ffesh caustic, maintain the interface lee. Another approach to water makeup isto odd wae to maintain the pectic ‘aviy ofthe cast inthe range of 1.10.0 .15, ‘The hydearton fom the caustic wash drum flows to the depropanizes eed coalesce where unces of caustic fom the cause wash drum are remored with the aid of coalescing media. Fresh water make-up is added tothe CHIOH + 1450, Neutralization HS, + 2 NAOH -> NaSO« + 2140 Inthe alkaline water wah dum, the hydeocarbon end aqueous phases ae seperated boy gavity setting aded by coalescing media. Previous designs provided only ray setting and larger vessel was required. With the auton of coalescing ‘modi, smaller vessel my be installed snd overall capita costs of a new grasrots faliy maybe deceased. ‘The design ofthe allalne water wash system i based om the olefin feed to the unit ‘When aylating propylene, the alkyl sulfites formed are more sable than those formed when alkylating butylene nd amyenes. Therefore, many enhancements re rade to the treating design when processing high eve of propylene. ‘The specification ofthe laine water wash n-ne static miners based on the type of olefin fed procesed. For units alkylating mostly buylenes and amen, DuPont spcitcs the inline mixer as « Hastelly C five element Sulzer SMV type static mixer witha droplet size of 300-400 microns. Note tat his droplet izes based on Sula’ corelations and are nt applicable to mixers provided by oer ‘vendo. Typical differential pressure across the mixer is 8 to 15 psi (0S to Ll ligjcm’). This presire drop should be monitored with diferent presse indicator vent the inteety and perfomance ofthe mixer For wits alkylating ‘propylene, DuPont specifies the five element in-line sac mixer to have thee spacers, one before cach of th final thre elements, The specified droplet size and ferential pressure drop speciation i not modified for propylene designs. The ‘propylene design enhancenents were developed in ode 0 serease the contact one ofthe allaline water and act effluent steam To resis coresion in the mixing 2006, Haste Cis the recommended piping material 4 fet (12 meter) upstream ofthe net efluenllaline water mix point and Aloy 20 is recommended downstcam of the sate mixer tthe drm. ‘The operating temperate ofthe alkaline water wash lo depends onthe olefin eed ‘ype processed. When processing butylenes and ampenes, DuPont designs the alkaline water wash to operate ata tempemtue of 120° (9°C) to fcliate decomposition of the remmning alkyl sulfites. However, DuPost designs the alkaline water wash to operte at 160°F (71°C) for units processing a high level of propylene. Hot alkylate producti used in the alkyatelakaline water exchanger to ‘maintain ths temperanse. Low pressure stean can be used in the sess relieved -Greulating alaline water este to supplement the equed est ton. Corosion and Foaling ln Sulfuric Acid Alkylation Units Page 13 Upstream ofthe aliylacaltaline water exchange, process water is added tothe eating alkaline water steam. Spent alkaline waters withdrewn and replaced by process water to contol the conductivity ofthe allaline water between 5,000 and 5000 pmhotm. Conductivity is @ function of taal disolved soiés (TDS) ‘concentration, Excessive TDS (10,000) can cause tight emulsion tha can result in caryove. Caustic is added continously to the crculaing alkaline water to ‘maintain an alkaline water pH of 12+ I. The alkaline water recirculation rte should +6 20-30% by volume ofthe et fluent ats ‘The design caustic and proces water makeup rates forthe unit depend on the olefin feed processed. Units processing propylene ae designed with ice as mach process water makeup and caste makeup to acount fer the increased dificult encountered in weuing operations. DuPoats design vales forthe rates are very conservative, ‘oven for butylene o amylen operation ‘The hydrocarbon from the allaline water wash flows 1 the water wash cxsescer were races of enusc from he alkaline water wash drum are removed wih the aid of eoulesing media. Preth water makeup is added to the net efuct 10 absorb alkaline water droplets that caved over fom the alkaline water wash drum. DuPont species the fesh water make-upinet client inline mixer as a 3ISL SS fve

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