Session III - Hydrogen Processing

A. Hydrogen Production 1. Hydrogen Manufacturing Question 1 How is CO2 corrosion mitigated in hydrogen units? Question 2 To make RFG and low sulfur diesel refiners need more hydrogen yet traditional sources like catalytic reformer hydrogen are !eing reduced" How are refiners meeting this challenge# $urchased hydrogen new or re%am$ed hydrogen $lants reco%ery systems etc"? &re any new feed sources or technologies !eing used to $roduce hydrogen? Question ' (hat is the $anel)s ad%ice on how to a%oid o%erheating of steam reforming furnaces? Question * Our methanator tri$s on high tem$erature monitored at a thermocou$le 2+, down in the !ed" This ensures that the tri$ occurs !efore the !ulk of the catalyst and reactor are o%erheated" &s the catalyst ages and deacti%ates is the -2+, $oint- still sensiti%e to a surge of CO2? .s there a safer strategy to follow for the $rotection of methanators as catalyst ages? Question + (hat methods are a%aila!le today for monitoring the sulfur content of the feed to a steam reformer? Recommendations as to the re/uired %olume of Co0o catalyst for the desulfuri1er in a hydrogen $lant de%iate su!stantially 2133, difference is not uncommon4" This is not the case for the other catalysts in the hydrogen $lant" (hy is this so? Question 5 (hat is the $anel)s recommendation concerning the use of a se$arate chlorine guard as $rotection for low tem$erature shift catalyst? Question 6 &re any refineries currently monitoring for methanol emissions from their hydrogen manufacturing facilities? .f so what le%els of methanol are !eing found? (hat analytical methods are !eing used? B. Hydrotreating 1. Reactor Bed Plugging Question 7 (hat is !eing done u$stream of hydrotreaters to minimi1e causes of !ed $lugging? 8lease discuss metallurgy corrosion control intermediate storage and filtration" Question 9 Has anyone found a relia!le method for filtering solids from a hea%y feed such as $roducts from a coker FCC: or other $rocesses? ;ist s$ecific micron si1es for ty$ical $articulate foulants" 2. Reactor Effluent Systems Question 13 Has anyone o!ser%ed high corrosion rates in the e<changers and stri$$er feed heaters downstream of the ;8 se$arator in a diesel H=> unit? .f so what was the cause and what materials are recommended in this ser%ice to a%oid such high corrosion rates? Could stri$$ed sour water contri!ute to the $ro!lem? Question 11 Has anyone e<$erienced fouling $ro!lems in the reactor feed?effluent $reheat e<changers on an FCC $retreat unit or 0HC unit? .f so what was the cause and how was it rectified? Has anyone tried antifoulant in@ection in this ser%ice? 2Aackground# refiner o$erates with HBGO TA8 Cnd$oint 13+3 F >G 3"925 CCR 3"+ wt, &>T0 Color D5"3 >E( 3"3+ %ol, F which comes directly from u$stream B=:)s and from gas !lanketed storage tanks" Treat gas is mi<ed with the HBGO u$stream of the $reheat e<changers"4 Question 12 (hat is the industry)s e<$erience with corrosion?erosion effects on alloyed reactor effluent e<changers in hydro$rocessing units? (hat new metallurgy 2e"g" du$le< stainless steels4 has !een tested and?or used for reactor effluent coolers 2and associated $i$ing4 to com!at ammonium !isulfide corrosion? :nder what conditions 2e"g" %elocity GH*H> concentration4 ha%e they !een tested or used and what has !een the e<$erience with them?

Question 1' &re refiners ins$ecting the $i$ing into and out of their reactor effluent coolers? .f so what methods are $referred? 3. atalysts and atalyst Sulfiding Question 1* >ilica u$take on hydrotreating catalysts is !ecoming an increasing concern" .s there a way to monitor u$take to effecti%ely $lan changeouts? &re there new reactor design criteria or new catalysts on the market to hel$ im$ro%e run length? Question 1+ Gi%en the reduction in ;?= ratio that occurs during the catalyst regeneration $rocess what is normally acce$ted as the minimum a%erage $article length for e<trudate catalyst loaded into a hydro$rocessing reactor? (hat is the minimum acce$ta!le $article length !elow which $ressure dro$ and flow maldistri!ution $ro!lems are e<$ected to occur? Question 15 (hat hot hydrogen stri$ $rocedures are used to free a hydrotreating catalyst !ed of hydrocar!ons and H2> for the $ur$ose of dum$ing the catalyst? Question 16 (hat le%el of refinery engineering su$er%ision is $racticed in the loading of catalyst in hydrotreating?hydrocracking reactors? Question 17 There a$$ear to !e some new de%elo$ments in catalyst dense loading technology" (hat im$ro%ements ha%e !een achie%ed commercially in terms of catalyst loading rate and %olume of e<tra catalyst installed? (ere there any negati%es e"g" higher >OR $ressure dro$? 8lease gi%e details of catalyst si1e and sha$e !ed si1e and unit ser%ice" Question 19 (hat analytical techni/ues are !eing used on a regular !asis in refineries to /uantify aromatics reduction in diesel and?or BGO hydrotreaters? How accurate and sensiti%e are these methods? Question 23 =iscuss the effects on acti%ity and $ressure dro$ when changing hydrotreating catalysts from 1?7- to 1?15O"=" and 1?15- to 1?23- O"=" &re there any differences in effects for lo!ed %s" cylindrical $articles? Question 21 & num!er of new highFacti%ity hydrocracking $retreat catalysts ha%e !een introduced during the $ast 2 years" (hat is the commercial e<$erience with these catalysts? Question 22 .n choosing a s$iking agent for $resulfiding what criteria should !e e%aluated 2e"g" en%ironmental solu!ility economic to<icity etc"4? Question 2' C< situ $resulfided catalysts ha%e !ecome more widely acce$ted within the industry" One main concern remains namely the $ro$ensity for e<otherms in units with large catalyst %olumes" How are e< situ $resulfided catalysts used safely and economically in large units? Question 2* (hat is the industry)s e<$erience with use of e< situ $resulfided hydrocracking catalysts? Has any increase in cracking acti%ity com$ared to in situ sulfided catalyst !een o!ser%ed? .s a li/uid $hase startFu$ $ossi!le with e< situ $resulfided hydrocracking catalyst? Question 2+ (hat $rocedures are !eing used for unloading s$ent hydrotreating catalyst? .nclude data on !oth wet and dry $rocedures and how they affect catalyst regeneration" !. Reactor Safety and Relia"ility Question 25 (hat means are refiners using to e<tend the life of H=> reactor %essels? Question 26 &re !ed differential and radial tem$erature s$read limits maintained the same from start to end of run or are they %aried as reactor tem$eratures are increased to maintain catalyst acti%ity?

Question 27 .n coF$rocessing coker na$htha with straightFrun diesel what $ercentages of coker na$htha ha%e !een successfully run without using a low tem$erature first stage $retreating reactor? Question 29 (hat guidelines are used for setting !ed tem$erature $rofiles in multiF!ed hydro$rocessing reactors 2e"g" e/ual !ed outlet tem$eratures e/ual (&AT)s ascending or descending !ed outlets4? Question '3 (hat has !een the e<$erience with using li/uid nitrogen for accelerated reactor cool down? How is this normally done and what are the !enefits $otential $ro!lems and risks? How wides$read is this $ractice? Question '1 (hat cleaning methods are used for multiF!ed hydro$rocessing reactors after unloading? .f water is used how is it remo%ed from the reactor !efore loading? (hat s$ecial methods are used to clean inter!ed internals and the mesh su$$ort for the catalyst? #. $eneral Process Question '2 .s anyone feeding HCGO 2FCC cycle oil or hea%y coker gas oil4 to a hydrotreated gas oils hydrocracker?hydrotreater? .f so what are the o$erating conditions 2(&AT H2 $artial $ressure ;H>B4 and yields? &re there any $ro!lems with FCC catalyst or coker fines? How are these hydrotreated gas oils used? Question '' Hield estimates from hydrocracking catalyst %endors show a decreasing trend in formation of cracked gases" =o actual commercial $erformance data %erify this trend? Question '* For hydrotreaters configured with se$arate li/uid and gas $reheat it has !een suggested that a small amount of hydrogen !e in@ected with the li/uid feed to reduce fouling on the e<changer train" =oes anyone do this and if so what is the ratio of hydrogen to feed charge? (hat other issues should !e considered? Question '+ .s !iodesulfuri1ation technology nearing commerciali1ation? (hen do $eo$le think this might actually reach the refiner? Question '5 .n startFu$ of hydrocracking catalyst is anyone $racticing simultaneous $resulfiding and ammonia $assi%ation? &re there any $ro!lems controlling GH2H> formation in the effluent $i$ing? Question '6 (hat routes does the industry utili1e to hydro$rocess =&O or !lends including =&O? 8lease $ro%ide s$ecific details" Question '7 Aeyond the normal $recautions of feed filtering and tank gas !lanketing of feedstock to distillate?hea%y oil hydrotreaters what new methods are !eing em$loyed to minimi1e fouling and e<tend run length? Has com$ositional analysis of feed streams resulted in significant findings relati%e to the mitigation of fouling? Question '9 =rastic reductions in sulfur are re/uired to meet Curo$ean diesel fuel s$ecifications or California clean air regulations" These reductions as well as seasonal changes in diesel $ool !lend com$onents are making it difficult to meet cloud $our lu!ricity and other $roduct s$ecifications" (hat $rocessing chemical treatment and !lending o$tions can !e used to ma<imi1e diesel $ool economics in this en%ironment? Question *3 (hat e<$erience ha%e refiners had in $rocessing atmos$heric reduced crude with BGO in low $ressure hydrotreaters to $roduce FCC feed? (hat $ercentage of reduced crude has !een $rocessed? (hat le%els of desulfuri1ation and CCR reduction are reali1ed? Question *1 .s anyone successfully hydrotreating full range FCC gasoline to reduce sulfur? (hat are the $roduct sulfur le%els and corres$onding 0OG and ROG octane losses" (hat were the initial sulfur 0OG and ROG le%els?

Session III - Hydrogen Processing

A. Hydrogen Production 1. Hydrogen Manufacturing %uestion 1 Ho& is '2 corrosion mitigated in (ydrogen units) A&R;OC(CG# To$soe uses stainless steel for those $arts of the hydrogen $lant that are e<$osed to CO2 containing condensate" The use of stainless steel then necessitates $rotection of your system against chlorides in !oth the feed and !oiler feedwater systems" The way we do that on the feed system is through the use of a chloride guard !etween the CoF0o desufuri1ation system and the 1inc o<ide system" (e use deminerali1ed !oiler feedwater as makeu$ with a s$ecification of less than 3"2 microhms conducti%ity" A.GFOR=# (e found that CO2 corrosion can !e controlled with a com!ination of the $ro$er amine sol%ent corrosion and inhi!ition $ractices and o$erating targets" The $ro$er amine sol%ent should not degrade significantly in CO2 ser%ice and yet $ro%ide good CO2 ca$acity" This many times eliminates 0C& =C& and 0=C&I although 0=C& can $ro%ide good ca$acity and minimal degradation $ro!lems if it is !lended or formulated with other com$ounds" 0any formulated $roducts are a%aila!le !ut most of these still suffer from some CO2 degradation and as a result are many times no !etter in the long run" One of the formulated sol%ents which we ha%e seen used successfully has !een Huntsman Jeff treat 0+13" Corrosion can still !e a $ro!lem e%en when using the $ro$er sol%ent !ecause of the aggressi%e nature of CO2" The use of corrosion inhi!itors in mi<ed CO2 and H2> en%ironments has !een $racticed with success o%er the last '3 years" One of the considerations that must !e weighed in selecting a good corrosion inhi!itor is the foaming nature of the $roduct" The addition of a defoamer to the corrosion inhi!itor is really not an acce$ta!le solution" &fter nonF foaming film $ersistency solids dis$ersion and $hysical $ro$erties are im$ortant" . agree with 0r" Aarloewen on the stainless steel" >tainless steel can also howe%er !e $rone to corrosion if the en%ironment is o<ygen free" >tainless steel does usually $erform well if o<ygen sca%engers are not used and the organic acids are controlled to a low concentration" &s a rule of thum! formic acid a!o%e * 333 ;C can aggressi%ely attack !oth car!on and stainless steel" .n high CO2 systems car!onic acid is usually the $re%alent acid !ut formic and other organic acids are more aggressi%e in the system" These acids are es$ecially aggressi%e in %ery low H2> en%ironments !ecause the iron does not form a $rotecti%e iron sulfide scale" &mine degradation $roducts ha%e !een found to act as chelants that can remo%e the $rotecti%e scales when they are formed" (e are currently trialing a new series of $roducts in gas $lants on the Te<as Gulf Coast to effecti%ely $rotect against corrosion in these high CO2 low H2> en%ironments" Finally to achie%e the !enefits of a good amine sol%ent and corrosion inhi!ition $rogram the unit must !e $ro$erly o$erated" C<cessi%e rich amine loadings and e<cessi%e tem$eratures are !oth an o$en in%itation to trou!le" >team usage and amine circulation must !e !alanced" The !est o$erating conditions for a gi%en unit may !e /uite different from another due to the design and re/uired through$ut" (e usually use ARECs TF>(CCT model to try to identify the !est o$erating conditions for the unit !efore starting any corrosion control $rogram or recommending a sol%ent change" C&.G# &ll of our =elaware City $lant units su!@ected to CO2 corrosion are either '3* or stainless steel or clad with it" RO0&G# The concentration of car!on dio<ide e<iting the low tem$erature shift reactor can a$$roach 23 mole $ercent" The resulting condensate in the high and low tem$erature knockout $ots has a %ery high le%el of car!onic acid and is e<tremely corrosi%e to car!on steel" The chromium content of these steels needs to !e at least 12 $ercent" Ty$e '3* is usually s$ecified" &lthough ty$e *13 or ty$e *'3 or any steel with 12 $ercent chrome is also satisfactory" >HOO:F. (&GG 2&ir 8roducts4# The $anel has suggested that stainless steel is common use to mediate the CO2 corrosion" Aut one thing . would like to share with the audience is that this could !e a $rocess ha1ard" (e ha%e e<$erience that the caustic in this case is a $otasium hydro<ide leeching out from the reforming catalyst and that caustic cracking of stainless steel material has the cause of a ru$ture of 2* inch stainless steel line" &fter a serious in%estigation and e<amination we found out that at certain tem$erature locations and circumstances this catastro$hic failure could ha$$en" TO0 A&COG 2=ow Chemical Com$any4# Corrosion results from a com!ination of $otentially corrosi%e effects" .n hydrogen $lants these include wet CO2 %a$or degradation $roducts of the %arious amines used erosion caused !y $articulates in the amine solution

flashing CO2 and high %elocity and locali1ed lack of metal $assi%ation" =ow)s e<$erience with G&>?>8CCK C=F 8lus has resulted in the following" Reduction of corrosion !egins with design criteria that minimi1e these effects" &mine %elocities should !e limited to ' f$s in car!on steel and 6 f$s in stainless steel $i$ing" Rich loading should !e limited to 3"*+ moles CO2 $er mole amine to minimi1e CO2 flashing" The a$$roach tem$erature of the lean F rich cross e<changer should !e limited to *+LF to minimi1e CO2 flashing" 8i$ing metallurgy should !e '3*>> for the rich amine circuit !etween a!sor!er and stri$$er" C<changer tu!ing for all four e<changers should !e '3*>>" O$erating guidelines include assuring ade/uate amine concentration and circulation to maintain the limit to the rich loading and ade/uate stri$$ing to achie%e the s$ecified lean loading" %uestion 2 *o ma+e R,$ and lo& sulfur diesel- refiners need more (ydrogen- yet traditional sources li+e catalytic reformer (ydrogen are "eing reduced. Ho& are refiners meeting t(is c(allenge. /urc(ased (ydrogen- ne& or re0am/ed (ydrogen /lants- reco0ery systems- etc.) Are any ne& feed sources or tec(nologies "eing used to /roduce (ydrogen) >&0:C;># .n the area of new hydrogen $roduction technologies 0arathon researchers ha%e de%elo$ed the HH>:;F $rocess for the manufacture of hydrogen from hydrogen sulfide" The $rocess uses redo< chemistry under mild o$erating conditions to con%ert H2> into hydrogen and sulfur" The $rocess em$loys two !asic ste$s the hydrogen sulfur $roduction and reco%ery ste$ and the hydrogen $urification ste$" & ma@or engineering firm has estimated that the ca$ital costs of the HH>:;F $rocess is '3 to +3 $ercent less than a claus tailFgas $lant com!ination due to fewer ma@or $ieces of e/ui$ment that are re/uired" The $rocess $roduces a!out 22 333 cu!ic feet of hydrogen $er ton of sulfur $roduced" .n addition to e%aluating internal a$$lications for this $rocess 0arathon is currently seeking e<ternal su$$ort for the construction of a demonstration unit in 1999" =etails of the $rocess can !e found in an G8R& $a$er that was $resented !y =r" 0ark 8lummer entitled -The HH>:;F 8rocess# & Balua!le Hydrogen Resource from Hydrogen >ulfide - and was $resented in the >$ring 199+ G8R& &nnual 0eeting" .n the area of se$aration technologies &ir 8roducts has a new gas se$aration mem!rane known as selecti%e surface flow or >>FT0 mem!ranes" & 3"+ to 1"+ million standard cu!ic foot $er day demonstration unit is in ser%ice and o$erates with full scale mem!rane se$arators" The distinguishing features of the >>FT0 technology is that this mem!rane %ersus a $olymer ty$e mem!rane kee$s the lighter com$onent on the high $ressure side in this case hydrogen and also the $ressure dro$ re/uired through the mem!rane is much lower" & recent article in the June issue of Today's Refining discusses the merits of the >>FT0 technology" . would also like to refer you for the more traditional hydrogen $urification technologies to a white $a$er of :O8 that discusses the selection criteria for $ressure swing a!sor$tion selecti%e $ermeation and cryogenic se$aration $rocesses" The $a$er is entitled -:O8 $rocess solutions for reformulated gasoline"- . s$oke with the gas se$aration folks at :O8" &lthough the $a$er has not !een u$dated since 1991 they feel that the !asic $rinci$les still hold for selection criteria" Hou may contact John Geeseman at :O8 at 27*64 '91F29'6 if you would like a co$y of this $a$er" T&>MCR# (ell in addition to addressing the first $art of the /uestion we can alle%iate the reformer hydrogen $roduction !y changing the reforming catalyst" &s a small $lug here for &creon Catalysts they ha%e de%elo$ed a reforming catalyst RG+72 that $roduces a high le%el of hydrogen yield with a wide range of octane %alues" This catalyst is currently !eing used in a!out 16 different units around the world and more details can !e o!tained directly from &creon" &s to the second $art of the /uestion there are a num!er of $ossi!le sources of $urchased hydrogen merchant hydrogen and this may de$end %ery much on the location and industrial area where the $lant is located" These sources include $urchased hydrogen from chlorine manufacturing and other $rocesses" >o they may well !e limited geogra$hically" There are also a num!er of com$anies licensing skid mounted hydrogen generation units and other com$anies that would setu$ with $roducing $lants in association with the hydrogen $roducers" HCGMC# .n our refineries we are ma<imi1ing hydrogen $roduction !y focusing on getting the most out of our e<isting assets" (e ha%e made significant $rogress in four areas# 14 we are de!ottlenecking our steam methane reformers through

enhancements to the 8>& systems Aenfield o$eration and heat remo%al systemsI 24 we are reco%ering as much hydrogen as we can from the fuel gas systemI '4 we are reducing re/uirement to $urge hydrogen from hydro$rocessing units !y focusing on makeFu$ hydrogen $urity controlI and *4 we are im$ro%ing the relia!ility and mechanical a%aila!ility of our hydrogen $roducing units" (e ha%e found that this last area is a significant source of additional hydrogen" JO>CCM# &t one refinery we recently com$leted a study to su$$lement the hydrogen source" One new technology we considered in mem!rane $urification from &ir 8roducts was >>FN" The >>FN technology was considered due to the lower hydrogen com$ression re/uirements and traditional mem!rane technology" The new technology is ca$a!le of $roducing hydrogen at a higher $ressure than the %ent gas or hea%y hydrocar!ons" >>FN mem!ranes are gas se$arating mem!ranes that com$rise a micro$orous adsor$ti%e material su$$orted on macro$orous su!strate" The >>FN mechanism $referentially $ermeates larger or more $olar gas com$onents to the low $ressure side of the mem!rane" The unit design considered increased hydrogen im$urity of a low $ressure se$arator or off gas stream from 57 $ercent to 93 $ercent hydrogen" 8roduct hydrogen reco%ery was estimated at 73 $ercent with an inlet feed $ressure of 22+ $sig and a $roduct hydrogen $ressure of 233 $sig" The %ent $ermeated was at + to 13 $sig" 0&;CM# (e ha%e found that the hydrogen reco%ery techni/ues and conser%ation in the refinery can only go so far in meeting the RFG re/uirements" :sually the ne<t ste$ that a refiner has to take in meeting these re/uirements is a large increment of hydrogen" One a$$roach that refiners are increasingly following is a usage of merchant hydrogen" Good e<am$les of such systems are those o$erated !y &ir 8roducts in the Gew Orleans and Houston area and the new system that is !eing installed !y &ir ;i/uide in the Cor$us Christi area" These systems take ad%antage of the fact that there are /uite a few sources of e<cess hydrogen !eing $roduced in %arious industries that we are not $erha$s familiar with i"e" ethylene $lants chlorine cells and a num!er of others" These merchant su$$liers will as a !usiness o$$ortunity to go out and seek these sources $ut in the collection systems the $i$elines the com$ression and the $urification systems" They will usually su$$lement these systems with their own steam reforming $rocesses to !alance out the hydrogen re/uirements" The sources from new ethylene $lants are /uite significant" (e are all aware of how much the acti%ity there is in ethylene $lant construction" For e<am$le a one !illion $ound $er year ethylene $lant can generate easily a sur$lus of *3 to 53 million cu!ic feet a day of hydrogen" .t might not !e $ractical for a refiner on an indi%idual !asis to go out and seek this su$$ly" Aut these merchant su$$liers are aggressi%ely trying to de%elo$ these $i$eline networks to accumulate these e<cess sources of hydrogen and to su$$ly a reasona!le and relia!le source of hydrogen" (e !elie%e that this ty$e of a$$roach will continue to accelerate in the industry" RO0&G# &shland has de%elo$ed a gasification $rocess called Hymeltt and is working with a Cn%iRes ;;C to commerciali1e this $rocess" Feed is introduced !elow the surface of a molten metal !ath ranging in tem$erature from 2 +33 to ' 333LF" &ll organic material in the feed is ra$idly dissociated into its elements" Hydrogen and nitrogen $rimarily e%ol%e as gases" The car!on and sulfur dissol%e in the metal" O<ygen in the feed e%ol%es as car!on mono<ide" The car!on content in the !ath increases with time and the o%erall reaction is endothermic" (hen the car!on content reaches a $reset le%el the feed is interru$ted and o<ygen is then in@ected into the !ath" The o<ygen reacts almost e<clusi%ely to $roduce car!on mono<ide in an e<othermic reaction with methane or steam sometimes added to $ro%ide an o%erall heat !alance for the system" The gas e%ol%ed in the first %essel contains more than 93 $ercent hydrogen and the gas e%ol%ed in the second %essel in e<cess of 93 $ercent car!on mono<ide which can !e shifted to hydrogen con%erted to $roducts such as methanol or !urned in a heater" (e !elie%e the $rocess can also !e o$erated at a $ressure in e<cess of *33 $ounds and the $rocess tolerates a wide range of feeds from methane to >=& $itch" &shland !uilt and o$erated a $ilot $lant from 1992 until 1995 with a nominal molten metal ca$acity of '33 $ounds" (hen the >=& $itch was fed the gas from the first 1one contained 92 $ercent hydrogen" (e $lan a larger scale testing in a $ressure ca$a!le %essel containing si< tons of molten metal" The larger scale testing should $ro%ide all of the critical design information for a commercial $lant with a molten metal ca$acity of 133 to 233 tons and ca$a!le of $roducing !etween 13 and '+ million standard cu!ic feet a day of hydrogen" This $lant is e<$ected to ha%e a high turn down ratio of * to 1 or !etter and !e ca$a!le of ra$id res$onses to change in feed rate making it ideal for $rocess or load following" (hen the heating %alue of CO $roduced !y the $rocess is %alued at 73 $ercent natural gas the cost of hydrogen is a$$ro<imately +3 $ercent of that $roduced !y con%entional steam methane reforming at the same $urity le%els" A&R;OC(CG# . am going to focus on another ty$e of technology for medium si1e hydrogen $lants" To$soe de%elo$ed a Haldor

To$soe con%ection reformer which is a new conce$t that com!ines in a relati%ely small $iece of e/ui$ment the radiant and waste sections of the con%entional reformer" .t is selfFsufficient for fuel and steam and does not e<$ort any steam" .t lends itself to modulari1ation and it is suita!le for $lants in of ca$acity u$ to 23 million standard feet a day" (e ha%e su$$lied a num!er of these $lants to fuel cell $ro@ects in %ery small ca$acities and ha%e a 13 0H >CF?= TCR $lant starting u$ in Curo$e right now" C&.G# &t our =elaware City $lant we $lan to con%ert an e<isting methanol $lant to concurrently $roduce hydrogen and methanol" This methanol $lant contains a feed $reFtreatment section and a con%entional steam methane reforming section for the con%ersion of feed streams to a hydrogen rich syngas stream" & $ortion of syngas will !e sent to a 8>& unit to $roduce high $urity hydrogen and the !alance of it will !e used to $roduce methanol $roduct" F;CTCHCR# (hile not directly related to hydrogen $roduction there is an FCC catalytic route that e<ists for refiners who are $ushing sulfur limitations in the gasoline $ool and are using a high 1eolite to matri< catalyst" &s a rule of thum! for a nonhydrogenated feed a!out ten $ercent of the feed sulfur will end u$ in the gasoline" This dro$s to a!out fi%e $ercent for a hydrotreated feed" (hen com$ared to an FCC catalyst that has a low concentration of matri< a catalyst with high concentration of an acti%e selecti%e matri< can show a reduction in sulfur of u$ to 23 to 2+ $ercent" &nd this can !e further enhanced !y using a high rare earth le%el" &dditional sulfur reduction has not !een demonstrated commercially in FCC:s that were already using a high matri< !earing catalyst $rior to the trial of the sulfur reducing catalyst" The $rimary sulfur reduction !enefit will occur when you are going from a %ery high 1eolite to matri< ratio catalyst to one that is low 1eolite to matri< ratio" F:>>C;;# Aack in 199* we tied into the air $roducts hydrogen $i$eline and it is truly a wonderful thing" FO>TCR# (hen we re%am$ed our refinery to 16L hea%y crude o$eration we made the commitment to make RFG and low sulfur diesel" &s $art of the re%am$ we startedFu$ a new coker a new CFHT 2Cat Feed Hydrotreater4 and re%am$ed our =iesel Hydrotreater to low sulfur o$eration" These changes re/uired an increase in chemical hydrogen consum$tion of 133 00>CF=" This was a large increase and much greater than we were currently $roducing inFhouse" >o to accommodate this increase we looked first to ;yondell an owner com$any which $roduces hydrogen as a !yF$roduct from their methanol and olefins $lants" (e negotiated a new contract for their methanol hydrogen and e<$anded the $urchase %olumes for the e<isting olefins hydrogen contract" This took care of much of our re/uirements" For the !alance of our demand we set u$ a longFterm contract with a $ro%en commercial hydrogen $roducer and !roker" They e<$anded their facilities e<$ressly for our re%am$" This was a good economic decision for us since they are more skilled at the economic $roduction maintenance and technology of an onF$ur$ose hydrogen $lant than we are and can !etter take ad%antage of the economies of scale" (e do em$loy a mem!rane se$aration system on the new CFHT which reco%er 13 00>C= of $ure hydrogen" 0&RM (C.>C 2AOC Gases4# For those refiners who are not fortunate enough to !e located along an e<isting $i$eline a stand alone hydrogen $lant from a gas com$any can also $ro%ide you hydrogen at a lower cost" AOC Gases and Foster (heeler ha%e teamed u$ to $ro%ide hydrogen to refiners u$ to +3 million feet a day and greater" This com!ination of gas com$any and $lant su$$lier can ty$ically achie%e sa%ings on !oth ca$ital and o$erating cost which are $assed on to the refiner" &dditionally the refiner)s risk is reduced since once a su$$ler agreement is reached costs are fi<ed and known" Finally the AOC?Foster (heeler $artnershi$ is uni/ue in that !oth com$anies retain ownershi$ of the facilities thus ensuring low life time hydrogen cost and high relia!ility" 8OORG.0& >H&R0& 2MT. Cor$oration4# The decision to !uild new $lants or re%am$ and make %ersus !uy is site s$ecific" .n make %ersus !uy decisions multi$le factors need to !e considered like transferring of risks associated with schedule cost maintenance ca$ital and on stream a%aila!ility to an industrial gas su$$lier" The choice !etween a new or a de!ottlenecked $lant is a function of the /uantity of hydrogen re/uired" & ma@or increase in hydrogen demand can often only !e met with a new $lant" &13F23, increase in ca$acity can !e accom$lished !y reco%ering hydrogen from refinery offFgas streams or !y re%am$ing a steamFhydrocar!on reforming ty$e hydrogen $lant" .f the refinery chooses to re%am$ a hydrogen $lant a %ariety of o$tions can !e considered a$$lied indi%idually or in com!ination to increase the ca$acity of the $lant" These o$tions are# F &dd a 8reFReformer in series with the reformer" C<$ected increase in ca$acity is 13F12 ," F &dd a ;ow Tem$erature >hift reactor in a 8>& !ased hydrogen $lant" C<$ected increase in ca$acity is *F+,"

F .ncrease reformer inlet tem$erature !y adding a reformer feed $reheater in the con%ection section" C<$ected increase in ca$acity is 'F* ," F .ncrease ca$acity !y increasing the inside diameter of the radiant tu!es !y u$grading metallurgy" (hile e<$ected increase in ca$acity %aries from reformer to reformer u$ to 23, increase has !een $ossi!le in a case study" F &dd a $ost reformer or a secondary reformer into the flow scheme" This has the $otential to increase ca$acity !y more than 23, $ro%ided the downstream heat reco%ery train and shift reactors are a!le to handle the increased gas flow rate" The technology for new hydrogen $lants is continuously !eing u$graded as new de%elo$ments in metallurgy and catalysts take $lace" The de%elo$ment of high acti%ity $reFreforming catalyst has ena!led the $reFreforming technology to !e well esta!lished !oth for new and re%am$ed $lant designs" 8ost reforming in con%ecti%e heat e<changer ty$e reformers currently in use in ammonia $lants can !e a$$lied to hydrogen $lants" MT. has done many de!ottlenecking studies" (e will study all the o$tions and $ro$ose the most cost effecti%e scheme for de!ottlenecking your hydrogen $lant" %uestion 3 1(at is t(e /anel2s ad0ice on (o& to a0oid o0er(eating of steam reforming furnaces) 8CTCR>OG# (e did ha%e one tu!e fail in our hydrogen heater and one of the contri!uting factors was $oor flame $atterns from dirt in the fuel gas to the !urners" (e ha%e gone to cleaner gas to hel$ $re%ent that" (e also ha%e the o$erators $erforming sur%eillance !oth o$tically and with an infrared de%ice to hel$ find the hot s$ots in the heaters and ad@ust the !urners accordingly" The tuning of the 8>& and other instruments as well as $re%enting u$sets all hel$ to $re%ent the $ro!lems in heaters" (e ha%e also recently gone to a $redicti%e maintenance system where we had a de%ice called HF>can" .t was $ro%ided !y a com$any called .C>CO" .t is a $ro$rietary ultrasonic method that crawls u$ the tu!es and gets a %ery com$lete ins$ection of the metal condition" This way we can !e $re$ared for the ne<t antici$ated down time with the a$$ro$riate num!er of tu!es on hand and ha%e a turn around well $lanned" RO0&G# 0ost of our recent $ro!lems ha%e in%ol%ed $oor firing $atterns in the fire !o<" &t high turn down ratios we ha%e e<$erienced e<cessi%e air leakage into the fire !o< where the tu!es enter through the floor" .n an effort to reduce e<cess air to the stack the o$erators would cut the air to the !urners and the o<ygen star%ed flame would !e $ulled o%er against the tu!es where additional air was entering into the fire!o<" The resulting flame im$ingement caused cree$ damage and e%entual failure" The tu!e entry holes ha%e su!se/uently !een sealed with ceramic fi!er to a%oid this leakage and $re%ent a recurrence of this $ro!lem" A&R;OC(CG# . am going to focus on the $otential of tu!e failure during start u$" >tartu$ is !asically an unusual o$eration where you ha%e %ery low mass flow through the tu!es and no heat of reaction" >o right away the normal relationshi$s !etween $rocess tem$eratures and furnace tem$eratures do not a$$ly" .n addition there are some %endors that recommend relati%ely high furnace outlet tem$eratures !efore you cut in the hydrocar!on feed in e<cess of 1 '33 to 1 *33LF" &t To$soe we like to see the furnace outlet tem$erature !elow 1 233LF" The final thing to em$hasi1e on startu$ and it really a$$lies to reforming furnace firing in general is that in todayOs refinery with a concentration of instrumentation in the control room it is sort of like the home office" The home office feels like they know e%erything that is going on" .n the control room they feel like they know e%erything that is going on" & reforming furnace is a classic $iece of e/ui$ment that you ha%e to monitor in the field and there is no su!stitute for it not only during startu$ !ut also as the run $rogresses" C&.G# Two causes that we ha%e seen where une<$ected loss of feed to the reforming furnace and also changes in the fuel gas !tus" (e ha%e im$lemented ad%ance controls that detect changes in the fuel gas gra%ity and make ad@ustments for that" (e also installed an >OB 2solenoid o$erated %al%e4 to close the main fuel gas %al%e on heater loss of steam flow loss of the draft fans and low le%el in the !oiler" (e also monitor the loading $rocedure of catalysts to make sure that there is a good e%en =elta 8 across all the tu!es to $re%ent hot s$ots" >HOO:F. (&GG 2&ir 8roducts4# . think the $anel and MT. ha%e suggested a num!er of %ery good recommendations" One area s$ecifically that . want to add to $re%ent a reformer furnace from a catastro$hic failure such as a melt down of reform tu!es" The $ractice we ha%e is to use two out of three %oting systems to shut down the high tem$erature reforming $rocess efferent and also as a !ack u$ to use two out of three %oting system to shut down on high tem$erature" This is at the flue gas tem$erature at the outlet of reform radiant section"

&G=CR> G.C;>CG 2Haldor To$sPe &?>4# . would like to $oint out that some %ery hot tu!es and some tu!e failures are associated with sul$hur $oisoning of the catalyst" This $articularly occurs in the to$ $art of the tu!es where the feed enters and where the tem$erature and 8H2 are low" The sul$hur $oisoned catalyst loses acti%ity for steam reforming and the feed $roceeds uncon%erted to the hotter $art of the tu!es leading to coking of the catalyst" This is worst in the hottest area !y the tu!e wall" The tu!es are o%erheated since little heat is a!sor!ed and de$osited coke can lead to channeling" The o%erheating of the tu!es F often worse in local areas F leads to misha$s" The situation !ecomes more critical the higher the content of higher hydrocar!ons in the feed" J.0 &AAOTT 2.C. Matalco4# First off . would @ust like to agree that it is %ery im$ortant to monitor the reformer tu!es out in the field during startu$" Bisual monitoring is e<tremely im$ortant" The second thing . would like to draw o$eratorsO attention to is an emerging $henomenon which we ha%e o!ser%ed on to$ fired reformers" This is around the use of new sha$ed reforming catalysts which ha%e indeed enhanced heat transfer and reduced tu!eFwall tem$eratures" Often the $osition of the and $eak metal tem$erature has mo%ed from a $oint on the to$ half of the tu!es down towards the %ery !ottom" The $oint . would like to make is that it is necessary to watch out when the reformer is loaded u$ again within increased firing as indeed is $ossi!le with the sha$ed reforming catalyst" (hen monitoring your tu!eFwall tem$eratures !e sure to check where the $eak tem$erature actually is" 0easuring the tu!eFwall tem$erature in the same $osition as !efore could well gi%e too low an answer" Hou need to check all the way down and check where the highest tem$erature is to a%oid any $otential for $remature tu!e failures" CR.C FC&ROG 2MT. Cor$oration4# =uring normal o$eration of the reformer we ha%e to take the $rocess outlet thermocou$le into consideration" This thermocou$le is su!@ected to high se%erity ser%ice due to the high $rocess effluent tem$eratures and as such is lia!le to drift" This means that $rocess outlet tem$eratures can actually read low when in fact the tem$erature in the reformer is much higher" MT. has e<$erienced drift at the $rocess outlet tem$erature of as much as 233LF" .n order to a%oid o%erheating of the reformer the following ste$s are recommended# 1" Tu!e wall tem$eratures should !e measured at least once $er shift using an o$tical $yrometer that automatically com$ensates for white wall reflection" O$tical $yrometers that do not ha%e this ca$a!ility will always indicate a higher tu!e wall tem$erature" :nder normal o$erating conditions tu!e wall tem$eratures should indicate 73LF to 133LF higher than the $rocess outlet tem$erature" 2" =e%elo$ a cur%e !ased on CH* sli$ in the $rocess effluent %ersus theoretical tem$erature of the $rocess effluent" Check the methane sli$ and theoretical tem$erature %ersus the indicated tem$erature and the tu!e wall tem$erature" '" 8eriodically 2once a month4 a calculation to determine the a$$roach to e/uili!rium should !e made" This will re/uire a full analysis of the reformer effluent gas" *" &lthough items 1 and 2 also a$$ly to startFu$ of the reformer care should !e taken to ensure that there is an ade/uate flow of circulating nitrogen through the reformer tu!es to $re%ent o%erheating" MT. uses a flow of 17+3 scfh?$er reformer tu!e as a minimum and 2+33 scfh?$er reformer tu!e as a ma<imum" .t is also recommended that a constant %isual ins$ection of reformer tu!es !e carried out during startFu$" (hen reformers suffer damage during heatFu$ in%estigations normally re%eal that constant sur%eillance of the reformer tu!es would ha%e alerted the o$erator in time to $re%ent ma@or damage to the reformer tu!es" AR:CC >COTT 2Aruce >cott .nc"4# One of the $ro!lems with shooting the tu!es with a $yrometer is guessing what the emissi%ity and the reflecti%ity of the tu!e is" . would kind of like to $oll the $anel and see if there is any e<$erience with C2TOs little !lack hole de%ice which is su$$osed to eliminate those concerns" H.GG.G># Go res$onse" %uestion ! 'ur met(anator tri/s on (ig( tem/erature monitored at a t(ermocou/le 2#3 do&n in t(e "ed. *(is ensures t(at t(e tri/ occurs "efore t(e "ul+ of t(e catalyst and reactor are o0er(eated. As t(e catalyst ages and deacti0ates- is t(e 42#3 /oint4 still sensiti0e to a surge of '2) Is t(ere a safer strategy to follo& for t(e /rotection of met(anators as catalyst ages) A&R;OC(CG# Ty$ically in most methanators there is a deacti%ation $attern that occurs that gradually mo%es down the !ed" . think

the o!%ious way if you ha%e sufficient instrumentation and thermocou$les is to $ick a lower s$ot in the !ed and use it as a tri$ $oint or to use rate of change as a triggering $oint for shutdown" C&.G# (e do not ha%e an automatic tri$" (e ha%e a hand switch that we tri$ when the T. software alarms set at a reasona!le tem$erature to alert the !oard o$erator of a runaway condutron" (e ha%e a $rocedure in $lace where if the tem$erature e<ceeds 7+3 F to acti%ate the hand switch to remo%e the $rocess gas from the methanator" JO>CCM# (e ha%e two !ed thermocou$les which ha%e high tem$erature and high rate of rise alarms" The methanator has a manual shutdown" .t also has an automatic shutdown on either !ed high tem$erature" The first thermocou$le is at the '3 $ercent $oint" The second is at the 63 $ercent $oint" >hutdowns and alarms are recommended for all thermocou$les due to the $otential for CO2 solution carryo%er" Aased on discussions with the :nited Catalyst .nc" during CO2 solution carryo%er the to$ 2+ $ercent to +3 $ercent of the !ed can !e cooled !y li/uid CO2 solution" &s the li/uid goes through the !ed it is %a$ori1ed deli!erating CO2" &s the CO2 is methanated high reactor tem$eratures can occur only in the !ottom half of the !ed" %uestion # 1(at met(ods are a0aila"le today for monitoring t(e sulfur content of t(e feed to a steam reformer) Recommendations as to t(e re5uired 0olume of oMo catalyst for t(e desulfuri6er in a (ydrogen /lant de0iate su"stantially 71883 difference is not uncommon9. *(is is not t(e case for t(e ot(er catalysts in t(e (ydrogen /lant. 1(y is t(is so) A&R;OC(CG# .n order to !e of real %alue an instrument in this ser%ices has to !e a!le to detect sulfur concentrations down to 13 $arts $er !illion" & modern desulfuri1ation system followed !y a hot 1inc o<ide system will reduce your sulfur le%el to well !elow those le%els" This is the $rotection system most $eo$le use unless they ha%e a known $ro!lem" There are some instruments a%aila!le and !eing used that can measure in the 13 $art $er !illion range le%el" The second $art of the /uestion discusses the /uestion of si1ing of the co!alt moly catalyst or desulfuri1ation system and why there is such a %ariation !etween licensors" . !elie%e the answer is that it reflects the fact these units are not si1ed for normal o$eration" The normal o$erations contaminant le%els for most units are e<tremely low" They are really si1ed for an u$set" >o the si1e of the reactor is set !y the conser%atism of the licensor" Hou should also recogni1e that these co!alt moly catalysts are only $artially sulfided due to the %ery low sulfur content in the feed and no formal sulfiding $rocedure normally !eing used" >o again that $ro%ides an area where there may !e differing o$inions !etween licensors as to @ust how acti%e that catalyst is" C&.G# To answer the first $art of the /uestion we do not ha%e a GC" (e use la! analysis and the o$erators take H2> draegers once a shift" 8CTCR>OG# Our hydrogen unit was designed for a wide range of feeds from natural gas ;8G)s and u$ toward light straight run" The reactor is designed fairly large to accommodate the %arious amounts of sulfur we could see in the feed" &s far as how we ha%e run so far we ha%e run @ust natural gas for four years" (e ha%e really an under utili1ed !ed in this case" The sulfur content of the reactor effluent is monitored with a lead acetate !u!!ler to make sure that we are not sending any sulfur farther downstream" &G=CR> G.C;>CG 2Haldor To$sPe &?>4# . should like to $oint out a risk which you may iccur if you run for a long time without sul$hur in the feed to a co!alt moly catalyst" The catalyst will lose all of its sul$hur as H2> to the gas %ery slowly" .f you then change to a feed which contains hea%y hydrocar!ons like !utane or na$htha you can ha%e a se%ere hydrocracking o%er the co!alt moly!denum catalyst" %uestion : 1(at is t(e /anel2s recommendation concerning t(e use of a se/arate c(lorine guard as /rotection for lo& tem/erature s(ift catalyst) HCGMC# (e do not recommend a se$arate guard !ed immediately u$stream of the low tem$erature shift catalyst" .f chlorides are sus$ected in the feedstock or im$ort recycle hydrogen it is ad%isa!le to remo%e them in the front !y $ro%iding chloride a!sor!ent catalyst !eds u$stream of the Qinc O<ide Reactor" This is done !ecause the chloride s$ecies ha%e to !e hydrogenated !efore they can !e a!sor!ed !y the catalyst" &lso most catalyst manufacturers recommend

installing this catalyst in a dry stream since chlorides are easily washed from the catalyst !y water and can !e trans$orted downstream" Chlorides can also !e introduced into the system through $rocess steam or the use of chlorinated sol%ents during maintenance" >team can !e easily eliminated as a source of $oison !y ensuring that the !oiler design $re%ents carryo%er of !oiler solids into the $rocess steam system" Ha%ing said all this . would like to $oint out that ammonia $lant o$erators ha%e installed guard !eds u$stream of the ;ow Tem$erature >hift Reactor consisting of the ;ow Tem$erature >hift catalyst itself" They do this !ecause it is e<tremely difficult and e<$ensi%e to remo%e chlorides from their $rocess air" JO>CCM# The concern is chlorides in the feed or chlorides from a leak in a waste heat !oiler or $rocess steam generator" (e currently use chloride guard catalysts in three units" The guard catalysts are loaded as a layer of catalyst on to$ of the main low tem$erature shift catalyst !eds" &t one refinery using Ga$htha reformer hydrogen as a feed we ha%e a chloride guard !ed on the inlet to the desulfuri1er reactors and the low tem$erature shift reactor" (e ha%e had one incident where we had a leak in a waste heat !oiler and the chloride !ed aided in the $rotection of the low tem$erature shift catalyst" The low tem$erature shift catalyst was $rotected" The amount of guard catalyst is de$endent u$on the se%erity of the chloride contamination" .f chloride contamination is sus$ected due to short low tem$erature shift catalyst life a$$ro<imately fi%e $ercent of the catalyst should !e loaded as guard catalyst" >am$les of the s$ent low tem$erature shift catalyst can hel$ determine the amount of guard catalyst re/uired" A&R;OC(CG# . mentioned earlier that To$soe would $ro%ide a chloride guard !etween the co!alt moly and the 1inc o<ide system" Howe%er for the first charge of the low tem$erature shift we would also $ro%ide a chloride guard on to$ of the low shift and then let the data from that first cycle determine whether it is necessary !y measuring what chloride $icku$ occurred during that cycle the o!%ious source !eing the steam system" R" R&J&0&G. 20angalore Refinery E 8etrochemicals ;td"4# (e ha%e chloride guard catalysts on to$ of co!alt moly!denum catalyst" Recently we found that chloride is esca$ing from co!alt moly!denum catalyst u$ to "+ $$m" . would like to know the $anelOs %iew on what should !e a ma<imum chloride content which can !e tolerated !y the reformer of catalyst" H.GG.G># Go res$onse" RO>> AR:G>OG 2:nited Catalysts4# One thing that you ha%e to kee$ in mind is that we ha%e seen cases where you ha%e chloride intrusion from the feed gas" .t shows u$ as a tem$orary $oison to !oth the reformer and high shift and a $ermanent $oison to the low shift" C%en after the low shift is changed and the chloride intrusion has !een fi<ed we ha%e seen ra$id deacti%ation from the chloride $oisoning continue on low tem$erature shift" (hat ha$$ens is that the chlorides come off the u$stream catalyst" :nless you change those the accelerated deacti%ation of the low tem$erature shift will continue" .t continues to come off e%en after the $erformance of the reformer and high tem$erature shift returns to normal" >o those should !e considered for changing including the 1inc o<ide and co!alt moly!denum " MCG CH;&8.M 2.C. Matalco4# (e !elie%e the most effecti%e low tem$erature shift catalyst solution is a self guarding low tem$erature shift catalyst" (hat this allows the hydrogen o$erator to do is to ma<imi1e the effecti%eness of the entire !ed for the CO shift acti%ity" =e$ending on the $oison that you are looking at the kind of catalysts that we offer can $ro%ide u$ to + to 23 times the amount of $oison retention that is needed to fully deacti%ate the catalyst" >o e%en though the catalyst is fully deacti%ated it is still recei%ing $oisons and a!sor!ing $oisons !eyond that $oint" C;M.G C&R0OG& C:&=RO> 2Cco$etrol4# &ccording to this we ha%e a lot of corrosion erosion $ro!lems in our to$$ing units @ust in transfer line to atomos$heric tower" Ha%e you any e<$erience in this kind of case? Could you recommend any o$eration $ractice for minimi1ing this? Could you recommend a s$ecial metallurgy? =oes car!on steel a$$ly for it? %uestion ; Are any refineries currently monitoring for met(anol emissions from t(eir (ydrogen manufacturing facilities) If so- &(at le0els of met(anol are "eing found) 1(at analytical met(ods are "eing used) H&HG# One of our (est Coast refineries with an >0R recently measured methanol in their emissions from that unit and found them to !e e<tremely low much less than any of the antici$ated re/uirements" That unit had !oth a low tem$erature shift and a high tem$erature shift" (e ha%e learned that the amount of methanol formed during the high tem$erature shift is e<tremely low under normal conditions and the amount can !e

controlled under the low tem$erature shift reaction through kinetics" .f we kee$ the tem$erature low enough on our low tem$erature shifts then the methanol $roduction is not %ery high at all" A&R;OC(CG# The emissions of methanol from hydrogen $lants is increasingly a concern" 0easurement of it is difficult in the CO2 %ent and somewhat easier in the condensate" To$soe has de%elo$ed a %ery accurate model to $redict the formation across the low tem$erature shift catalyst" (e com$ared it with one refiner and came within three $ercent of the measured %alues" For a unit utili1ing @ust a low tem$erature shift not a high tem$erature shift the emissions for a 63 million standard cu!ic foot a day hydrogen $lant ranged from +33 to ' 333 $ounds of methanol $er day" The methanol formation as was $ointed out is sensiti%e to tem$erature" & 23 degree decrease in tem$erature in the o$eration of the low shift will decrease the methanol formation !y a factor of two" .t is sensiti%e to s$ace %elocity i"e" higher s$ace %elocity will reduce methanol formation" The lower the CO concentration the lower the methanol formation and the more steam the lower the methanol" To$soe recently introduced a new low emission catalyst" .t went into ser%ice in the $ast month in the (est Coast" .t reduces emissions !y a factor of eight from the ty$ical catalyst" JO>CCM# 0ost of the methanol $roduced in hydrogen $lants from low tem$erature shift concentrates in the $rocess condensate" The le%el in the condensate de$ends on the o$erating condition of the low tem$erature shift s$ecifically tem$erature new or used catalyst steam to car!on ratio the amount of CO and CO2 in the feed" (e ha%e sam$led the $rocess condensate infre/uently and it has ranged !etween 1 233 and * 333 $$m with an a%erage of 2 533 $$m" >am$les were analy1ed !y an outside la!" :nited Catalyst re$orts le%els *33 to 533 $$m for new catalysts and recommends higher acti%ity catalysts to reduce methanol concentrations" Aased on recent 0&CT concerns we are in the $rocess of ree%aluating all the $rocess condensate streams in the CO2 %ent for methanol" The analytical method for the %ent and $rocess condensate is GCFF.= utili1ing G.O>H method 2333 in a manner consistent with :">" C8& R017 or >:00&R canisters in accordance with methods TOF12 and TOF1*" &nalysis $erformed !y analytical $rocedures from method TOF12 for G0OC and C8& R017 for methanol" The &8. has $etitioned the C8& to either 214 eliminate CO2 %ents for miscellaneous %ent re/uirements for 0&CT . 224 after further re%iew of the data and if a$$ro$riate and feasi!le the C8& could add control re/uirements for methanol from hydrogen $lant %ents to refinery 0&CT .. rules or 2'4 list hydrogen $lants as a se$arate source category and e%aluate the need for regulation" >HOO:F. (&GG 2&ir 8roducts4# (e are currently monitoring the methanol emissions from one of our larger hydrogen $lants in Gorthern California" Recently we analy1ed for the cold $rocess condensate from another hydrogen $lant in 8asadena Te<as" (e measured a!out 163 $$m methanol" The measurement was $erformed on the H8+793 gas chromatogra$hy and used in a =A wa< column" J.0 &AAOTT 2.C. Matalco4# (e also know that a num!er of refineries are increasingly concerned to monitor and minimi1e their emissions" =etermining the total make of methanol is slightly com$licated !ecause it $artitions !etween the CO2 and the $rocess condensate" The $rocess condensate then itself is often stri$$ed and there!y leads to a %a$or emission" (e !elie%e that the !est means of monitoring the !y$roduct methanol routinely is to take a sam$le of this cooled $rocess condensate" The water sam$le can !e analy1ed !y gas li/uid chromatogra$hy for methanol" Furthermore the methanol in the CO2 can then !e sim$ly calculated !y means of well tried and trusted models" .n terms of what those le%els of methanol are it de$ends on gas conditions dry gas com$osition and steam to dry gas ratio" Tem$erature is %ery im$ortant and also the /uantity of catalyst %olume and the catalyst age also $lay a $art" Finally the inherent catalyst selecti%ity is the most im$ortant feature of all in limiting the methanol $roduced" For instance $otassium do$ed low tem$erature shift catalysts which ha%e now !een $atented and are now !eing further de%elo$ed will gi%e significantly lower rates of methanol formation" &nd they will do this without sacrificing any ca$acity to a!sor! $oisons and only taking a small acti%ity hit" (e ha%e e<$erience already with one of these ty$es of catalysts in meeting the needs of a $lant which had methanol emissions $ro!lems" B. Hydrotreating 1. Reactor Bed Plugging %uestion < 1(at is "eing done u/stream of (ydrotreaters to minimi6e causes of "ed /lugging) Please discuss metallurgycorrosion control- intermediate storage and filtration.

%uestion = Has anyone found a relia"le met(od for filtering solids from a (ea0y feed- suc( as /roducts from a co+er, >- or ot(er /rocesses) ?ist s/ecific micron si6es for ty/ical /articulate foulants. %uestion 3< Beyond t(e normal /recautions of feed filtering and tan+ gas "lan+eting of feedstoc+ to distillate@(ea0y oil (ydrotreaters- &(at ne& met(ods are "eing em/loyed to minimi6e fouling and eAtend run lengt() Has com/ositional analysis of feed streams resulted in significant findings relati0e to t(e mitigation of fouling) A&R;OC(CG# (ell the su!@ect of $lugging and how to a%oid it is a $erennial /uestion" . am going to $ro%ide the !ase starting $oint on a%oidance" The first $oint is u$grade the metallurgy in the u$stream units $articularly in the hot and high %elocity areas" Hour indicator of whether you ha%e a $ro!lem is the iron content of the feed going to the hydrotreater" .f it is higher than one $art $er million then you are in trou!le" 8refera!ly . ha%e o$erated units that needed to !e as low as oneF/uarter of a $art $er million in order to reach a 2 1?2 year cycle" The second factor that can influence that metals le%el is your fractionation $erformance in the u$stream unit" .f you do not ha%e clean se$aration again that can result in e<cess carryo%er of metals" .t is !een widely re$orted that you want to a%oid o<ygen contact with your feeds" =o not store itI if $ossi!le feed it hot" .f you ha%e to store it !lanket it with an inert material nitrogen or natural gas" &gain mo%ing further downstream in your feed surge drum if you ha%e one on your unit do not forget to !lanket it with hydrogen or a natural gas" &%oid hot s$ots in your heater firing" That is really a generic comment !ut it is something not to !e forgotten a!out" Then you are into treating the sym$toms which is the traditional feed filters and graded !ed system to $ro%ide the means of trying to kee$ the solids from coming in and then dealing with the solids when they come in" . would like to s$end @ust a moment to talk a!out feed filtration" .t is something that e%eryone wrestles with i"e" how do you in fact design these units? .n many cases the starting $oint is you ha%e to $lan to run these units any feed filters at least 23 to '3 degrees a!o%e their cloud $oint" >econdly you ha%e to make some assum$tions a!out the solids loading that you are going to design for" .f it is an e<isting unit you can get some data !ut many times you are making a @udgment for a unit that you do not ha%e data for" There are a num!er of units a%aila!le" They are the !ack flow %ariety the !ack flushing %ariety and there are 8aul Ronick and 8etter Baco and 8roguard" One of the issues you ha%e to deal with in designing these units is what si1e filter? & 2+ micron is ty$ically a starting $oint and it has !een shown that a 2+ micron filter will filter material down to much smaller si1es" Finally you ha%e to !ackflush it with something" (here will that something go? .f it is feed or $roduct and if you ha%e a %ery high solids loading you may find yourself dealing with a %ery high $ercentage of recycle in effect that you had not antici$ated" There are systems that $ro%ide !ack flushes with steam or gas to minimi1e that $ro!lem" Finally you may conclude that while you want some $rotection !ut continuous !ack flushing filters are too !ig of an in%estment" 0any refiners ha%e had success with cartridge ty$e filters" There ty$ically a starting $oint is 13 micron filters and then you mo%e u$ or down de$ending on your inter%al of change out" &gain something to remem!er is those filters also ha%e to !e a!o%e the cloud $oint" &s your tem$erature re/uirement goes u$ to reach that target you may ha%e to go away from standard filter elements and go to fi!erglass filter elements" A.GFOR=# &s 0r" Aarloewen said the $lace to really start on these $ro!lems is first a good understanding of what is going on u$stream and second a good knowledge and understanding of what the feed is made u$ of and then lastly what is going on within the hydrotreater heat e<changer system and the !ed itself" (e found that reactor !ed $lugging can !e caused !y either de$osition of corrosion $roducts formed u$streamI or $olymeri1ation of the hydrotreater feed either in tankage in the heat e<changer or sometimes e%en on the reactor !ed" .n any of these cases a layer formed on to$ of the reactor !ed causes the $lugging" The reduction of corrosion $roducts and $articulates in hydrotreater feed streams can !e accom$lished !y se%eral methods" &s 0r" Aarloewen said identifying sources of corrosion u$stream is really critical to successfully eliminating these $ro!lems" .f it is corrosion related and effecti%e corrosion control $rogram in the crude unit o%erhead condensing system the FCC Gas Con or the saturated and unsaturated gas $lants can many times eliminate the $ro!lem altogether" O!%iously there is a tradeoff !etween im$lementing a chemical solution %ersus u$grading unit metallurgy" >ometimes metallurgical solutions are the most cost effecti%e and sometimes chemical" 0any times the effect of -incidental- streams introduced into these systems is not fully e%aluated" These would include o<ygenated wash waters in o%erhead condensing systems that can cause iron o<ide formation and then

su!se/uently migrate to the hydrotreater !edI or $urchased condensate that might contain $olymeri1ation $recursors" (hen the feeds are characteri1ed the im$act of these incidental streams must !e fully e%aluated to make sure that they are not going to cause a $ro!lem" &lthough unusual we found a few cases where corrosion actually occurs in intermediate tankage or in $reheat e<changers" This can !e effecti%ely addressed !y either installing a more corrosion resistant metallurgy or an effecti%e chemical treatment $rogram" & well designed dis$erssant ty$e antifoulant $rogram can !e used to effecti%ely com!at $ressure dro$ !uildu$ due to inorganic foulants !ut these are usually effecti%e only if they are a$$lied !efore the !ed fouls significantly" .t is also im$ortant to make sure the to$ of the reactor !ed is designed to acce$t the smaller dis$ersed $articles" 0r" Aarloewen already co%ered intermediate tankage !ut $olymeri1ation mechanisms can also occur in the $reheat e<change e/ui$ment" .dentifying the source of the $olymeri1ation and the mechanism is critical in designing a $ro$er anti$olymerant $rogram to address reactor !ed fouling resulting from $olymer formation" C&.G# One other item . could add to $re%ious comments is that on the intermediate tankage !e careful where your draw $oint is" Hour draw $oint could !e too low and you could !e $ulling in water and sediment" Geedless to say you need to drain your tanks regularly" . ha%e some e<$erience in our =elaware City $lant on a furnace oil hydrotreater" (e $lan to u$grade it to '15; stainless steel when re$lacement is re/uired howe%er it may not !e @ustifia!le" To reduce $lugging they ha%e installed >ha$ed >u$$ort Aalls and they are also using a Galco dis!ursement which has !een %ery effecti%e in dis$ersing $olymeri1ed hydrocar!ons" The sha$ed su$$ort !alls are made !y Haldor To$soe" F;CTCHCR# (ith res$ect to $articulates we know of se%eral refiners that are relia!ly filtering large $articles greater than 2+ microns from gas oil feeds" For smaller $articles such as FCC catalyst fines from FCC fractionator !ottoms these cannot !e relia!ly filtered !ecause of their small si1es" .f left in the feed these fines will accumulate in the interstitial s$aces of the hydrotreating catalyst causing $ressure dro$ and maldistri!ution" .n one $articular case that we know of a!out 6 weight $ercent of a$$ro<imately 2 micron FCC catalyst fines was measured on the s$ent hydro$rocessing catalyst from a unit $rocessing FCC fractionator !ottoms" (e !elie%e that the most relia!le method to remo%e these small $articles from the feed is to distill it $ossi!ly in the feed of a =C: or a fluid coker or in a B&C tower" &nd o!%iously this assumes that the $roduct streams from these units will !e going to the hydrotreater" (ith res$ect to $olymeri1ation . concur with the $re%ious comments" &ntio<idants ha%e !een used in the $ast with some measure of success" These are usually in@ected into the rundown to tankage" For na$thenic acid corrosion refiners ha%e !lended feeds to a total acid num!er of less than 3"+ mil MOH $er milligram and used stainless steel grades with greater than 2"+ wt, moly!dnum with success" Corrosion inhi!itors ha%e !een used !ut unfortunately the most effecti%e $hos$horous !ased inhi!itors are also catalyst $oisons" FO>TCR# (e $roduce well o%er 23 m!$d of CHGO at our refinery" The /uality is %ery $oor so it is essential to treat all the feed at our Cat Feed Hydrotreaters and to ma<imi1e the run cycle" >o we s$end a lot of tome on our feed filter design" Aut we ha%e found out !y e<$erience that no matter how good our filtration system is at our hydrotreater it can !e defeated !y the sheer /uantity of fines in CHGO if the fractionator is not designed or run $ro$erly" >o to $rotect our CHGO /uality we install two redundant wash oil s$ray headers a!o%e the CHGO draw section" Cach s$ray can deli%er 133, of the re/uired wash oil and each is designed to deli%er a minimum '3, o%erla$" Aut good design is not enough" &t turnaround time we re/uire a $rocess engineer to witness and a$$ro%e the s$ray test $rior to closing u$ the %essel" >ometimes there is an o!struction in a no11le or other $ro!lem that $re%ents a good s$ray" C%en though there is intense $ressure to get the unit !ack in o$eration it $ays to make sure your s$rays are right" (e ha%e had some success with the installation of a coke remo%al system on the coker fractionator" (e filter a sli$ stream from the !ottom of the fractionator cool it to a!out '33LF and then $ass it through a standard cloth filter" This tends to $re%ent coke !uildu$ in our fractionator as well as lower the coke fines in our HGO" H&HG# .n !oth our diesel and na$htha hydrotreaters we e<$erienced $lugging $articularly a crust that would form on the to$ of our !eds" (e do not ha%e any gas !lanketing on our tanks or anything of that nature" (e ha%e sim$le coalescers u$stream on our crude unit rundown streams mostly for water remo%al" Our hydrotreater feed is not $retreated in any other way" (e ha%e found success !y using the graded !ed method of loading our catalyst and we also eliminated the trash !askets which were initially $ut into those reactors as $art of original design" They were totally ineffecti%e in doing

what they were su$$osed to do and were often a hindrance" Once we remo%ed these !askets and went to a graded !ed we no longer had a $lugging $ro!lem at all" Often times we used to ha%e a +3 $ound $ressure dro$ de%elo$ o%er the life of the catalyst" Gow we ha%e none at all and our catalyst can run until it really needs to !e changed out for catalytic reasons rather than for $ressure dro$ constraints" HCGMC# &fter e<$erimenting with se%eral filtration de%ices we ha%e concluded that in our situation sand filters are the most relia!le de%ices for filtering solids from hea%y feed streams such as Hea%y Coker Gas Oil" 8ro$er si1ing and grading of the filtering medium is essential to o$timi1e $articulate remo%al" (e target remo%al of $articles larger than 23 microns" &ctual $articulate !alances around our Gas Oil Hydrotreater reactors ha%e shown that inert solids coming from the Hea%y Coker Gas Oil smaller than 23 microns readily $ass through the reactors" JO>CCM# &t one lu!e oil hydrotreater hydrotreating gas oils and the deas$halted %acuum tower !ottoms 2+ micron filters were added and later changed to 13 micron filters im$ro%ing the first !ed fouling" The unit was re%am$ed increasing the hydrogen recycle from a$$ro<imately 1 2+3 to * 333 standard cu!ic feet $er !arrel of hydrogen im$ro%ing the total reactor fouling" Catalyst $ressure dro$ no longer limits the reactorI the reactor is limited to catalyst acti%ity" &t a second hydrotreater we ha%e 2+ micron cartridge feed filters" (e recently e<$erienced a high $ressure dro$ in the to$ !ed that was attri!uted to iron sulfide from the reaction of iron and sulfur in the feed" The unit $rocesses na$thenic and $araffinic feedstocks" (e ha%e since loaded high %oid s$ace to$$ing in the reactor with $romising results after se%en months" >tartFofF run $ressure dro$ in the to$ !ed decreased from nominal '3 $si to less than 13 $si" (e ha%e had the most success when the ty$e of !ed $lugging has !een identified and traditional a$$roaches ha%e !een used to reduce the $ro!lem" (e ha%e had more success with !ed grading than scale !askets for reducing to$ !ed $lugging" (e ha%e also used nitrogen !lanket feed tanks in com!ination with si1e !ed graded catalysts on the to$ !ed for im$ro%ing $ressure dro$" These related e<$eriences su$$ort the discussion last year around the fi%e causes of reactor !ed $lugging" That is trash solu!le iron car!onaceous coke catalyst !ed coking and catalyst !ed fines" 8CTCR>OG# . agree with the $re%ious comments" . would like to throw a little fine tuning on a cou$le of them" (e ha%e noticed that our filters $lug u$ more if we feed resid as %acuum tower !ottoms" (e see less $lugging in the filters if we feed this e/ui%alent resid material as reduced crude !efore it has gone through the %acuum heater and the %acuum tower where may!e some cracking some coking or some other reaction has occurred" (e ha%e not isolated the mechanism for that yet" (e run a fairly hot %acuum transfer tem$erature a!out 673LF" On !ack washing the filters we had set u$ instrumentation and did not take full ad%antage of it for a while" (e then did some fine tuning and found that we were missing some of our !ackwashes" >o we started looking at shorter times in the !ack washing cycle and we found a!out half of our filter elements were not !eing effecti%ely cleaned" (e ha%e also noted that o%er time our filter elements tend to accumulate something that does not !ackwash off" (e therefore ha%e a s$are set" (e send one set out for sonic cleaning to clean the residual material" .n another refinery we ha%e a distillate hydrotreater in which we now treat reduced crude as well as distillates" That unit was not designed with the filter !ecause it was only going to ha%e distillate feed" (e did get a significant successful run until we had an u$set in the unit where the recycle com$ressor had gone down" (e ha%e seen a significant increase in reactor $ressure dro$ in na$htha units as well when we ha%e u$sets with the com$ressor and start !ack u$" (e get a ste$ change in $ressure dro$ in the reactor" The last thing . would say is make sure you ha%e a good %a$orFli/uid distri!ution in your reactor so you do not ha%e all the hydrogen going down one side and all the oil down the other causing coke formation down in the reactor !ed" >&0:C;># .n fact there is a few more things to add here" (e set a sodium s$ecification of 3"+ $art $er million on our 5+ 333 !arrel $er day distillate hydrotreater at the Ro!inson refinery" &fter se%ere reactor fouling and some e<changer fouling from salt treated $urchased diesel stocks" . think this would a$$ly to any distillates that you would !e mo%ing o%er salt water also" This s$ecification in fact did eliminate the $ro!lem" &s has !een mentioned many times dissol%ed o<ygen ethers $ero<ides and diFolefins will cause $olymeri1ation and can cause crusting when solids either in the feed or corrosion $roducts in the $reheat e<change are !ound u$ !y the $olymer" .n one na$htha hydrotreater we were actually getting a!out three month runs due to reactor $ressure dro$ where we would ha%e to go in and skim the !ed due to this $olymeri1ation mechanism" (e sol%ed that $ro!lem !y adding an acti%e su$$ort" (e are using criterion 71*FHc cylinders and !alls on to$ of that reactor !ed" Currently we are on a nine month run with no $ressure dro$ increase and are cautiously calling this a success as the acti%e su$$ort a$$ears to !e hydrotreating the $olymer" . would also add that we do not see much

success in hot hydrogen swee$s" . think once you ha%e a $olymer formed or you ha%e $luggage you $retty much ha%e to go in and skim or dum$" .n general 0arathon has not had great success with chemical treatments with antifoulants to current hydrotreater reactor !ed fouling !ut we are still looking" T&>MCR# (hile . agree with all of the remarks that ha%e $re%iously !een made es$ecially 0r" AarloewenOs let me a$$ly my remarks to the hea%ier materials" .t is always difficult to s$ecify and find the right filter for the @o!" Trying to !e definiti%e on the ty$e si1e range and the /uantity is always e<tremely difficult es$ecially in hea%y oil $rocessing" .n downstream of our e!ulated !eds of course we ha%e to deal with catalyst fines as well as the $ossi!ility of some car!onaceous material and ty$ical corrosion or fouling ty$e materials" These ha%e to !e dealt with !ecause you are going into downstream $rocessing on some of the $roducts" Traditionally we ha%e used !asket strainers and made of Johnson screen" They also are ty$ically in multifilter arrangements and often controlled on a 8;C system or directly from the =C>" O!%iously in hea%y oil $rocessing !ack flush filters re/uire a tremendous /uantity of !ack flush and !ecome somewhat cum!ersome to use" >o we ha%e concentrated on a !asket ty$e filter" The sintered metal filters ha%e $ro%en to !e worth their while !ut not so much in the hea%y oil systems" One of our recent de%elo$ments with one of our clients has !een in Ja$an with a scra$ed surface filter on the hot hea%y oil $roduct from the HFoil unit and that of course is going into se$aration and fractionation" >o we are %ery interested in taking out all of the $articulate matter that may !e $resent" Gow this ty$e of filter is not new !ut the a$$lication downstream on the downstream side of the e!ulated !ed system is /uite recent and we are finding that we ha%e a$$ro<imately ' $si constant $ressure dro$ on the scra$ed surface filter" (e would not ad%ise to going to lower than a!out *33 micron on the filter si1e on the hea%y oil $rocesses !ecause you will !e changing filters or !ackwashing them constantly" >o we are looking at taking out anything from *33 u$ to 1 733 micron si1e !ecause we are dealing with the $ossi!ility of catalyst fines coming o%er" Going u$ a little !it now from the hea%ier oil we ha%e some other details concerning a s$ecial catalyst guard !ed to $re%ent fouling on the to$ of the main catalyst in some of the downstream hydrotreaters" The catalyst H0C 7*1 made !y &creon was mainly designed as a demetali1ation catalyst with a s$ecific structure and low acidity" .t can acce$t feedstocks with some as$haltenes and metals" .t can a%oid the $lugging !y the radicals created in the heater !y thermal degradation of the hea%y feedstock !ecause of its acidity !eing %ery low !y using a s$ecial alumina" The radicals can !e hydrogenated !efore they are in contact with the higher acidity of the hydrotreating catalysts" The constituents of the feed streams as already mentioned mainly the $araffinic and aromatic characters are im$ortant for the tendency to foul" Aut the o$erating tem$erature as we ha%e heard is also an im$ortant $arameter" .t has !een mentioned also that flushing is sometimes worthwhile and that can !e done to remo%e some of the solu!le materials" Aut of course it has its limitations" Hea%y $olyaromatic structures are sometimes /uite difficult to remo%e" Hydrogen stri$$ing has !een mentioned !ut as already noted that is not the !est of solutions" .t works in some cases !ut not in others" CR&.G H&RBCH 2:O84# Aed fouling a$$ears to !e most $ro!lematic in gas oil hydrotreaters $rocessing HBGO HCGO and im$orted intermediate stocks" Ty$ically the cause of the fouling can !e related either to 214 inade/uate desalting 224 e<cessi%e coke fines 2'4 na$hthenic acid corrosion or 2*4 gums" Gums are most commonly encountered when $rocessing $urchased intermediate stocks that ha%e !een e<$osed to o<ygen" .n some instances $refractionation of the $urchased stocks has $ro%en effecti%e in reducing fouling tendencies in the hydrotreater $reheat e<changers and catalyst !eds" Ga$hthenic crudes re/uire s$ecial materials considerations as car!on steel chromeFmoly!denum steels and certain '33 series stainless steels are su!@ect to na$hthenic acid corrosion 2G&C4" G&C occurs at tem$eratures within the range of 2'3F'63oC with the $eak corrosion occuring at tem$eratures of 26+F273oC" Corrosion is most $ro!lematic at high %elocity or im$ingement locations" G&C can occur either in the $reheat train of the hydrotreating unit or in u$stream facilities" The resultant iron na$hthenate corrosion $roducts can e%entually $reci$itate as iron sulfide in the %oid s$aces of the lead catalyst !ed" Our e<$erience has indicated that G&C is generally not a $ro!lem in hydro$rocessing units when o$erating with feedstocks ha%ing acid num!ers less than 1"+ mg MOH?g" .n crude units and %acuum units G&C is of concern when $rocessing crudes with acid num!ers e<ceeding 3"+ mg MOH?g" .ndustry e<$erience has indicated that a minimum of 2"+, moly!denum is re/uired to a%oid G&C" (hereas &olderS T$ '15; generally satisfied this minimum 0o re/uirement the &modernS T$ '15; a%erages only 2"3,

0o" Thus the current :O8 recommendation for G&C ser%ice is to either s$ecify T$ '15; with a 2"+, 0o re/uirement or s$ecify T$ '16; which has 'F*, 0o" HCGO streams can contain su!stantial le%els of coke $articles" 8ro$er definition of the $articulate loading and $article si1e distri!ution is essential for s$ecifying a$$ro$riate filtration e/ui$ment" .n some cases the loading and $article si1e distri!ution has necessitated ela!orate filtration efforts" Aackwash cartridge and solid !ed filters 2or a com!ination of these4 ha%e !een used with %arying degrees of success" (hile $ro$erly designed filtration e/ui$ment is re/uired for the !ulk of the $articulate remo%al the lead reactor of most units is e/ui$$ed with a to$ filter !ed consisting of se%eral layers of s$eciali1ed high %oidage guard catalysts" These s$eciali1ed guard catalysts are ty$ically graded !y sha$e si1e and acti%ity" .n se%ere ser%ice a !y$assa!le guard reactor is s$ecified" AR.&G 0OH>C 2Haldor To$soe4# . think most $eo$le in the industry agree that the si1e of the filter used is more dictated !y what can !e tolerated in terms of !ackflashing cycle or change out fre/uency rather than the technical design" (hat that means is most $eo$le ha%e a larger o$ening than they really should and $assing materials to the reactor no matter what" .n that scenario a $ro$erly designed graded !ed will not only ena!le you to in some cases remo%e trash !askets !ut also enhance your gas?li/uid distri!ution and there!y your catalyst utili1ation and run length" A.;; F&HCH 2Aaker 8etrolite4# For hydrotreaters that ha%e e<$erienced an increase at $ressure dro$ in the reactor due to iron sulfide $lugging of the u$$er $art of the reactor !ed the use of a $ro$rietary antifoulant that agglomerates the iron sulfide has !een %ery successful" These $rograms are used at high rates for 7 to 12 hours after which you go !ack to normal o$erations" (e ha%e seen a!out an 73 $ercent reco%ery in the $ressure loss" R&H FR.T>CHC 2General &tomics4# (e know of two refineries in Curo$e that are using electrostatic se$arators for remo%ing catalyst fines from FCC slurry !ottoms $roducing a lowFash hydrotreater feedstock" The ad%antage is that there is no $lugging with small catalyst $articles" >&0.R 0OH&00C= H&;&(&G. 2>audi &ramco4# For 0r" Ainford as a comment to what you ha%e said and what 0s" Hahn stated do you e<$ect $olymeri1ation for straight run na$htha if we do not ha%e a gas !lanket on the tank? =o you agree on remo%ing the trash !askets of the reactor? 0r" 8eterson how can we ensure the $ro$er gas li/uid distri!ution of the !ed? 8CTCR>OG# (e ha%e seen some $oor reactor distri!utor designs in the $ast resulting in a lot of li/uid going down one side and the gas going down the other" (e had what we called carrots of coke forming" >ock loading of the catalyst also $romoted these distri!ution $ro!lems" (e ha%e gone to well dense loading which we will talk a!out a little !it later and we ha%e gone to well designed distri!utor trays to make sure that the li/uid is dri$$ing or is !eing s$rayed down e/ually o%er the whole cross section of the !ed and that the gas also gets into all the areas" There are %arious $ro$rietary tray designs that we %iew as successful and it is the homemade ones that tend to get you in trou!le" =uring the installation of the tray in the reactor we want to make sure that the startu$ crew and the construction crew engineers check the distri!utor tray for le%elness with a water test" 0ake sure all the water is not $ouring down one side with li/uid star%ation on the other side" A.GFOR=# Regarding the $rocessing of straight run materials if there is no unsaturates in the stream . would not e<$ect to see any $olymeri1ation in tankage" That could !e checked for with a sim$le !romine num!er" There are a cou$le of things to watch for" One is intermittent re$rocessing of slo$ oil or reco%ered oil streams !ack to the front of the crude unit" >ometimes you can get unsaturates that come !ack through from the reco%ered oil" >o you want to make sure you do not ha%e any incident related $olymeri1ation as a result" >econdly without gas !lanketing in the tankage you are still su!@ect to corrosion in tankage" (hat may look like a $olymeri1ation $ro!lem may actually !e a corrosion $ro!lem in tankage that is carrying downstream" Regarding the remo%al of trash !askets we are really !y no means e<$ert on that" . would defer that to one of the catalyst su$$liers to answer" A&R;OC(CG# . would like to comment !riefly on distri!utor tray design" One /uick and dirty indicator is if you ha%e %ery large tem$erature gradients across the reactor diameter either at the inlet !elow a /uench 1one or at the outlet at the !ottom of the !eds"

>econdly if you do not ha%e %ery good instrumentation To$soe has done a lot of work in the design of distri!utors" (e ha%e de%elo$ed models that characteri1e the $erformance of the three ma@or ty$es of designs that are a%aila!le chimney tray !u!!le ca$ and To$soe tray" (e could gi%e you an analysis" 8&:; FC&RG>.=C 2Galco?C<<on Cnergy Chemicals4# On u$stream corrosion control $lease remem!er that when the $H of the crude unit o%erhead water is in e<cess of 6 iron sulfide !ecomes insolu!le and a rag layer !uilds" . cannot tell you how many times . ha%e run into that rag layer continually growing and $uking o%er causing a $retty !ad $ressure dro$ $ro!lem across the hydrotreater reactor" 0o%ing down the tower as far as na$hthanic acid corrosion control goes to address one of the $anel mem!erOs concerns on $hos$horous !ased chemistry we do ha%e a nonF$hos$horous !ased chemistry that is e<tremely effecti%e" &s a last ditch effort to hel$ alle%iate reactor !ed $ressure dro$ we ha%e !een 73 $ercent effecti%e in reducing the $ressure dro$ $ro!lem !y using dis$ersant ty$e chemistries" & ty$ical treatment takes from 12F62 hours to com$lete de$ending on the se%erity of the situation" 8ressure dro$ reductions in e<cess of '+ $si ha%e !een achie%ed" JOHG &RG=T 2&rndt E &ssociates4# . would like to relate two things on feed filters" &s 0r" Aarloewen said cold feed can !e a $ro!lem" Mee$ feed tem$erature well a!o%e cloud $oint T 23LF" Feeding from cold tankage can make your filter cycle like mad" (atch out for $eriods of high cold feed rates" >econdly watch your !ack flush" Ha%e $lenty of $ressure a%aila!le to get enough !ack flow to clean the filter and get the gunk out of the whole element" .nsufficient !ack $ressure will rattle the filter cake !ut not remo%e it from the system" :$on forward flow the filter @ust $lugs u$ immediately" TH.CRRH =&R=C 28all Cor$oration4# One technology that 8all Cor$oration has a$$lied in many refineries worldwide is feed filtration !y automatic selfF cleaning filter" .nstalled on a different streams such as coker gas oil diesel or %acuum gas oil 8all technology has $ro%ided significant reactor !ed $rotection" 8ressure dro$ in the reactor !eds in all these a$$lications has remained fairly constant o%er a %ery long $eriod of time" .t was said that usually $eo$le want to remo%e $articles e/ual or !igger than 2+ micron" One $oint . would like to address is the efficiency of the remo%al" .f you work out a few hundred of $$m of $articles in the feed and if you ha%e a feed filtration which has an efficiency of say 13 to 23 $ercent when com$ared to a filter which can deli%er 99"99 $ercent efficiency the difference in terms of solids going to the reactor can !e in terms of tons" .n other words one could remo%e 2+ micron?articles with a low efficiency filter and e<$erience reactor $lugging" The e<treme efficiency of 8ace filter guaranties that no reactor $lugging could occur" & second comment is a!out recycled !ackwash %olume" Our technology is a gas assist technology" The main feature of this technology is that you can achie%e a %ery low !ackwash %olume ty$ically !elow one $ercent of the feed" Therefore the /uantity of the li/uid you ha%e to re$rocess is e<tremely low" 8&:; >QH0AOR>M. 2Gorton C88C4# &s $eo$le ha%e mentioned many refiners ha%e gone to graded !eds in addition to filtering for remo%ing materials on hydrotreaters" .t is im$ortant to note that you need to know the source of the $articles re/uiring remo%al whether it is fines metal $articulates or solu!le materials !ecause that will affect the way you design the graded !ed and the ty$es of materials you use in a graded !ed" Gorton de%elo$ed macro $orous rings and s$heres that we understand ha%e !een used in hydrotreater a$$lications since the early 1973s" The a%erage $ore si1e is o%er 133 microns thus allowing these guard !eds to actually filter out the $articulates" Therefore the $articulates are not @ust $lated out onto the guard !ed !ut it is actually filtered into the guard !ed rings and?or s$heres" 2. Reactor Effluent Systems %uestion 18 Has anyone o"ser0ed (ig( corrosion rates in t(e eAc(angers and stri//er feed (eaters do&nstream of t(e ?P se/arator in a diesel HBS unit) If so- &(at &as t(e cause and &(at materials are recommended in t(is ser0ice to a0oid suc( (ig( corrosion rates) ould stri//ed sour &ater contri"ute to t(e /ro"lem) >&0:C;># High corrosion rates ha%e !een a $ro!lem in the e<changers downstream of the low $ressure se$arator !oth in 0arathonOs Gary%ille diesel hydrotreater and Ro!insonOs hydrocracker" &lthough the configurations are different in these units in !oth cases the root cause of the $ro!lem was under de$osit corrosion from ammonium chloride salt formation in the '+3 to *33LF tem$erature range" Aoth systems use car!on steel !undles at this $oint in the effluent train" .n !oth cases the failure occurred on the shell side of the tu!es as a feed from the low $ressure se$arate is !eing $reheated going to the stri$$er or the de!utani1er"

.t is sus$ected that minor water carry o%er or at least saturated conditions downstream of the low $ressure se$arator lead to salt de$osition where %a$ori1ation occurs" >tri$$ed sour water if $ro$erly stri$$ed should not contri!ute to corrosion in these e<changers" Check your stri$$ed sour water for chlorides iron calcium total dissol%e solid and total hardness in addition to ammonia H2> and dissol%ed o<ygen" :O8 $ro%ides s$ecifications for this as indicated !elow" :O8)s (ater (ash Quality Guidelines Chlorides w$$m D+ .ron w$$m D2 Calcium w$$m D3"+ Co$$er w$$m D3"3+ T=> w$$m D13 Total Hardness D1 $H 6F9"+ H2> w$$m D133 GH' w$$m D133 =issol%ed O2 $$! D23 &mmonia will always !e $resent in the low $ressure se$arator so . do not !elie%e stri$$ed sour water is a $ro!lem" The key to eliminating corrosion in our case was to eliminate any chloride source to the unit" .n the case of the hydrocracker we installed a net gas chloride guard !ed on one of Ro!insonOs reformers so that all of the hydrogen has now !een treated and the $ro!lem has gone away" &nother $otential corrosion mechanism to !e aware of in this ser%ice is erosion? corrosion in the reactor effluent or tu!e side of these e<changers" .f unit rates are !eing $ushed !eyond the original design an analysis of the tu!e %elocities in the reactor effluent !undles should !e $erformed" Check to make sure that the water wash for ammonium !isulfite salt is !eing in@ected in the correct e<changers and at the $ro$er rates" This contri!utes to the higher %elocities" Tu!e %elocities a!o%e 13 to 23 feet $er second are not recommended" 0&;CM# (ith res$ect to the use of sour water in the water wash in our new designs we would recommend that the water wash !e done with condensate or with !oiler feedwater if it is a%aila!le" This will a%oid any $ossi!ility of some high salts concentration that may !e in sour water stri$$er !ottoms" .f it is not a%aila!le . would tend to agree that generally you would e<$ect sour water stri$$er !ottoms to !e an acce$ta!le water wash medium" Aut generally we would s$ecify that it !e with !oiler feedwater" . also agree that the chlorides which $ro!a!ly would !e e<$ected to !e coming in with the hydrogen to the hydrotreater can contri!ute to the unusual corrosion in these systems downstream of the reactor effluent coolers and in the coolers themsel%es" These e<changers are normally car!on steel systems for a diesel desulferi1er" (e ha%e seen refiners use stainless steel tu!es in the air coolers in order to slow down this corrosion rate" There ha%e !een some significant failures in the industry in these ty$es of air coolers in the last se%eral years" .t is something that really needs to !e continually watched" . think the %elocity and erosion effects ha%e contri!uted to /uite a num!er of these failures" >o you should !e watching your unit to make sure that the %elocities are !elow 23 feet $er second as a reasona!le target" The /uestion also asked a!out corrosion in feed heaters downstream" This would !e the stri$$er feed heater" . would like to $oint out that refiners o$erate these stri$$ers at %arious $ressure le%els" >ome refiners attem$t to o$erate at a sufficiently high $ressure to get the off gas through the scru!!ing system and into the refinery fuel system without %a$or com$ression" &s you raise the $ressure of the stri$$er the tem$eratures that is needed to $reheat the feed increases" The !ottoms tem$erature of the stri$$er towers increases also" This is going to accelerate corrosion" The feed heaters which ha%e !e car!on steel tu!es may need to !e u$graded to car!on?moly steel @ust to offset the corrosion from H2> as you mo%e into higher feed tem$eratures" .f you are ha%ing feed heater $ro!lems look at maldistri!ution across your heater" 0ake sure that there is no high tem$erature areas in some of the tu!es due to $oor flow distri!ution" A&R;OC(CG# . would like to confirm what 0r" >amuels $ointed out as the $rimary causes namely ammonium chloride corrosion" The most effecti%e way to address that is not to $our your money into metallurgy !ut to go after the chlorides" .t is e<tremely difficult to identify @ust what metallurgy is o$timum" Gormally the most likely source of the chloride is the off gas from the catalytic reformer" The use of the chloride tra$ there normally sol%es the $ro!lem" Occasionally you might ha%e chloride contaminant coming in with the hydrocar!on feed" For this situration in %ery e<treme cases you might go all the way to desalting the feed"

C&.G# (e ha%e had in a cou$le of our $lants corrosion in the stri$$er feed heater of a diesel hydrotreater" This was attri!uted to high tem$erature sulfur attack" (e u$graded the tu!e metallurgy to nine chrome to correct the $ro!lem at our =elaware City $lant" .n ;ouisiana $lant we u$graded to fi%e chrome in the stri$$er re!oiler heater and also in the feed !ottoms e<changer" AOA RO==CH 2Roddey Cngineering >er%ices .nc"4# Concerning the first $art of the /uestion on corrosion in the stri$$er feed e<changers . did not hear anyone mention water carryo%er into the low $ressure se$arator" Gormally the flow goes from the high $ressure se$arator to the low $ressure se$arator" >hould you ha%e water interface le%el control $ro!lems in the high $ressure se$arator you can form a tight emulsion in the low $ressure se$arator" That water can carry o%er into the stri$$er and concentrate the salts when the water %a$ori1es in the feed e<changer" Bery low le%els of salt can cause a %ery serious $ro!lem" . know of at least one client who has installed a coalescer in the feed going to that e<changer with some success on reducing the rate of corrosion in the stri$$er feed e<changer" H&HG# (e did something /uite similar" (e determined that our salts were coming from a water carryo%er from the low $ressure se$arator" (e installed a demister in our low $ressure se$arator and that seems to ha%e sol%ed our $ro!lem" %uestion 11 Has anyone eA/erienced fouling /ro"lems in t(e reactor feed@effluent /re(eat eAc(angers on an , /retreat unit or MH unit) If so- &(at &as t(e cause and (o& &as it rectified) Has anyone tried antifoulant inCection in t(is ser0ice) 2Aackground# refiner o$erates with HBGO TA8 Cnd$oint 13+3 F >G 3"925 CCR 3"+ wt, &>T0 Color D5"3 >E( 3"3+ %ol, F which comes directly from u$stream B=:)s and from gas !lanketed storage tanks" Treat gas is mi<ed with the HBGO u$stream of the $reheat e<changers"4 8CTCR>OG# (e ha%e in@ected antifoulant in our FCC feed hydrotreater e<change stream since day one at the %ery strict ad%ice of our licensor" He also warned that if we e%er take it out for any $eriod of time do not $ut it !ack in again !ecause anything that accumulated is going to slough off and $lug u$ the reactor !ed" (ell we ha%e heeded his ad%ice and we got a four year run" (e are afraid to try anything different right now !ecause it has !een successful" The feed to the unit com$rises %acuum gas oil sometimes atmos$heric gas oil and light cycle oil directly from our FCC unit" .n resid cracking season we ha%e fed reduced crude and %acuum tower !ottoms into the unit" &ll of these feeds are direct from their units" (e ha%e at times though had to slo$ some oil to a tank which unfortunately is not gas !lanketed" >o far we ha%e !een lucky" (e ha%e not had any ma@or $ro!lems" 0onitoring for $ressure dro$ without =8 cells across e<changers where you are dealing with 3 to '333 $si $ressure gauges range is kind of hard to see a difference in $ressure dro$ !uild u$ from time to time" (e are monitoring the tem$eratures in the e<changers" The feed tem$eratures change de$ending on what the feed to the unit is so heat transfer coefficients %alues are a little hard to calculate as well" Our hydrogen is mi<ed with oil downstream of the feed e<changers !ut u$stream of the fired reactor charge heater" A&R;OC(CG# &gain normally the hottest shell in the feed effluent e<changer train will need some ty$e of $eriodic cleaning" .deally that is longer than your turnaround cycle" The cold heat $reheat shells ty$ically do not foul a lot" ;ater on it is $ointed out and it is mentioned in the /uestion that one methodology is to use some makeu$ gas or recycled gas in@ection into the feed to reduce fouling" That has worked in some units !ut for other units it has not" Finally at the end of that trick a list of a$$roaches you are u$ to additi%es and the use of antifoulants and antio<idants to try to e<tend the cycle length" A.GFOR=# Regarding the /uestion -has anyone tried an antifoulant in@ection of the ser%ice? - we ha%e used antifoulants successfully many times in these a$$lications" 0ore im$ortantly . wanted to go through a little !it of what was not $ro%ided in this /uestion that is really critical to understand the nature of the fouling and then trying to design a solution around it whether that !e mechanical o$erational or chemical" >ome key information that is missing from the data $ro%ided is characteri1ation of the feedstream itself" Things that need to !e identified and tests that should !e run are first the !romine num!er which would gi%e a measure of unsaturated material since a high degree of unsaturates may !e indicati%e of a higher fouling rate" Filtera!le solids and e<isting gums should !e measured on a re$resentati%e sam$le" This would indicate a $otential to de$osit e<changers or carry through to the reactor !ed" 8yrolle nitrogen should !e measured" This would /uantify the le%el of nitrogen !ased fouling $recursors which can sometimes !e %ery significant in regards to fouling" Finally total acidity and metals content should !e identified" &cids either as a result of feedstock contamination or naturally

occurring and metals that may !e either entrained or dissol%ed in the feed can catalytically accelerate fouling" Trying to sol%e this $ro!lem or gi%e some direction on this s$ecific instance really needs some more characteri1ation work on the feedstream itself !efore an effecti%e chemical solution could !e a$$lied" ;;OH= (.GGCR 2Conoco4# One of our FCC feed hydrotreaters e<$erienced this fouling $ro!lem a$$arently due to an air leak or other $ro!lems in the %acuum tower" (e fi<ed the %acuum tower and ha%e not e<$erienced the fouling again" %uestion 12 1(at is t(e industry2s eA/erience &it( corrosion@erosion effects on alloyed reactor effluent eAc(angers in (ydro/rocessing units) 1(at ne& metallurgy 7e.g.- du/leA stainless steels9 (as "een tested and@or used for reactor effluent coolers 7and associated /i/ing9 to com"at ammonium "isulfide corrosion) >nder &(at conditions 7e.g.- 0elocity- DH!HS concentration9 (a0e t(ey "een tested or used- and &(at (as "een t(e eA/erience &it( t(em) T&>MCR# This /uestion is one that has come u$ many times !efore during G8R& meetings in one form or another" .t is often a case of economics when you are using a $articular alloyed effluent e<changer" This has to !e @ustified during the design stage" .n one of our units we ha%e .ncoloy 733 which has !een used with e<cellent results from an erosion corrosion stand$oint" This $articular e<changer does not ha%e symmetrical $i$ing which . will mention in a moment and it has a three !ank arrangement" There is $erha$s some e%idence of maldistri!ution !ut no e%idence of erosion?corrosion" Ty$ically we like to ensure that !oth the metallurgy and the $i$ing design are correct and that the standard design criteria are followed" (e strongly !elie%e in symmetrical $i$ing" .t is essential for longe%ity of e<changer life when ser$entine tu!e design is used" Ao< header arrangements $ro%ide /uite satisfactory o$eration although we ha%e o!ser%ed !oth sidewall erosion and corrosion in one effluent e<changer" O!%iously it is e<tremely im$ortant also to ensure that you ha%e good water in@ection and we design for indi%idual water in@ection to each $ass inlet" The ty$ical ma<imum tu!e %elocity is around 23 feet $er second at the inlet $i$ing to the e<changer" The ty$ical water in@ection re$resents a!out fi%e $ercent of the feed flow rate with the water effluent ha%ing a ma<imum of a!out four $ercent of ammonium !isulfide salts" ;ast year we heard from the $anel figures from two $ercent to eight $ercent !ut we standardi1e at a!out four" HR. and .F8 ha%e no e<$erience with =u$le< stainless steel and we ha%e used car!on steel killed car!on steel and that is a function of the H2> concentration" (e ha%e used '21 '15 and '*6 stainless steel" . can say that car!on steel is $retty !ad news though" For the last $art of the /uestion most of our licensees ha%e e<amined the inlet and outlet $i$ing of the effluent coolers during $lanned turnarounds using :T testing methods" =uring o$eration we to recommend thermal infrared techni/ues to determine whether there is maldistri!ution from !oth tem$erature and flow and we find that there are lots of s$ecialist com$anies that come in and do that" The chea$er way of course is to !uy your own camera in%est a few thousand dollars and do it that way" RO0&G# &mmonium !isulfite salts will de$osit in effluent coolers if the $roduct of the ammonia and H2> $artial $ressures e<ceeds 1*3 $sia2" This is easily attained in %acuum gas oil units and a water wash must !e used to $re%ent solid de$osition" Car!on steel is acce$ta!le if the %elocities are limited to 23 feet $er second and the concentration of ammonium !isulfites limited to fi%e $ercent" (e recently re$laced the car!on steel effluent coolers on our largest unit with alloy 223+ du$le< !undles due to re$eated failures of these !undles" The shell side inlet %elocities were almost *3 feet $er second on this unit" :se of higher grade du$le< materials will allow higher %elocities and salt concentrations howe%er we ha%e not o$ted to do this since our water wash rate has !een set !y the re/uirement to ha%e 23 $ercent water in the li/uid $hase after in@ection" There ha%e also !een recent re$orts of entrainment of a/ueous water into the se$arator %a$or outlet line at higher salt concentrations" This a$$ears to set an u$$er limit of a!out ten $ercent ammonium !isulfide no matter what the metallurgy of the coolers" C&.G# .n our =elaware City $lant the only erosion?corrosion $ro!lem we ha%e had is on the reactor effluent e<changers" (e had to re$lace a !undle and $ill!o< due to $olythionic acid and corrosion" This was due to the fact that neutrali1ation was not done $ro$erly" The first three e<changers off the reactors are '3* stainless steel tu!e material" The fourth e<changer is car!on steel followed !y eight air coolers" The tu!es and the header !o<es of the air coolers are .ncoloy 733"

The inlet and outlet $i$ing for the air coolers is car!on steel" The $i$ing configuration has !een changed to a concentric flow $attern" The diameter of the $i$ing has also !een enlarged to a lower %elocity" There is also water and chemical in@ection in the u$stream $i$ing" &t our ;ouisiana $lant we e<$erienced some erosion?corrosion in the car!on steel tu!es of our reactor air effluent coolers in one of our hydrotreaters as well" (e ha%e successfully used CFAR.TC on one train in this ser%ice and ha%e @ust ordered a new cooler made of .ncoloy 72+ for the second train" FO>TCR# >ince we are running high concentrations of Bene1uelan crude this is a $articular $ro!lem for us" .n fact we are $erforming a com$rehensi%e re%iew of our ammonium !isulfide susce$ti!ility" .f you are contem$lating or already running higher nitrogen crudes like some of those from Bene1uela . recommend $erforming this re%iew $rior to this o$eration if $ossi!le" (e chose du$le< stainless steel for the effluent air cooler tu!es for our new CFHT" (hile du$le< stainless steel is less e<$ensi%e than some other alloys the welding and fa!rication is to !e %ery carefully watched# things like the selection of the weld $rocedure the welding rod metallurgy and /ualifying $rocedures for the welders" CrosionFcorrosion of the inlets of the car!on steel tu!es is a common $ro!lem for us in our older units" For these we are in%estigating the use of ferrules 2essentially a >> insert4 for the inlets of the coolers where most damage takes $lace" &gain the de%il is in the details of fa!rication" The trick here is that the ferrules ha%e to !e carefully ta$ered to $re%ent locali1ed eddies at the end of the ferrule" JO>CCM# (e ha%e a 223+ du$le< stainless steel shell and tu!e e<changer in high $ressure '333 $sig ser%ice" The e<changer is se$arator off gas and wash water on the tu!e side %ersus recycle gas" .t has !een ser%iced since 1992" .n 199+ we $ulled the e<changer offline for ins$ection due to the ser%ice change in the new a$$lication" The ins$ection showed no %isi!le corrosion or mechanical defects" Belocity at the inlet is 15 feet $er second and the salt concentration in the decanted water is 3"' weight $ercent" AOA RO==CH 2Roddey Cngineering >er%ices .nc"4# . refer e%ery!ody to the 8iehl article that has !een discussed in years $ast at G8R& meetings which discusses inF de$th the $henomenon of %elocity and salt concentration and the M factors which affect the corrosion susce$ti!ility to e<changers" On the in@ection of water . heard one of the $anelists say that they in@ect water to each one of the !ays" (hile that can !e done %ery successfully and it has !een on some units there ha%e !een $ro!lems in units where water in@ection to each !ay had !een tried" .t is tough to mi< water and ha%e a three $hase system in a downflow en%ironment" (hen you in@ect it downflow there should !e a no11le or s$ray" .t is a lot easier to mi< three $hases when you ha%e got an u$flow condition and it is a lot easier to $redict the flow regime in an u$flow condition where good mi<ing is achie%ed" . will caution you a!out in@ecting into each one of those !ays" CR&.G H&RBCH 2:O84# For se%ere ser%ice the use of alloy tu!es may !e desira!le" &lloy construction not only $ro%ides ma<imum insurance against corrosion !ut it can also allow certain design limits on %elocity M$ and !isulfide contents to !e rela<ed" Howe%er it should !e noted that rela<ation of the GH*H> design limits can ha%e an ad%erse effect on downstream $i$ing and e/ui$ment" .t should also !e noted that while alloy construction minimi1es GH*H> erosionF corrosion $ro!lems other forms of attack can !ecome $ro!lematic" Ta!le 1 $ro%ides recent sur%ey data with res$ect to the e<$erience with alloy construction in reactor effluent air cooler 2RC&C4 ser%ice" .n Ta!le 2 these data are sorted !y material" &lloy 733 >'173' 2du$le<4 T$ '21 and &lloy *33 2monel4 ha%e all $erformed well" &lloy 72+ should !e a !etter choice o%er &lloy 733 !ut e<$erience to date is limited" T$ *'3 >'1+33 2du$le<4 and &loni1ed car!on steel ha%e all failed for reasons gi%en in the ta!ulation" >ur%ey data with res$ect to e<$erience with alloy $i$ing in ser%ice downstream of the RC&C is as follows# K Bery few $lants ha%e used alloy construction for RC&C inlet or outlet $i$ing" K Two $lants with outlet $i$ing of >'173' ha%e had no $ro!lems after fi%e years and se%en years of ser%ice res$ecti%ely" K One $lant used &lloy 733 inlet $i$ing which failed !ecause of $olythionic acid stress corrosion cracking" K One $lant used HFFmodified $i$ing which failed !y chloride stress corrosion cracking in three years" &lloy 733 suffers from the same shortcoming as the austenitic stainless steels namely susce$ti!ility to intergranular 2$olythionic acid4 stress corrosion cracking if used in the sensiti1ed condition" .f &lloy 733 is to !e used for headers the car!on content must !e low 2!elow 3"3',4" &lloy 72+ is a $referred choice as it contains sta!ili1ing element" Ta!le 1 Reactor Cffluent &ir Coolers with &llo% Construction
Plant KD NH4HS Peak InjectionWater Balance Tube Design

02 03 04 07 08 10 13 13 13 14 14 15 18 19

0.23 0.61 0.19 0.31 0.03 0.25 0.44 0.44 0.44 0.43 0.43 2.00 0.24 0.20

(wt-% 4.7 5.4 9.5 6.0 4.8 5.3 5.5 5.5 5.5 3.5 3.5 17.2 3.0 10.3

!elocit" (#is 6.7 5.8 4.6 6.7 6.7 4.0 4.9 4.9 4.9 5.2 5.2 5.8 4.3 5.8

M S M S S S M M M M M M S S

$ %i&e Hea$ers (!r Y 2+ 17+ N 4+ Y 4+ Y +1 N 2+ P 0** P 6+ P 2+ N 8*** N Y Y Y ,9+ 16+ 12+

'aterial (eature s s Alloy 825 Alloy 800 S31803 S31803 S31803 Alloy 825 S31500 U-Tube S31803 U-Tube Alloy 800U-Tube )llo" *++ )llo" 825 )llo" *++ Tp 321 U-Tube Tp 321 U-Tube

26 0.22 5.1 4.6 M N 8+ S31803 30 1.06 4.5 2.7 M N 9~*~* Alloy 800 32 8.10 13.8 4.0 M N 3 Tp 430 32 8.10 13.8 4.0 M N 11**** Alloy 800 34 0.43 3.3 6.4 S N 1+ Alloy 800 825 o! 39 0.23 5.8 4.3 M N 1 Alo" #S U-Tube 39 0.23 5.8 4.3 M N 26+ Alloy 400 U-Tube 40 0.68 12.4 - S Y 22+ Alloy 400 U-Tube 41 0.24 5.6 10.1 S N 9**** S31803 44 0.26 4.3 3.0 S Y 2+ Alloy 800 45 0.67 8.6 7.3 M N 7+ S32304 98 $ $ $ $ $ 9+ Alloy 800 -

Gote KK Failed !y sulfide cracking at startu$" Gote KKK Failed following 2 years of $lant downtime" Gote KKKK =estroyed in a fire" M$ U Calculated M$ Fluid Corrosi%ity Factor GH*H> U Calculated Foul (ater &mmonium Aisulfide Content 2wtF,4 Belocity U Calculated 0a<imum Tu!e Belocity 2m?s4 (ash (ater .n@ection > U >ingle 8oint :$stream of RC&C 0 U 0ulti$le 8oints to .ndi%idual Aundles Aalanced Header =esign 2i"e" Aalanced .nlet?Outlet 8i$ing Configuration4 ? H U Hes 8 U Aalanced .nlet :n!alanced Outlet :n!alanced G U :n!alanced Ta!le 2 8erformance of &lloy Tu!es in Reactor Cffluent &ir Coolers 0aterial >ur%ey Results &lloy 733 :sed in 9 $lants" Go failures !y erosionFcorrosion"

One failure !y $itting in a coastal unit after 2 years idleness" Current li%es u$ to 16 years" &lloy *33 :sed in 2 $lants" Go failures" Current li%es u$ to 25 years" >'173' :sed in 5 $lants" Go corrosion failures" One destroyed !y fire" Current li%es u$ to 7 years" &lloy 72+ :sed in 2 $lants" Go failures to date" Gew installationsI OM to date" Ty$e '21 :sed in 2 $lants" Go failures to date" Current li%es u$ to 15 years" >'1+33 :sed in 1 $lant" Failed !y sulfide stress cracking on startFu$ .m$ro$er weldment microstructure Ty$e *'3 :sed in 1 !undle" Failed in ' years" C> w?&luminumFrich surface :sed in 1 !undle" Failed in 1 year" >'2'3* :sed in one $lantI OM after 6 years" %uestion 13 Are refiners ins/ecting t(e /i/ing into and out of t(eir reactor effluent coolers) If so- &(at met(ods are /referred) 0&;CM# This /uestion deals with ins$ection of $i$ing into and out of the reactor effluent coolers" From a design stand$oint we would recommend that $ro%ision !e made in the $i$ing for corrosion $ro!es" &fter the unit is in o$eration there should !e an ins$ection $rocedure esta!lished to routinely ins$ect these $i$es while the unit is o$erating" .t is im$ortant to closely ins$ect these $i$es at each turnaround to document the effects of corrosion" The $atterns of corrosion can !e monitored $articularly if you will set u$ your ins$ection $rocedure to look at high tur!ulence areas" The $i$e should !e checked for corrosion in at least four $lanes" RO0&G# (e are currently relying on ultrasonic thickness measurements" (e take :T readings u$stream and downstream of all welds on all el!ows and also at the outer most $oint which !isects the angle of that el!ow" The three $hase flow which e<ists in these coolers makes it difficult to assure e%en flow distri!ution of the water wash and we generally re/uire symmetric inlet and outlet $i$ing on these e<changers to minimi1e flow maldistri!ution" (e are also considering a new techni/ue which would allow us to take mo%ing radiogra$hic scans of this $i$ing and dis$lay it and %iew it digitally as o$$osed to on film as is done with normal < ray techni/ues" This will allow us to detect $itting which might !e missed !y s$ot :T readings" FO>TCR# (e ha%e used radiogra$hic e<amination for many years due to the un$redicta!le locali1ed nature of ammonium !isulfide and ammonium chloride attack encountered in these systems" VFray also allows you to e<amine the areas co%ered !y insulation" :T thickness methods tends to get s$ecific $oints and does not really allow a com$lete $rofile of your $i$e" &utomated :T scans 2utili1ing crawlers4 can !e used to gi%e a more thorough measurement !ut the surface must smooth for these to work" F:>>C;;# .n 8ort &rthur we ha%e a 1 533 $sig :O8 :ni!on unit that hydrotreats a!out *3 $ercent of the feed to our FCC:" (e ha%e identified the $i$ing around the effluent air fan as !eing %ery critical" (e use ultrasonics to ins$ect it" (e ins$ect it once e%ery si< months and we ha%e /uite a few more thickness monitoring locations on this $i$ing than we would ty$ically ha%e in other ser%ices" (e ha%e had to re$lace $ortions of this $i$ing on two occasions" The first one was due to erosion" :O8 had originally installed a mi<ing $late downstream of the air fans which caused this erosion" . am sure that there was a

good reason for the $late !ut we took it out and we ha%e not had the $ro!lem again" (e ha%e also re$laced $ortions due to general thinning" H&HG# . would concur with most of what has !een said already $articularly a!out checking for $laces of high %elocity and $otential erosion $oints" (e ha%e learned the hard way on that a few times" .n addition to the methods already discussed we are using sheer wa%e and eddy current to ins$ect some of our $i$ing" (e ha%e found that to !e /uite effecti%e if you get an e<$erienced s$ecialist to do your scanning for you" A.;; JOHG> 2Te<aco RE0 .nc"4# . agree with the $anel i"e" <Fray and do your !est to look at all of those $oints that you feel are trou!lesome" &lso if you ha%e a change in $rocess and you ha%e not !een measuring go !ack to measuring fre/uently the thicknesses of metal in and out of those air fans" &ny significant change in $rocess will make a change" On the last /uestion we found some tu!e laminations on 733 alloy tu!es in fin fans and traced it !ack to manufacturing $ro!lems" (e re$laced those with 72+ alloy and ha%e not seen any $ro!lems with 72+ alloy" (e understand another refiner on the (est Coast had seen some laminations with 733 alloy tu!es as well" >o !e aware of that $ro!lem" 3. atalysts and atalyst Sulfiding %uestion 1! Silica u/ta+e on (ydrotreating catalysts is "ecoming an increasing concern. Is t(ere a &ay to monitor u/ta+e to effecti0ely /lan c(angeouts) Are t(ere ne& reactor design criteria or ne& catalysts on t(e mar+et to (el/ im/ro0e run lengt() F;CTCHCR# The key to $lanning change out is accurate measurement of silicone in the feedstock" Aecause silicone is added to a delayed coker at %aria!le rates !ased on the antifoam re/uirements which %ary with the coking cycle silicone in the coker na$htha is %aria!le" This means that s$ot measurements of silicone content will %ary widely and will not accurately re$resent the a%erage silicone of the coker na$htha feed" Therefore a%eraging a num!er of s$ot sam$les taken throughout the coker cycle should accurately re$resent the actual a%erage silicon content" The !est measurement howe%er of a%erage silicone content of coker na$htha feedstock is the a%erage silicone u$take o%er a catalyst cycle" &k1o Go!el recommends that good records !e ke$t of s$ent catalyst silicone content" This is !est done !y o!taining three se$arate catalyst sam$les when the catalyst is discharged from the unit" These sam$les include# to$ of the main catalyst !ed" This sam$le will indicate the silicone u$take ca$acity of the catalyst grade used" >econd we recommend a sam$le from the !ottom of the reactor which identifies whether the !reakthrough has occurred" Third a com$osite sam$le which indicates the actual silicone $icku$ of the unit during the run" .f a refiner monitors the antifoam usage at the coker o%er the run and measures the silicone $icku$ of the catalyst during the cycle the delta !etween the two will gi%e a good measurement of fraction which has !een a!sor!ed !y the catalyst" This num!er when a$$lied to ongoing silicone antifoam usage can then !e used to $redict the silicone fed to the coker na$htha hydrotreater as accurately as feed analytical measurements" A&R;OC(CG# One additional factor to gi%e you an idea when you are a!out to fall off the cliff is monitoring sulfur content on the na$htha hydrotreater" Just !efore your silicon ca$acity is all used u$ you will start to see s$ikes on the nitrogen" 0ore and more refiners are also looking at nitrogen as hea%ier crudes are !eing introduced to their crude slate" >o that is a warning that will gi%e you a!out two weeks !efore you are out of !usiness" HCGMC# (e $ractice those things that 0r" Fletcher mentioned" (e monitor >ilicon 2>i4 u$take !y tracking silicone consum$tion at the =elayed Cokers and direct measurement of >ilicon in the feed to the Ga$htha Hydrotreater" (e reconcile these %alues with analysis of the s$ent catalyst to assist in $lanning future catalyst changeouts" (e continue to use &k1o Go!el)s MFF7** in our Coker Ga$htha Hydrotreaters with good results" This catalyst and similar catalysts from other %endors are designed with high surface area to maintain acti%ity while remo%ing the silica" . would also refer you to the 199* G8R& QE& transcri$t $age 127" .t contains an e<cellent gra$h $ro%ided !y 0ehmet &sim of &k1oFGo!el correlating >ilica u$take to fresh catalyst surface area" Finally . would like to $oint out that the !est way to im$ro%e this situation is to reduce silicone consum$tion at the =elayed Cokers" 0ost o$erators of =elayed Cokers in@ect more silicone antifoam than is re/uired" Gew techni/ues to control Coke =rum outage can go a long way to manage and ultimately reduce silicone addition" JO>CCM# =ue to a contamination in the crude we e<$erienced silicon in the straight run feed to a na$htha desulfuri1er" &fter identifying the contamination the catalyst was changed out four times within a si< month $eriod without $oisoning

the downstream reformer catalyst" The unit charge rate and daily feed analysis !y atomic a!sor$tion 2&&4 were used to calculate a total silicone weight on the catalyst" Com$aring the calculated weight to the catalyst %endor estimates and analysis of to the $receding catalyst a $rediction was made to $lan the ne<t catalyst changeout" The && instrument was cali!rated using a s$ike feed to a 3"' detection limit" &fter each catalyst change out a sam$le of different !ed locations in the reactor were analy1ed for metals to determine the take u$ for future change out $lanning" (e changed catalyst after first shut down to a higher surface area a higher $ore %olume catalyst for higher silica takeu$ !ased on research com$leted !y another refinery e<$eriencing the same contamination" (e considered inserting test $lugs different catalysts in the to$ of the reactor for the e%aluation of silica take u$ %ersus catalyst %endor estimates $er one catalyst manufacturerOs recommendations" Our $ro!lem occurred o%er a year ago" (e did an e<tensi%e literature research" & technical $a$er $resented !y Terry Reid of &k1o entitled -Coker Ga$htha Hydro$rocessing# >olutions for Trou!leFFree O$erations- is an e<cellent resource" The $a$er clearly summari1es o$erating catalyst %aria!les not recently a%aila!le in one location until now" The $a$er clearly defines guidelines some of which we learned through $ainful e<$erience" T&>MCR# . agree with the $receding comments" 8erha$s you might want to consider ha%ing a s$are charge of catalyst !ut that is always an e<$ensi%e o$tion" One way to im$ro%e the run length of course is to design the reactor with a s$ace %elocity of a!out two or less" The first consideration though is for the diolefins and the second consideration is for hydrotreating when it comes to the silica $oisoning" Gow our e<$erience is that you can $ro!a!ly go u$ to a!out eight weight $ercent of silica as >.O2 with the co!alt moly catalysts !efore you can say that the catalyst is essentially dead" The surface area is %ery im$ortant to assure longe%ity of o$eration" The form of the silica which affects the catalytic $erformance is not fully known !ut is assumed to !e >.O2" .t is also assumed that %irtually all of the silica is from the antifoam agents used in the coker o$eration and it generally goes to the na$htha cut" The formula for that antifoam is generally known !y the antifoam manufacture and you can get some of that information from your su$$liers" .t is generally su$$lied in a $olyglycol form" For total life estimation this has !een mentioned already you need to know the %olume of catalyst in the reactor" (hen you are a$$roaching that eight $ercent calculated num!er that is when . think you will see some !ad $erformance" &s guidelines we ha%e e<$erience with feed silica le%els of !etween one and two $$m in Germany and similar le%els in .taly and >weden" For :">" domestic licensees we ha%e units designed for u$ to fi%e weight $$m of silica in the feed" For >outh &merican we are looking at units ca$a!le of handling 13 weight $$m in the feed" :sually for that ty$e of situation you need more catalyst and you need a surface area of a$$ro<imately 233 s/uare meters $er gram $er cc" There are limits howe%er and there is a need to im$ro%e the catalyst and ha%e a higher $ore %olume for higher tolerance" The main idea is to design the catalyst %olume which will gi%e you at least a two year life !ased on the e<$ected feed silica content" (atch your delta T and watch your delta 8 and you should !e in good sha$e" & delta T of less than *3 C is good and you may ha%e to recycle to kee$ it at this le%el" =&B.= =iC&0.;;O 2Criterion Catalyst Co"4# . agree with e%erything the $anel has said" &dditionally there are catalysts s$ecifically designed for silica u$take that will hold more than the le%els 0r" Tasker mentioned" Criterion =GF1*3 has !een analy1ed at 11 wt, >i 222, >iO24 after remo%al from a commercial GHT treating 133, coker na$htha" One other thing we ha%e o!ser%ed with customers" =e$ending on the age of the catalyst and the unit design if you are s$iking silica in your feed it can carry through e%en though the catalyst has not reached its normal u$take ca$acity" >o if you ha%e a critical ser%ice like a reformer downstream you might want to $ay close attention to your antifoamer addition and !e aware that if you $ass s$ikes through they will get into the $roduct" (hen you get !ack to normal addition rates the $roduct will !e silica free again" %uestion 1# $i0en t(e reduction in ?@B ratio t(at occurs during t(e catalyst regeneration /rocess- &(at is normally acce/ted as t(e minimum a0erage /article lengt( for eAtrudate catalyst loaded into a (ydro/rocessing reactor) 1(at is t(e minimum acce/ta"le /article lengt(- "elo& &(ic( /ressure dro/ and flo& maldistri"ution /ro"lems are eA/ected to occur) C&.G# &s a general rule once the length o%er diameter 2;?=4 ratio dro$s !elow three you will see a noticea!le increase in the $ressure dro$" Hour catalyst su$$lier can su$$ly s$ecific information on a gi%en reactor configuration" F;CTCHCR# (e !elie%e that this answer really has three as$ects# 214 (e !elie%e that the minimum a%erage length for

regenerated catalyst is a!out 2"+ millimeters for 1?23th inch diameter catalyst" (ith this catalyst length the $ressure dro$ will $ro!a!ly not !e a $ro!lem in the ma@ority of units" The a%erage length should !e greater than 2"7 millimeters which should gi%e a satisfactorily low $ressure dro$ for any unit a!le to use 1?23th inch diameter catalyst" This minimum should !e increased as the catalyst diameter grows '"+ millimeters for 1?13th inch and an ;?= of at least of at least one for larger si1esI 224 e/ually im$ortant in determining fitness for use is the catalyst length distri!ution" The content of short catalyst $articles has a large im$act on the $ressure dro$" Generally the concentration of catalyst $articles with an ;?= of less than one should !e less than 1+, of the total catalyst $articles" Fines content should !e less than one $ercent !y weightI 2'4 other im$ortant considerations are the side crushing strength 2W'"+ $ounds $er millimeter4 and the Com$act at Aulk =ensity 2CA=4 2D13, increase com$ared to fresh catalyst4" The CA= is directly linked to %oid %olume which has a large im$act on $ressure dro$" A&R;OC(CG# The real issue with how much degradation and down si1ing of $articles you can tolerate is what $ressure dro$ you can tolerate" C%ery new unit is designed for a start of clean $ressure dro$ and has an allowance for fouling" That fouling allowance can !e used u$ with $articulates or it can !e used u$ as you install a smaller catalyst and e%ery catalyst will !ecome somewhat smaller on regeneration" One data $oint that we ha%e is for a catalyst that started out as 1?15th inch catalyst with a '#1 ;?= ratio" &fter one regeneration and 2of course4 screening out fines the ;?= ratio dro$$ed to 2 to 1 and that unit saw a$$ro<imately a 13 $ercent increase in $ressure dro$ which was not a $ro!lem for them" T&>MCR# Of course this /uestion was aimed at ty$ical hydro$rocessing catalysts and $erha$s we should include the growing num!er of !ottoms u$ grading $rocesses such as our HFOil $rocess which uses large /uantities of catalyst" Of course we would like to ha%e a decent way of reusing that catalyst and regeneration !y itself does not /uite cut the mustard" (e ha%e a new $rocess which . ha%e mentioned !efore at other G8R& meetings the re@u%enation $rocess" That allows us to significantly reduce our catalyst costs !y re$rocessing the catalysts instead of sending it to metals reclamation" >o o!%iously we ha%e a great concern o%er the $otential degradation of the e<trudate when !eing handled in regeneration and re@u%enation $rocesses" Aut we find that the si1e reduction or $article !reakage is ty$ically /uite low" The ty$ical ;?= ratio for the 1?'2nd inch e<trudate is in the range of two to fi%e" ;?=s of 1"+ to 2 are acce$ta!le !ut ;?=s of 1"3 or less are not so desira!le" Gow for fi<ed !ed o$erations this could cause $ro!lems with maldistri!ution" The smaller the $article the greater the likelihood that it will migrate to the to$ of the !ed in an e!ullated !ed" >o the $ro!lems faced for ; o%er =s of one or less is loss from the !ed as catalyst fines" (e should try and eliminate those $articles in the regeneration or re@u%enation $rocess !y screening" This of course is fairly ty$ical for most e< situ regeneration $rocesses for ty$ical hydro$rocessing catalysts" J.0 >C&0&G> 2CR. .nternational .nc"4# C< situ catalyst regeneration $rocesses ha%e !een designed to minimi1e attrition and loss in ;?= ratio during the regeneration $rocess" >creening of the catalyst is also standard $ractice to remo%e the chi$s and fines generated during the use and unloading of the catalyst from the reactors" ;?= ratios in the 1"+ to three range are ty$ical of regenerated material and normally not a concern for most units" .f a customer has a reactor that is $articularly sensiti%e to $ressure dro$ CR. offers an additional ser%ice of length grading to remo%e short $articles that are not remo%ed !y standard screening" This allows for the return of a $roduct with a%erage lengths com$ara!le to fresh" %uestion 1: 1(at (ot (ydrogen stri/ /rocedures are used to free a (ydrotreating catalyst "ed of (ydrocar"ons and H2S for t(e /ur/ose of dum/ing t(e catalyst) C&.G# .n our ;ouisiana $lant after the charge is taken out the reactor section is swe$t with hydrogen at +33LF until we can not detect water in the high $ressure se$arator" Tem$eratures are then cut for reactor cooldown" The recycled gas flow continues until the reactor is cooled down to 233 to 173LF at which time once through nitrogen is used" ;i/uid nitrogen su$$lied !y a truck is %a$ori1ed to 3LF and cools the reactor down to 13+LF" F;CTCHCR# &k1o Go!el recommends cutting out the heater at around '+3LF allowing the reactor to !egin cooling down" &$$ro<imately 12+LF shut down the treat gas com$ressor slowly reducing the $ressure while maintaining a slight $ositi%e $ressure to ensure no o<ygen enters the system" The catalyst can !e maintained indefinitely under these conditions" >ome %ariations can include stri$$ing with hot sour hydrogen at less than 633LF" The H2> content must

remain a!o%e 1 333 $arts $er million to $re%ent reduction of the metals" (ashing with ;CO or higher aromatic content feedstock $rior to hydrogen stri$$ing is sometimes used to achie%e %ery low hydrocar!on contents" FO>TCR# Our $rocedures call for a 13 hour hot hydrogen swee$ of the catalyst !ed at 533LF" (e then cool down to a$$ro<imately 1+3LF on hydrogen circulation !efore nitrogen $urge and cooldown" H&HG# On our diesel hydrotreater we swee$ with hydrogen in a recycle mode at 533LF and 1 333 $ounds of $ressure for three to fi%e hours" Then we switch to li/uid nitrogen again as we cool" (e swee$ once through and then we $ressure u$ with nitrogen to a!out 1 333 $ounds and then %ery /uickly lower the $ressure to 1ero" (e call this a -$o$"- (e go through nitrogen $o$s se%eral times" (e found that %ery effecti%e in mo%ing remaining hydrocar!on out from low $oints to where we can drain it off" This seems to ha%e reduced our total shutdown time considera!ly" HCGMC# (e closely monitor and control reactor o$eration during startu$s shutdowns and $rocess u$sets to stay within $redetermined guidelines" 8ro$er monitoring and control of the reactor tem$erature and $ressure cou$led with $ro$er documentation and record kee$ing should e<tend the life of the reactor" . would also add that $ro$er training of fire fighting and emergency res$onse crews to take a$$ro$riate $recautions around the reactors will also directionally e<tend their life" =uring turnarounds we ha%e used automated ultrasonic scans acoustic emissions measurements and traditional internal ins$ections to monitor %essel integrity" JO>CCM# The only thing . ha%e to add is for units handling hea%y feedstock we usually switch to a light %irgin feed !efore shutdown" 8CTCR>OG# (e ha%e shortened the time for the hot hydrogen stri$ down to @ust a few hours and we watch to see if any hydrocar!on accumulates in the se$arator downstream" >imilar to 0r" Cain)s comment we would use diesel to flush out the hea%y material in our FCC feed hydrotreater" &fter this cou$le hour swee$ we switch to nitrogen" .f you ha%e a multi$le reactors in a hydrotreater and are only going to change catalyst out in the lead reactor the hot hydrogen stri$ could lead to desulfiding of the other reactors if you do not ha%e an H2> source" (e ha%e gone to shortened times and go with nitrogen cool down" >&0:C;># . agree and directionally we are mo%ing away from the historical longer hot hydrogen swee$s" (e see diminishing returns once the hot se$arator le%el sto$s !uilding" (e are going to more nitrogen use" T&>MCR# 0ost of the comments were already made" (e generally look at a guideline for hydrogen stri$$ing of a!out 233 standard cu!ic feet of $ure hydrogen $er cu!ic foot of catalyst" That seems to !e /uite effecti%e" The tem$erature at which you do it of course will !e a function of the feed that you ha%e in the system !ecause you want to get all of that material out and the duration" O!%iously we want that as minimum as $ossi!le and ty$ically 12 hours will do it" The nitrogen swee$ing is a good way to go" Aut of course that de$ends on your com$ressor" &s has !een mentioned you may want to in%est that e<tra money and !ring in li/uid nitrogen and do the swee$ as a once through o$eration" %uestion 1; 1(at le0el of refinery engineering su/er0ision is /racticed in t(e loading of catalyst in (ydrotreating@(ydrocrac+ing reactors) FO>TCR# ;HOG=C;;FC.TGO Refinery has '7 fi<ed catalyst !ed %essels and a working in%entory of *"7 00 $ounds of catalyst" Rather than assigning the unit engineers to manage this asset we ha%e centrali1ed this under 2 Catalyst Coordinators" They do e%erything related to catalyst" ;et me gi%e you a list of their res$onsi!ilities# They work with the engineering o$erations and catalyst technical staff to determine !est catalyst selection and load configuration for each reactor" They design and maintain catalyst loading de%ices" They de%elo$ment catalyst handling >O8s CO8s safety $rocedures" These are custom de%elo$ed for each catalyst @o! and $ro%ided to the catalyst handling contractor for e<ecution" They $ro%ide roundFtheFclock su$er%ision of catalyst handling acti%ities during turnarounds" They maintain all fi<ed catalyst in%entories $recious metals !alances and work with financial $eo$le to $ro$erly account for these"

>ince we started this $ractice 16 years ago we ha%e had not one incident if im$ro$erly loaded catalyst" 0ore im$ortantly we ha%e had only contractor ;(=. in 16 years" Our success here is mostly due to the fact that we ha%e two %ery high /uality indi%iduals who take $ride in their work" They see that not only their work !ut the work of their contractors is done safely and e<$ertly" This might not !e for e%eryone !ut for a refinery of our si1e this hel$s our focus on catalyst issues" This allows the engineer to focus on o$timi1ing the o$eration rather than su$er%ising catalyst handlers" F:>>C;;# (e o!%iously do not ha%e as many reactors and we use $rocess engineers e<tensi%ely to su$er%ise !oth the unloading and the loading of all of our catalyst reactors in the refinery" They also work on the front end to de%elo$ the sco$e of work" They hel$ select the catalyst contractor that does the @o!" &s . mentioned we ha%e around the clock co%erage on the unloading of the catalyst" (e try to collect a good com$osite sam$le of what we are taking out of the reactor so that may!e we can learn some things a!out it and determine if it is regenerata!le" (e also ha%e around the clock co%erage on the loading" These engineers do more than @ust technical ty$e su$$ort" They coordinate the work !etween our maintenance staff and the catalyst handler so it is a $retty ma@or effort on their $art" H&HG# (e ha%e one field engineer that follows the catalyst loading and unloading around the clock in addition to some of their other duties" (e !ring in a catalyst s$ecialist to do our loading and unloading inert" >o we do not directly load" (e @ust sort of monitor and make sure they are loading as $er our diagrams and instructions" F;CTCHCR# .n general we agree with the comments stated so far" Our general o!ser%ation is that not enough su$er%ision is !eing used" (e ha%e o!ser%ed se%eral cases of maldistri!ution in hydro$rocessing units where the catalyst was dense loaded at a slant" &nd in all cases the refinery did not ha%e engineering su$er%ision during the entire loading" .n concurrence with some of the other comments we recommend that a team !e formed !etween the $ersonnel from the refinery and the loading contractor" (e further recommend that e%enness of catalyst le%els and loading density !e determined at different loading heights and checked with the e<$ectations" Further we recommend that it is essential to check the reactor internals i"e" the condition the cleanliness including the su$$ort and also look for a contractor who has a%aila!le %ideo camera monitoring during the load" HCGMC# (e $rocess 6, hea%y coker na$htha in one of our diesel hydrotreaters" The coker na$htha is coF$rocessed along with light coker gas oil straight run diesel and FCC light cycle oil" & '"+ year run was o!tained without $ressure dro$ $ro!lems" JO>CCM# (e ty$ically staff for a reactor loading with refinery engineering including !oth mechanical and $rocess engineers" The engineers are trained !y the res$onsi!le $rocess unit engineer and ha%e full authority for the direction of the reactor loading" =uring times when numerous reactors are loaded simultaneously we ha%e hired consulting engineers on retainer who ha%e e<$erience at the refinery to assist in the su$er%ision of the loading under the direction of the $rocess engineer" >&0:C;># (e ha%e a catalyst e<$ert technical e<$ert to o%ersee catalyst loading $urchases and so on" Aut we do in fact use unit engineers as 0s" Fussell descri!ed in each refinery to do the loading" (e ha%e sto$$ed the $ractice of training our engineers for inert entry and we do not allow the engineers to go in during dense loading to take measurements in inert systems" (e also are trying to use the catalyst loading com$any technology the %ideo technology where the engineer can actually !e in %oice contact with the contractor in the reactor and o!ser%e what is going on a %ideo screen" That has $ro%en %ery !eneficial" T&>MCR# . must laud 0r" FosterOs a$$roach or ;COs a$$roach" .t seems to !e a %ery useful one and %ery good engineering $ractice" From a licensor $oint of %iew we o!%iously re/uire some engineering su$er%ision for the reactor internals as well as the loading !ecause we ha%e a little !it more to $rotect" (e ha%e some guarantees that need to !e met and we ha%e to make sure that the catalyst is loaded correctly" AOA RO==CH 2Roddey Cngineering >er%ices .nc"4# . ha%e !een trou!leshooting in hydrotreaters and hydrocrackers for many years and one of the flaws with our industry is that there has !een and still is as far as . am concerned insufficient su$er%ision of catalyst loading throughout the industry" . think we ha%e underestimated the $ro!lems that are caused !y $oor catalyst loading" . am $leased to hear some of the comments from the $anel !y $eo$le stressing em$hasis on su$er%ising catalyst loading" (e offer a consulting ser%ice to train the refinery engineers on catalyst loading" . was with :O8 when dense loading

was first started" . ran dense loaders in reactors for a num!er of years" The many years of e<$erience /ualifies RC> to offer catalyst loading ser%ices" (e can either su$er%ise and coordinate the catalyst loading or we can train your $eo$le to !e !etter at doing that @o!" AR.&G 0OH>C 2Haldor To$soe4# . @ust want to add one thingI 0r" Roddey ga%e me a lead in there" (e feel that it is essential to ha%e su$er%ision" John 0iller $u!lished a %ery good two $age article in the 0ay 1976 issue of Hydrocarbon Processing on $ages +' and +* entitled -.nclude Tech >er%ice Cngineers in Turnaround .ns$ections - a!out this %ery su!@ect and what the $ay!ack was" &s an e<am$le of how things can go wrong we had one unit that did not ha%e any su$er%ision and they loaded the grading on the !ottom and the catalyst on to$" J.0 QC.A.G 2Huskey Oil4# (e do kee$ our $rocess engineers around the clock 2* hours for catalyst loading" One thing we found with the catalyst s$ecialist is they are %ery $oor in math and they will load a reactor totally wrong e%en if they ha%e a good loading diagram" They get $ounds and kilograms confused and millimeters and inches confused" .t is essential you ha%e a good $erson that knows how to do math right there" %uestion 1< *(ere a//ear to "e some ne& de0elo/ments in catalyst dense loading tec(nology. 1(at im/ro0ements (a0e "een ac(ie0ed commercially in terms of catalyst loading rate and 0olume of eAtra catalyst installed) 1ere t(ere any negati0es- e.g.- (ig(er S'R /ressure dro/) Please gi0e details of catalyst si6e and s(a/e- "ed si6eand unit ser0ice. 8CTCR>OG# (e recently used a contractor to dense load a FCC feed hydrotreater reactor as recent as last Friday" This contractor uses the Total de%elo$ed densicat system" . used to run a densicat when it was first !rought out many years ago" .t has !een more an e%olution than a re%olution in the densicat design" There was some concern for gradation of $article si1e in a radial manner" .t seemed like there would !e !igger $articles towards the outside of the reactor and smaller $articles towards the center" 8art of the e%olution of the densicat was to change from uniform linked layers of ru!!er stri$s to %arying lengths changing the sha$es of the stri$s doing a few other things on the distri!ution of the catalyst to the ru!!er stri$s" They also changed the direction and rotation e%ery 12 su$er sacks in our case" The su$er%ision @ust to tack onto the last /uestion we ha%e engineers around the clock with the catalyst com$any and they were %ery good catalyst loading com$any" The reactor that we loaded was a single !ed of 7 533 cu!ic feet a!out +3 feet in de$th" The densification that we got was %ery close to the com$acted !ulk density as $redicted !y the catalyst manufacture" &s far as the !enefits of dense loading these ha%e !een discussed at $ast G8R& sessions and %arious articles" There is some concern a!out the initial $ressure dro$ of the system" Aut we feel that the !uild of $ressure dro$ is slower with dense loading" >o if you integrate it o%er the whole run of the cycle you can $ro!a!ly ha%e a lower $ressure dro$ or a longer run !y not de%elo$ing coked areas or hot s$ots or ha%ing to cut short the cycle !ecause of some means other than $ressure dro$" &s . said !efore good dense loading does not make u$ for $oor distri!ution of li/uid and %a$or" Hou ha%e to ha%e e%erything working $ro$erly" T&>MCR# (ell there are a num!er of s$eciali1ed $rocesses for dense loading of catalysts and most com$anies ha%e either their own or $referred $rocedures" &t .F8 we ha%e the cata$ack $rocess and we generally get a!out 13 to 1+ $ercent more e<trudate in the reactors" For s$herical catalysts of course it $acks /uite well !y itself and the im$ro%ement is generally less due to this characteristic" Ty$ically we see three to fi%e $ercent im$ro%ement !ut we ha%e seen u$ to ten with s$heres" Our e<$erience has !een with e<trudate catalysts and a!sor!ants of "5 to 1"2 millimeter diameter u$ to three to fi%e millimeter diameter a!sor!ance" The e<trudate length is ty$ically four to si< millimeters long" (ith s$heres our e<$erience has !een with three to fi%e millimeter diameter s$heres" On %essel diameter we ha%e successfully dense loaded catalysts into %essels u$ to 25 feet in diameter for a!sor!ance and 1' to 15 feet diameter catalysts" (e feel that it really does hel$ from a channeling %iew$oint and we e%en recommend it for %essels as small as three feet in diameter" .t is rather difficult to get a man into something smaller than that" (hen you are dense loading you ha%e to consider what constraints you might ha%e in the system and !ed $ressure dro$ might !e one of those if you ha%e not got enough recycled com$ressor ca$acity or head" (e find that we get !etter tem$erature distri!ution and o%erall much im$ro%ed o$eration"

On the $ressure dro$ side we do see the estimated $ressure dro$s which are $erha$s four to eight $ounds higher than sock loading !ut it de$ends on the catalyst %olume" F;CTCHCR# Our colleagues in Ja$an re$ort a new loader de%elo$ed !y and called .decat" .t has a %aria!le height that allows a uniform distance !etween the catalyst !ed surface and the loading machine" Therefore theoretically this would gi%e a more uniform !ed density" &ccording to the de%elo$er this method reduces %ariations in !ulk density in radial cross section of the catalyst !ed as com$ared to a loading method in which a catalyst loader is fi<ed at the to$ of a reactor" >ome su!stantial increases in loading rate ha%e !een re$orted es$ecially when com$ared to a fi<ed $osition dense loader" .n addition this method will minimi1e catalyst !reakage and fines generation during the loading which is o!ser%ed in high free fall loading" &nother technology has !een re$orted out of Ja$an which uses laser !eam technology to ensure an e%en !ed surface during the loading" %uestion 1= 1(at analytical tec(ni5ues are "eing used on a regular "asis in refineries to 5uantify aromatics reduction in diesel and@or E$' (ydrotreaters) Ho& accurate and sensiti0e are t(ese met(ods) RO0&G# Our control la!s do not measure aromatics in either diesel or BGO hydrotreater $roducts routinely" 0ost of these analyses are $erformed in our RE= la!s" (e ha%e used F.& &>T=1'19 and su$er critical fluid chromatogra$hy or >FC &>T=+175 for diesel streams" =iesel is outside the recommended sco$e for F.& !ut it is still widely used in the industry" The re$roduci!ility determined for gasoline sam$les ranges from three to '"+ $ercent" Howe%er for diesel sam$les the &>T0 cross check $rogram re$roduci!ility is closer to ten $ercent" The color of many diesel streams makes F.& difficult and somewhat su!@ecti%e" The re$roduci!ility of the F>C method is four $ercent" Geither method does a good @o! in se$arating multiring $artially saturated molecules" They cannot generally distinguish !etween Aen1ene and tetralyn for instance" .n F.& tetralyn would !e detected as aromatics and in >FC as monoaromatics" For BGO or %acuum gas oil analyses at &shland we use an inFhouse H8;C method and this method is e<cellent for %irgin streams including residues where a se$arate ste$ is used to remo%e the as$haltenes !efore further analysis" The method se$arates the feed into saturates monoaromatics diaromatics greater than dies $olar aromatics with re$eata!ility for each fraction !eing three $ercent two $ercent one $ercent two $ercent and "+ $ercent res$ecti%ely" Howe%er we ha%e ne%er !een a!le to !alance hydrogen consum$tion and re$orted aromatic ring loss across either la!oratory or $lant hydrotreating reactors using this techni/ue" (e ha%e concluded that the changes in ring saturation num!ers are close to the uncertainty of the tests" 8rior to using this method we used mass s$ec method &>T0 ='2'9 with which if the o$erator was %ery meticulous $ro%ided e<cellent resolution of $artially saturated multiring aromatics" HCGMC# (e routinely monitor aromatics reduction in our high $ressure diesel hydrotreaters using su$er critical fluid chromatogra$hy" .n our FCC feed $retreaters we monitor relati%e aromatics reduction with refracti%e inde< and aniline $oint" (e are in the $rocess of de%elo$ing an H8;C method for routine use" From our e<$erience the H8;C techni/ue will !e no !etter than the >FC in terms of sensiti%ity" Howe%er the H8;C method is !etter at handling the increased concentration of $olar materials which are $resent in the gas oils" JO>CCM# (e are currently using F.&" (e are considering >>C as the test method" >>C $ro%ides a re$eata!le answer and takes a fraction of the time as F.& !ut it is more e<$ensi%e and more com$le<" (e are also using a $ectros$ect G>2'3 diesel aromatics analy1er with some success for control $ur$oses which uses mid infrared s$ectrosco$y" 8ectros$ect results are close to the F.& results and work close to >FC results as !oth re$orted !y $ectros$ect and !ased on our e<$erience" F;CTCHCR# . concur with the comments that ha%e !een made $re%iously" (e ha%e seen F.& >FC H8;C and clay gel se$arations" . guess the only comments . would add are that in concurrence with $re%ious comments F.& is not acce$ta!ly accurate no !etter than a!out three $ercent a!solute !ut is /uick and ine<$ensi%e" The >FC is slowly re$lacing H8;C as the more accurate al!eit more e<$ensi%e and cum!ersome method for gas oil aromatics" Aoth methods ha%e an accuracy of around one $ercent a!solute when $ro$erly calculated" High $ressure li/uid chromatogra$hy gi%es information on aromatics distri!ution o%er the !oiling range and is %ery useful for !enchmarking FCC feed" 8rediction can !e made as to how many monoaromatics go into the gasoline diaromatics into the ;CO three to four ring aromatics that will go to coke only" The three to four ring aromatics are %ital information for coking tendency for the FCC feed and can !e used to !enchmark resids"

F:>>C;;# .n 8ort &rthur we recently started doing aromatic saturation testing on the feed and $roduct to our :ni!ond unit on a regular !asis" (e used the Fina modified Criterion method" . do not ha%e the s$ecifics on that !ut . am sure Criterion would !e more than ha$$y to discuss the method with you" (e do not feel like the accuracy is all that great !ut the test is re$eata!le and we do see trends" (hen we take the deas$halted oil out of our :ni!ond unit the saturation of aromatics goes u$ tremendously" >o we definitely see trends with the testing" C;M.G C&R0OG& C:&=RO> 2Cco8etrol4# t(is attendee as+ed t(at t(is 5uestion "e /ut into t(e transcri/t =o you ha%e any e<$erience for reaching high yields in =0O 2u$ to +5, in %olume4 for hea%y residue with *3F+3 K13F1 mm of $enetration in a =C0CV deas$halting unit with ;8G sal%ent %acuum !ottoms o!taining +, cut of concar!on in =0O? =o those new technologies include high yields with high /uality? H.GG.G># XGO RC>8OG>CY %uestion 28 Biscuss t(e effects on acti0ity and /ressure dro/ &(en c(anging (ydrotreating catalysts from 1@<4 to 1@1:4 '.B.- and 1@1:4 to 1@284 '.B. Are t(ere any differences in effects for lo"ed 0s. cylindrical /articles) F;CTCHCR# (ith res$ect to the $ressure dro$ effects we ha%e seen a num!er of general rules of thum! that can !e used for sock loading $ressure dro$" They are 1?7 inch cylinders e/ual 1?13 inch /uadrolo!e 1?15th inch cylinders are e/ual to 1?23th inch /uadrolo!e and 1?23th inch /uadrolo!e is twice 1?13th inch /uadrolo!e" The dense loading changes these relationshi$s !ecause the cylinders do not achie%e the same density increase as is achie%ed !y the sha$e catalyst" (ith res$ect to the acti%ity effects the catalyst si1e and sha$e definitely affect catalyst acti%ity" >ha$e catalyst decreases the effecti%e catalyst diameter relati%e to the a$$arent catalyst diameter" Thus fast reactions and reactions in%ol%ing large molecules ha%e the largest si1e effects" There is $ractically no im$act on catalyst acti%ity for gas $hase reactions !etween the 1?23th and the 1?13th inch catalysts" Howe%er demetali1ation shows %ery large si1e effects with im$ro%ing acti%ity and ultimately metals ca$acity with the smaller si1es" H=> also e<hi!its a significant si1e effect of a!out 1+ $ercent !etween the 1?13th and the 1?23th inch /uadrolo!e catalyst" The H=G e<hi!its a somewhat smaller si1e effect a$$ro<imately ten $ercent" Catalyst $ore diameter feed molecular weight and si1e affect all these %alues" A&R;OC(CG# . will share with you num!ers as we go from 1?23th inch to 1?15th and then down to 1?7th inch and . am dealing with lo!e $articles now" For denitrogenation ser%ice as in hydrocracking $retreat relati%e acti%ity would go from 133 to 93 to then 53" >o there is a significant reduction in acti%ity as you go to larger $article si1e" The reason that you go the other way is !ecause you need $ressure dro$ relief in units that ha%e !een $ushed well !eyond their original design ca$acity" From a $ressure dro$ stand$oint if you start at 1?7th inch we would see almost a dou!ling of $ressure dro$ to go to 1?15th and another 23 $ercent increase to go to 1?23th" JO>CCM# O!%iously the smaller the diameter of the catalyst the less diffusion resistance there is and it is going to !e more $ronounced with hea%ier feeds" ;o!e catalyst further reduces fusion resistance" .n our commercial e<$erience at high $ressures ty$ical of lu!e oil hydrotreating the differences !etween lo!e and cylindrical were not measura!le" .n commercial o$eration" Aut the differences were a$$arent at the $ilot $oint le%el" %uestion 21 A num"er of ne& (ig(-acti0ity (ydrocrac+ing /retreat catalysts (a0e "een introduced during t(e /ast 2 years. 1(at is t(e commercial eA/erience &it( t(ese catalysts) H&HG# (e $ilot tested se%eral of the new hydrocracking catalysts that are out and selected one !ased on H=G acti%ity" (e ha%e since loaded these and ha%e seen /uite a !it of success" Our (est Coast refineries ha%e seen a one to two year cycle length on these nickel moly catalysts to date and so far they are e<ceeding $ast cycle $erformances o%er their $re%ious catalysts" A&R;OC(CG# To$soe introduced a new high acti%ity denitrogenation catalyst TM+++ in late 199+" To date it has !een installed in 1* units of which si< are in hydrocracking $retreat ser%ice" The first of these hydrocrackers went online in >e$tem!er of 1995 and the remaining were started u$ early this year" &ll of them are doing %ery well and o$erating at lower tem$eratures at this $oint in their cycle than $re%ious ones" To$soe will !e introducing another new more acti%e catalyst than this one in the s$ring of ne<t year"

F;CTCHCR# &k1o Go!el $roduces many high acti%ity hydrocracker $retreat catalysts !oth licensed with :O8 which include HCM HC8 and more recently HCT as well as o$en market grades such as MF7*' and 7*5" :O8 recently $u!lished a $a$er and $resented it yesterday in our technical seminar co%ering the commercial $erformance of the HC8 in four refineries around the world" These results show an a%erage 2+ $ercent increase in H=G %olume acti%ity com$ared to the $re%ious generation of catalysts such as HCM" .n one case this translated to o%er a 23 degree lower o$erating tem$erature re/uirement and the sta!ility was e/ui%alent to the reference HCM" The e<tra acti%ity can !e used to e<tend cycle length or to reduce the $eriod of nitrogen sli$ commonly seen at end of run" T&>MCR# (e ha%e seen the introduction of se%eral higher acti%ity catalysts o%er the last few years and there ha%e !een some a$$arent marked im$ro%ements !ut we ha%e to recogni1e that these are !ased on initial acti%ities and we are waiting right now to determine the catalystsO longe%ity to make sure that they are confirmed" The indications are that o%erall life may !e less than !efore" Aut on the other hand some of the commercial tests ha%e shown a lower initial acti%ity !ut then %ery sta!le o$erations with the HR'*7 and HR'53 mild hydrocracking catalysts" M.RM GOB&M 2Criterion4# (e ha%e introduced a $rocess called Century which is a ste$ out technology in manufacturing" This new catalyst line $roduces two catalyst $roducts the =G193 and also HCR from :O8 $art of our license catalyst that we $ro%ide" The HCR was the focus of a $a$er from :O8 at the last G8R& &nnual 0eeting" (ith the =G193 and HCR we ha%e o%er se%en units in the industry and of the acti%ity ad%antages of this catalyst are wellFknown in terms of unit o$erations a!out 1'5 %olume metric $ercent acti%ity increase" %uestion 22 In c(oosing a s/i+ing agent for /resulfiding- &(at criteria s(ould "e e0aluated 7e.g.- en0ironmental- solu"ilityeconomic- toAicity- etc.9) A&R;OC(CG# (e attem$ted to summari1e some of the !enefits of %arious sulfiting chemicals that are used and $ut together three slides in which we will !riefly re%iew " Hydrogen sulfide is the first of these" This is fairly widely used in Gorth &merica !ecause it is a%aila!le in most refineries" .t is chea$" On the down side one of its draw!acks is that it is rarely a%aila!le in the rates and the $ressures that you need" >o you are ine%ita!ly limited in the s$eed at which you are a!le to sulfide" &nd s$eaking from $ersonal e<$erience . know many $eo$le get frustrated and do not do a thorough @o! of sulfiding !ecause of the $ressure of getting their unit online" The ma@or ad%antage of car!on disulfide is low cost low decom$osition tem$erature and high sulfur content" Howe%er it is %ery flamma!le has low auto ignition tem$erature and high %a$or $ressure" &nother sulfiding catalyst dimethyl sulfide has !een used and is moderate in cost moderately high in sulfur content" Howe%er on the down side it has high %a$or $ressure and se%ere odor $ro!lems and has !een !roadly re$laced !y dimethyl disfulide" . ha%e highlighted two of the s$iking agents that are most !roadly used dimethyl disfulide and tertiary nonyl $olysulfide" The dimethyl disulfide has moderate costs low %a$or $ressure and lower decom$osition tem$erature than dimethyl sulfide" Howe%er it still has a significant odor $ro!lem and is /uite to<ic" Howe%er !ecause of the $rice factor has it is still /uite !roadly used worldwide" Gormal !ulymer merca$tan is really @ust a -throwF away- on this list" .t is theoretically $ossi!le to use it !ut !ecause it has such an atrocious odor in minute /uantities it is %ery rarely used" Tertiary nonyl $olysulfide has !een /uite widely used" The odor is much im$ro%ed low decom$osition tem$erature low %a$or $ressure low to<icity" Howe%er there is no free lunch" .t is e<$ensi%e" Hou also ha%e to kee$ the tem$erature u$ !ecause it gets %ery %iscous at lower tem$eratures" Fslide 3GFinally of the three that . mentioned TA8> or tertiary !utyl $olysulfide is one of the most !roadly used and has low odor lowest decom$osition tem$erature and low to<icity" Offsetting that is it is e<$ensi%e" =0>O is from a characteristic stand$oint the $referred material i"e" low to<icity low odor and low flamma!ility" One factor to kee$ in mind it must !e used in solution with water !ecause of a high free1e $oint" (e did not ha%e a good reading on $rice" ;ast yearOs QE& indicated that it was moderately $riced" F;CTCHCR# (ell it is difficult to add to 0r" Aarloewen)s com$lete answer !ut . will a$$roach it differently" (e would say that s$iking agents for $resulfiding are differentiated !y the following criteria" 1" cost $er $ound of sulfur" 2" the en%ironmental im$act risk i"e" odor to<icity an %a$or $ressure"

the !y$roduct yields" That is how much water and hydrocar!on such as methane ;8G or na$htha is $roduced $er $ound of sulfur" *" their decom$osition conditions" +" the energy of sulfiding" That is the sulfur in the feed $er +3 degree tem$erature rise" 5" their suita!ility for e/ui$ment and sulfiding $rocedure" (e !elie%e that all the common agents are effecti%e for sulfiding !ut not all are recommended for some sulfiding $rocedures and reactor conditions" Our recommendation is that you contact your catalyst %endor for their ad%ice" JO>CCM# (e ha%e had se%eral !ad e<$eriences with sulfiding agents due to unforeseen e%ents" (e agree en%ironmental economics and to<icity should !e some of the criteria for selection" Howe%er numerous other factors must also !e considered including side reactions intermediate com$ounds and the $rocess units) design and downstream $rocessing" .ntermediates formed during the sulfiding $rocedure can !e as or more ha1ards and odorous as the sulfiding agent" .ntermediates should !e considered for to<icity and the en%ironmental ha1ards also" >ide reactions can cause undesira!le $roducts using some sulfiding agents" >ide reactions may determine if gas or li/uid $hase or in situ or e< situ sulfiding is $referred" (e would recommend consulting the su$$ly or the sulfiting agent and the catalyst su$$lier for the recommended sulfiding $rocedures" (e also recommend de%elo$ing formal written $rocedures and formal o$erator training" Ha1ardous analysis with o$erators should !e considered !efore changing" Gumerous $a$ers and data are a%aila!le for $resulfiding agents and sulfiding $rocesses" . recommend reading them as much a $ossi!le !efore changing" >&0:C;># . would only add that a $a$er is a%aila!le from Gaylord Chemical entitled -Cn%iroF># &n C<ce$tional >ulfiding &gent O$erationally >afe and Free From Odor-" .t is a 1991 $a$er that com$ares /uantitati%ely the relati%e merits of a num!er of sulfiding agents" 8arts of this re$ort were $u!lished in the >e$tem!er 17th 1979 Oil and Gas Journal" .t gi%es a good o%er%iew on to<icity and also degradation tem$eratures and $hysical $ro$erties" T&>MCR# O!%iously weight has to !e gi%en to each of the criteria detailed i"e" en%ironmental solu!ility economic to<icity etc" to come u$ with the agent which fits the refinerOs needs !est" The general $ro!lems already mentioned associated with the s$iking agents are the tem$erature at which it will con%ert to H2> good control of the e<otherm released good control of distri!ution to ensure the catalyst is all $resulfided" &nd of course one has to consider the $ossi!ility of flaring sur$lus H2>" Gow =0=> has !een the work horse . think of the s$iking agents used today !ut how a!out something a little !it different called &ddF.tF.n? &ddF.tF.n *33 is !eing used in Curo$e /uite e<tensi%ely" .ts !enefits are low odor easy to handle and re/uires no s$ecial classification and la!eling" .t has disassociation tem$erature of around a!out 1'3 to 1+3LF" .t is dialkyl $entosulfide" .t has a!out *3 wt , of sulfur on it" &nd this is something which . will add to the transcri$t a little !lur! on this &ddF.tF.n" C=(&R= >0.TH 2:O84# :O8 has found in discussions with refiners that the criteria for selection ty$ically rank as follows# safety and handling en%ironmental and to<icity su$$lier relia!ility and cost" This assumes the sulfiding additi%e has !een tested and?or a$$ro%ed !y the catalyst su$$lier" &ll of the $ro$erties listed as well as high solu!ility good low tem$erature handling $ro$erties low decom$osition tem$erature low nitrogen and low H2> trace /uantities are im$ortant" :O8 offers a $roduct SA-200 Sulfding Additive, which meets all of these criteria and is a$$lica!le to hydrotreating and reforming catalysts" J.0 >TOGC 2;ouisiana =e$artment of Cn%ironmental Quality4# >ometimes the sulfiding takes on an as$ect of !eing a test of a new material" .n the ;ouisiana regulations we ha%e a%aila!le a tem$orary e<em$tion for testing" >o if you get into something like this where you feel like that would !e useful to you it is a way of making sure that you are not going to !e %iolating an en%ironmental regulation while you are testing something new" Hou do ha%e to actually test and make a re$ort if you use this e<em$tion and you ha%e to ask for it ahead of time" 2>ee ;&C ' ..." +2'"A4 %uestion 23 EA situ /resulfided catalysts (a0e "ecome more &idely acce/ted &it(in t(e industry. 'ne main concern remains- namely- t(e /ro/ensity for eAot(erms in units &it( large catalyst 0olumes. Ho& are eA situ /resulfided catalysts used safely and economically in large units) HCGMC# (e in@ect hydrogen into the li/uid feed of one diesel hydrotreater at a

'"

rate of +33 standard cu!ic feet $er !arrel" The feed to this unit is %ery reacti%e com$rised of light cycle oil and light coker gas oil" =esign issues that we consider when in@ecting hydrogen into li/uid feed include# 14 the total recycle gas rateI 24 the thermal design of the heat transfer e/ui$mentI '4 the metallurgy of feed effluent e<changers heaters and associated $i$ingI *4 the reacti%ity and sta!ility of the li/uid feedI and +4 the sta!ility of the flow regime" . refer you to the 199' G8R& QE& Transcri$t $age 96 Question 23 for additional information" This reference includes work done !y >yncrude Canada" Their research de$artment had done work concerning the chemistry of free radical saturation and other items" F;CTCHCR# Curocat which is &k1o Go!elOs $artner for $resulfiding catalysts has sulfided and assisted in the acti%ation of o%er 1 333 hydro$rocessing units worldwide including many units with large catalyst %olumes" The a$$lica!ility of sulfided catalysts s$ecifically to a%oid large e<otherms in%ol%es many unit s$ecific and catalyst s$ecific %aria!les" Therefore a single generic answer cannot !e $ro%ided" The Curocat technical ser%ice grou$ has de%elo$ed a %ariety of techni/ues to assist the refiner in re%iewing the unit conditions and simulating the acti%ation such that a safe and effecti%e catalyst acti%ation can !e $lanned for %irtually any hydrotreating a$$lication" FO>TCR# For economic reasons we no longer use e< situ $resulfided catalysts for our large units" .n the $ast we ha%e used these in one of our CFHTs 2the %olume was a!out '33 333 l!s4" (e did ha%e one incident se%eral years ago when we e<$erienced an e<otherm of '+3LF" (hat ha$$ened was that our catalyst su$$lier used only a single sulfur s$ecies when they $resulfided our catalyst so all the decom$osition 2and e<otherm4 occurred at once" ;ater we worked with a catalyst su$$ler that $resulfided the catalyst with multi$le sulfur s$ecies instead of @ust one" >ince each s$ecies had a different decom$osition tem$erature this resulted in a gradually ascending decom$osition $rofile" >o !ased on our e<$erience may recommendation would !e to work with your catalyst su$$lier to design in a gradually ascending decom$osition $rofile that takes into account your catalyst %olume and heat remo%al ca$a!ilities" F:>>C;;# (e ha%e !een using e< situ $resulfided catalyst in 8ort &rthur for /uite a long time" (e use it on our :ni!ond unit as well as our distillate hydrotreaters and we ha%e had no $ro!lems with e<otherms" (e ha%e used !oth Curocat and GCR. and we followed their startu$ $rocedures" On our :ni!ond unit which is the largest catalyst %olume we ha%e we ty$ically see a!out a +3LF e<otherm across the unit when we start u$" =&G.C; J" GC:0&G 2Tricat .nc"4# (e ha%e recently commerciali1ed a true e<Fsitu $resulfiding $rocess at our $lant in Germany" .n contrast to earlier technologies our catalysts are com$letely sulfided such there are no e<otherms during startu$ since the e<othermic sulfiding reactions ha%e already !een com$leted e<Fsitu" The catalyst is free flowing and sta!le in air" .t therefore can !e handled safely during the loading $rocedure in air" %uestion 2! 1(at is t(e industry2s eA/erience &it( use of eA situ /resulfided (ydrocrac+ing catalysts) Has any increase in crac+ing acti0ity com/ared to in situ sulfided catalyst "een o"ser0ed) Is a li5uid /(ase start-u/ /ossi"le &it( eA situ /resulfided (ydrocrac+ing catalyst) T&>MCR# &s a $artial answer for this one we do ha%e some e<$erience with e< situ H=T catalysts in 8ortugal and in .ndonesia" (e found that initially the control of the e<otherm was difficult !ut it !ecame easier later" There is a fairly /uick consum$tion of hydrogen during the initial o$eration and you may get a little $ressure di$ during that $eriod" This can im$act on the com$ressor $erformance" >ometimes it is difficult to allow for such changes in the design of the com$ressor" For the in situ sulfided catalyst it may !e $ossi!le to control the initial o$eration !etter !ut the o%erall sulfiding may not !e as efficient as the e< situ $resulfided catalyst" The cost has to !e weighed and it is o!%iously a little !it more e<$ensi%e for e< situ than in situ !ut . think there are other factors which weigh on the side of e< situ $resulfiding" F;CTCHCR# Curocat again our $artner for $resulfiding catalysts re$orts that they ha%e sulfided o%er eight million $ounds of nickel moly and nickel tungsten hydrocracking catalysts for more than *3 unit acti%ations" From this e<$erience they ha%e seen some hydrocracking a$$lications which showed im$ro%ed $erformance" (e !elie%e this to !e due to a more com$lete sulfiding throughout the reactor resulting in a more fully acti%ated catalyst" .n some cases H=G

acti%ity at the $retreat catalyst has also !een a$$ro%ed with the $resulfided catalyst" This also im$ro%es hydrocracker catalyst $erformance" Curocat has $artici$ated in the li/uid $hase acti%ation of a hydrocracking catalyst that had !een e< situ $resulfided" This unit $erformance has met the refinerOs e<$ectations" Men 0ayeau< 2CR. .nternational4# Hydrocrackers re$resent a ma@or challenge in regards to using $resulfuri1ed catalysts without e<cessi%e e<otherms" The catalyst %olumes are large and the catalyst is usually acti%ated gas $hase !ecause of the $otential for runaway hydrocracking" The high acti%ity 1eolytic catalyst can start cracking the startu$ oil well !efore the catalyst can reach a high enough tem$erature to com$lete the sulfiding" C%en under these less than ideal conditions CR.Os actiC&T $resulfuri1ed catalyst has !een successfully a$$lied" CR.Os $rocess generates a %ariety of sulfiding com$ounds that acti%ate o%er a wide tem$erature range resulting in a gradual acti%ation with minimal e<otherms" O%er the $ast three years actiC&T has !een used successfully in a do1en hydrocracker startu$s re$resenting more than fi%e million $ounds of catalyst" 0ost recently +33 333 $ounds of $retreat and cracking catalysts was started u$ gas $hase with reactor delta Ts of less than *3LF" .n our commercial e<$erience and in acti%ity tests !y se%eral catalyst manufacturers the acti%ity of actiC&T $resulfuri1ed cracking catalyst is as good if not slightly !etter than that from the !est in situ sulfiding $rocedures" %uestion 2# 1(at /rocedures are "eing used for unloading s/ent (ydrotreating catalyst) Include data on "ot( &et and dry /rocedures and (o& t(ey affect catalyst regeneration. H&HG# (e unload our hydrotreaters only dry and we do it with inert atmos$here with a s$ecialty contractor" (e kee$ a 1"3 F 2"3 $ound nitrogen $urge going out the !ottom of the reactor as we dum$" (e load directly into !ins and then toss in some dry ice on to$ and seal them u$" (e ha%e had no $ro!lems with this techni/ue" (e are aware that there are su$$liers who can use a wet method where they ha%e a s$ecial chemical coating that they will $ut on your catalyst to $re%ent iron sulfite fires" Howe%er the draw!ack to this techni/ue comes if you $lan to regenerate or e%en to send it off for dis$osal you ha%e to $ay e<tra to ha%e those $eo$le stri$ off this coating material" F:>>C;;# On our distillate hydrotreaters in 8ort &rthur we do gra%ity dum$ using a dry method" On our :ni!ond we ha%e to %acuum the catalyst out and we also do it dry" (e do ha%e some e<$erience at our Aig >$rings refinery on our gas oil hydrotreater using the wet method" (e ha%e !een %ery successful with that method in Aig >$rings" .t has reduced the nitrogen use during the dum$ing and the dum$ing goes much /uicker" The catalyst !asically slimes out of the reactor %ery nicely" There are some concerns a!out regeneration" >o if you do $lan to regenerate you might want to look into that a little !it closer !efore you use the wet method" There are also some dis$osal issues as 0s" Hahn referred to" 0&;CM# From a new design stand$oint we see the industry going to the dry techni/ue" There are also some ad%antages in the designing and streamlining of these reactors when you do go with that a$$roach" :sing a %acuum a$$roach you can eliminate some no11les on the reactor %essels and you do not ha%e to $ut the reactor %essel on a $edestal" Hou can lower it on a skirt directly on the ground" There is /uite a !it of cost sa%ings to !e reali1ed in streamlining the design in that fashion" RO0&G# (e ha%e wet unloaded s$ent BGO catalyst and also s$ent catalyst from our aromatics desulfuri1er unit and ha%e decided against this $rocedure" (et unloading leads to sewer $luggage e<tra freight for s$ent catalyst shi$$ing leakage from s$ent catalyst containers and $luggage while dum$ing" .t was also difficult for catalyst regeneration com$anies to handle" (e had one incident where one of the s$ent catalyst containers leaked !lack li/uids onto the highways" (e currently use dry unloading e<clusi%ely" This is done under an inert gas !lanket" The catalyst is !ottom unloaded into leased catalyst flow !ins" >&; TORR.>. 2CR. (oodlands4# The choice of dum$ing method de$ends on cost timing and catalyst reuse or dis$osition decisions" For those choosing the reuse o$tion CR. has worked with customers to regenerate catalyst dum$ed !y !oth wet and dry dum$ing techni/ues" (et dum$ing methods are usually chosen to $rotect reactors against 8olythionic &cid >tress Corrosion Cracking of Tem$erature Cm!rittlement as an alternati%e to inert entry" (et dum$ing techni/ues can !e di%ided into two categories# those which use hydrocar!on and those using sodaFash or water flooding to $assi%ate the reactor system"

CR. has noted a significant increase o%er the $ast 13 years in the num!er of s$ent catalysts that re/uire hydrocar!on remo%al $rior to regeneration" (hether the dum$ed catalyst contains high le%els of hydrocar!on or e%en s$ecial $assi%ating oils like CATnap CR.)s new optiCAT-Plus catalyst regeneration technology allows for efficient oil remo%al and /uality regeneration of classically difficultFtoFregenerate catalysts without significant cost $enalty to the customer" &lthough sodaFash dum$ed catalyst has traditionally !een considered unsuita!le for reFuse there are circumstances where these catalysts ha%e successfully !een regenerated and loaded for additional cycles" Gi%en that this decision is de$endent on customer $reference and e<$erience CR. can assist refiners in identifying reFuse o$tions for sodaFash dum$ed catalyst !y $erforming la!Fscale regenerations followed !y $hysical chemical and $ilot $lant $erformance e%aluations" !. Reactor Safety and Relia"ility %uestion 2: 1(at means are refiners using to eAtend t(e life of HBS reactor 0essels) C&.G# (e ha%e $erformed internal %isual and dye $enetrant ins$ections along with acoustic emissions ins$ections sheer wa%e e<aminations" (e ha%e an outside firm to $erform a fit for ser%ice ins$ection" F;CTCHCR# The most im$ortant as$ect of reaching a normal '3 year %essel life is a good ins$ection $rogram" & $lan should !e in $lace to ins$ect all com$onents on a regular schedule" The heat u$ and cool down cycles contri!ute to reactor stresses" .t is im$ortant to follow the manufacturerOs recommended heat u$ and cool down rates" &%oid shock in the reactor with water during shutdowns" Finally failures ty$ically occur in the attachments such as the internals the outlet collectors etc" to the reactor" These are usually the result of $oor design such as high stress and $oor materials selection" .ns$ections around these areas is es$ecially im$ortant" F:>>C;;# On our :ni!on unit we follow s$ecial shutdown and startu$ $rocedures to minimi1e any damage to the reactors" (e also use se%eral different nondestructi%e testing methods such as acoustic emissions re$lications wet fluorescent mag $article testing ultrasonics " (e do all of this on the reactors as well as the high $ressure se$arator" HCGMC# (e in@ect hydrogen into the li/uid feed of one diesel hydrotreater at a rate of +33 standard cu!ic feet $er !arrel" The feed to this unit is %ery reacti%e com$rised of light cycle oil and light coker gas oil" =esign issues that we consider when in@ecting hydrogen into li/uid feed include# 14 the total recycle gas rateI 24 the thermal design of the heat transfer e/ui$mentI '4 the metallurgy of feed effluent e<changers heaters and associated $i$ingI *4 the reacti%ity and sta!ility of the li/uid feedI and +4 the sta!ility of the flow regime" . refer you to the 199' G8R& QE& Transcri$t $age 96 Question 23 for additional information" This reference includes work done !y >yncrude Canada" Their research de$artment has done work concerning the chemistry of free radical saturation and other items" %uestion 2; Are "ed differential and radial tem/erature s/read limits maintained t(e same from start to end of run- or are t(ey 0aried as reactor tem/eratures are increased to maintain catalyst acti0ity) A&R;OC(CG# The /uestion deals with radial tem$erature limitations across the reactor and %ertical across !eds of hydrotreating reactors" & wellFdesigned reactor and distri!ution system should gi%e you a radial tem$erature gradient on the outlet of the !ed of ten degrees or less" &nd after a mi<ing de%ice fi%e degrees or less with em$hasis on less" The ma<imum radial tem$erature that you should !e a!le to li%e with is %ery much a function of feedstock ty$e $rocessing o!@ecti%e and catalyst ty$e" For e<am$le 1eolite cracking catalyst is much more sensiti%e and you would want to a$$ly tighter limits than on a less se%ere ser%ice like distillate hydrotreating" One of the $ro!lems is that most hydro$rocessing reactors es$ecially the old ones do not ha%e a lot of tem$erature measurement and so you are only looking at a %ery small fraction of the reactor" Hou do not ha%e a high assurance that you are looking at the worst s$ots" Our recommendation would !e to ha%e tem$erature sensing $oints near the wall on the inside of the reactor" TodayOs technology allows retrofitting that /uite readily through e<isting no11les" Our recommendation would !e not to %ary the allowa!le gradient either in the radial direction or in the a<ial direction as the run $rogresses e%en though coking does cause some deterioration of gradients"

The real issue that you ha%e to deal with is $rocess control" Hou want to !e assured of ha%ing ade/uate $rocess control e%en in an u$set condition" .n a %ertical or a<ial direction you ha%e criteria as to ma<imum tem$erature rise !ased on your a%aila!le /uench gas" That is a function of the recycle com$ressor and it may also !e a function of the /uench %al%e actually $ro%iding the /uench" F;CTCHCR# The radial tem$erature $rofile is an indicator of li/uid flow distri!ution through the reactor" ;i/uid flow distri!ution is influenced !y !ed $ermea!ility resulting from catalyst loading and is affected !y the li/uid distri!utor and the li/uid mass %elocity in the catalyst !ed" ;i/uid distri!utors can !ecome fouled with scale and alter the li/uid distri!ution" .rregular catalyst loading tends to $romote channeling or flow maldistri!ution" This can result in increasing radial tem$erature differentials as the catalyst cycle $rogresses" :nits with li/uid mass %elocities less than 2 333 l!?ft2"hr are es$ecially $rone to flow distri!ution $ro!lems" One a$$roach to o$eration is to set limits for !oth radial and !ed delta tem$erature that ne%er change" .n the e%ent that %ariances e<ceed the limit the cause for the %ariance should !e in%estigated and understood" Quench and other strategies may !e em$loyed to reduce the delta tem$erature within the limits" .f a reasona!le understanding of the cause of the high tem$erature differential is found and a risk assessment is made there could !e a decision to knowingly e<ceed these limits" .n this case skin tem$eratures and gas makes should !e closely o!ser%ed and guide the decision $rocess" .t is critical that there are ade/uate skin tem$erature measurements to make a sound decision" >&0:C;># &t our Ro!inson hydrocracker the !ed delta tem$eratures are critical o$erating $arameters and are not changed during the course of the run" (e ha%e reached ma<imum !ed delta TOs !efore and !iased other !ed tem$eratures to maintain through$ut and con%ersion with %iolating critical o$erating $arameters" (e ha%e not reached our ma<imum radial delta tem$erature of '3LF on each !ed in the $ast" Aefore we would change any tem$erature limitation as mentioned earlier the unit /uench ca$a!ilities would ha%e to !e e%aluated to ensure that in fact there is sufficient reser%e /uench a%aila!le in the e%ent of a tem$erature e<cursion" Ty$ically the num!er one hydrotreater !ed delta tem$erature limit of 11+LF on this hydrocracker is the limiting factor on how much cracked stock can !e $rocessed" Hydrogen is also a limit as to how much cracked stock can !e $rocessed" T&>MCR# . agree with e%erything $eo$le ha%e said" For the radial tem$erature delta we ty$ically see in the order of 9 to 11LF and feel that that is /uite normal for start to endFofFrun" .n some cases we ha%e seen that the delta T is considera!ly less" .n one H=> unit 11"+ feet in diameter we ha%e o!ser%ed a radial delta T of less than 2LF at 1LC e%en with %ery acti%e catalyst" C;.Q&ACTH &;;CG 2Criterion Catalyst4# There was a $a$er $u!lished !y >hell in 197* which gi%es details regarding the tem$erature $rofiles in trickle !ed reactors" The $a$er discusses irregular flow $atterns which are relati%ely common in trickle $hase hydrotreating" Their findings were that irregularities in catalyst $acking density and flows of the different $hases can lead to a!normal flow $atterns" These flow $atterns can lead to a situation where a finger of li/uid channels through the catalyst causing hot s$ots due to lack of gas to carry away the e<otherm and coking as well" The $a$er deri%es an e/uation to calculate ma<imum delta T allowed !efore these hot s$ots and coking can occur" The e/uation shows that ma<imum delta T is a function of inlet tem$erature acti%ation energy !ed height gas %elocity and gas density" .n other words for hea%y feeds with the low %a$ori1ation and low gas rates the highest $otential for e<cessi%e e<otherms can occur" CR&.G H&RBCH 2:O84# .n hydrocracking ser%ice good reactant distri!ution effecti%e /uench 1one mi<ing and catalyst !ed uniformity are essential to minimi1e radial tem$erature s$reads" &n e<tensi%e tem$erature monitoring system must also !e in $lace so that the o$erator has detailed knowledge as to the radial tem$erature $rofiles e<isting within the catalyst !eds" The o$erating se%erity within a hydrocracking !ed should !e limited in accordance with the se%erity of the radial tem$erature gradients" Of $rinci$al concern is the ca$a!ility to $ro$erly control reaction rates at all !ed locations in the e%ent of an u$set condition" &s reaction se%erity or a<ial rise in a hydrocracking !ed is increased it is generally e<$ected that the radial s$read at the !ed outlet will also increase due to the accelerated increase in reaction rate that is e<$erienced in the hot 1ones" &s an o$erating cycle $rogresses the relationshi$ !etween the catalyst !ed a<ial rise and the se%erity of tem$erature s$read at the !ed outlet may change" This will de$end as to whether the radial tem$erature s$read is due to $oor

li/uid distri!ution inferior /uench 1one mi<ing efficiency or $ermea!ility %ariations within the catalyst !ed" .f the radial gradients are the result of e<treme !ed $ermea!ility %ariations then it is e<$ected that the radial gradients at a gi%en reaction se%erity will worsen as the cycle $rogresses" .n this situation the !ulk reaction se%erity or !ulk a<ial rise may ha%e to !e lowered as the cycle $rogresses in order to $ro$erly control reaction rates at all !ed locations" .n certain hydrocracking !ed en%ironments the hydrogenation reactions may !ecome thermodynamicallyFlimited as end of cycle conditions are a$$roached" .n this situation the catalyst tem$erature res$onse may change towards end of cycle and this may result in a slight reduction in the reaction rate in the hotter 1ones of the catalyst !ed" %uestion 2< In co-/rocessing co+er na/(t(a &it( straig(t-run diesel- &(at /ercentages of co+er na/(t(a (a0e "een successfully run &it(out using a lo& tem/erature first stage /retreating reactor) >&0:C;># &t Ro!insonOs 5+ 333 !arrel $er day distillate hydrotreater unit we ha%e $rocessed u$ to 6 333 !arrels a day of coker na$htha along with %irgin diesel and FCC light cycle oil since June of 1995" The unit limitation in $rocessing this coker na$htha has !een handling the stri$$er o%erhead na$htha $roduction and is not related to e<changer fouling or reactor e<otherms" The coker na$htha is fed hot from the cokers through 23 micron filters" Occasionally the coker na$htha is stored $rior to $rocessing" &ll storage is !lanketed" The stored feed is stri$$ed with hydrogen coalesced and filtered" &long with the coker na$htha it is common to $rocess a!out 2+ to '3 $ercent of the feed as FCC light cycle" The ty$ical feed has a '2L &8. gra%ity u$ to a 12 !romine num!er and an a%erage of 3"5 weight $ercent sulfur" Two $arallel reactors contain o%er 533 333 $ounds of regenerated co!alt moly catalyst" There is no inner !ed /uenching" The ty$ical total delta T is a!out 5+LF with a 513LF inlet start of run tem$erature" The coker na$htha itself has an &8. gra%ity of 53 a 3"+ wt , sulfur and a ='613 distillation fi%e $ercent $oint of 73LF and 9+ $ercent $oint of '7+LF" HCGMC# (e $rocess se%en $ercent hea%y coker na$htha in one of our diesel hydrotreaters" The coker na$htha is co$rocessed along with light coker gas oil straight run diesel and FCC light cycle oil" (e see a ' 1?2 year run without any $ressure dro$ $ro!lems" F;CTCHCR# .n addition to the routine $rocessing of coker na$htha with %irgin na$htha a few refiners $rocess coker middle distillate and?or coker na$htha with other middle distillate streams" These units ty$ically suffer from !oth silicon $oisoning and $ressure dro$ !uild u$ $ro!lems" The concentration of coker na$htha is usually not high 2D'3,4" &$$ro$riate grading at the to$ of the reactor in con@unction with low inlet tem$erature is usually sufficient to mitigate the $ressure dro$ !uildu$ tendency of the coker na$htha" >ince a few refiners ha%e !een successful in running coker na$htha without a guard reactor 2low tem$erature diolefin saturation4 it seems that the right catalyst system at the correct o$erating conditions can work" H&HG# (e run a!out 23 $ercent coker na$htha com!ined with %irgin diesels and some coker light gas oil all in our diesel hydrotreater without any $ro!lems" (e do not ha%e a low tem$erature first stage !ut our first reactor !ed is /uite small which may hel$ us succeed in that endea%or" %uestion 2= 1(at guidelines are used for setting "ed tem/erature /rofiles in multi-"ed (ydro/rocessing reactors 7e.g.e5ual "ed outlet tem/eratures- e5ual 1AB*2s- ascending or descending "ed outlets9) F;CTCHCR# The $ro$er answer de$ends on many factors and as such it is difficult to gi%e a com$rehensi%e answer" The o$timum reactor tem$erature $rofile for a unit wihtout significant limits is de$endent u$on the feedstock the goals of the hydro$rocessing unit and the time on stream of the unit" Howe%er recycle gas /uench rate and?or makeu$ hydrogen contstraints usually significantly reduce the reactor tem$erature $rofile o$tions" &t >OR one might decide to minimi1e the deacti%ation in the first !ed !y running an ascending $rofile and not using /uench" This can also !e dri%en !y high acti%ity in the first !ed re/uiring a low inlet tem$erature to reduce the tem$erature rise across the first !ed" .n other units one might ma<imi1e the reactor inlet tem$erature !y o$erating with a descending $rofile" =escending $rofiles are useful for ma<imi1ing the metals $icku$ rate of demetali1ation catalysts and ma<imi1ing aromatics saturation" &fter the middle of a run a descending $rofile is almost always o$timal until the unit hits the ma<imum allowed reactor tem$erature" &t COR one ty$ically ma<imi1es the reactor

(&AT 2inlet tem$erature $lus 2?' K !ed dT4 !y !ringing all !ed outlets to the ma<imum allowed reactor tem$erature" >ome s$ecific cases are gi%en !elow" =iesel Hydrotreater F 0ore modern diesel hydrotreater designs will ha%e two or more !eds" :sually minimum /uench is used !ut sometimes /uench is used to control reactor outlet tem$erature in order to kee$ a good $roduct color" FCC 8retreatment F (hen the o$erating target is H=> 2constant H=> o$eration4 and insufficient hydrogen is a%aila!le refineries ty$ically a$$ly minimum /uench or control the o%erall e<otherm not to e<ceed liscenser)s recommendation" On the otherhand refiners that want more midFdistillates usually o$erate in e/ual outlet tem$erature mode" Resid Hydrotreater F Just after $resulfiding the catalysts are so acti%e that target sulfur is attained at %ery low tem$erature" (e recommend e/ual (&AT mode of o$eration to a%oid metal $oisoning of the downFstream H=> catalyst for the first 2F* weeks of o$eration" &fter that we recommend the following settings 2as an e<am$le4# Aed 1 2Guard Aed4# Aase (&AT 2!elow 623LF at inlet4 Aed 2 2H=04# Aase T 13F23LF in (&AT Aed ' 2H=>4# Aase T 23F*3LF in (&AT Aed * 2H=>4# C/ual outlet of Aed ' .f the refiner re/uires high con%ersion we recommend a flat (&AT for Aed 2 ' and *" .n this case $roduct sulfur increases gradually after the (&AT reaches its ma<imum" H&HG# (e run with a slight ascending tem$erature $rofile across the first two !eds of our hydrotreater reactor and then all the rest ha%e e/ual !ed tem$eratures" A&R;OC(CG# From a design $oint for a low to moderate heat release feed we would design for e/ual !ed outlet tem$eratures" (e would ad@ust the !ed si1es so that we ha%e a$$ro<imately the same tem$erature rise across the !eds" The effect is that all of the catalyst o$erating at the same a%erage !ed tem$erature which is the most efficient from the catalyst utili1ation stand$oint" Howe%er when you are dealing with %ery reacti%e feeds with olefins or %ery reacti%e sulfur aromatic com$ounds it may not !e $ossi!le to li%e with those design goals and you may ha%e to acce$t a larger tem$erature rise for the first !ed" >imilarly as was mentioned !y 0r" Fletcher in a resid hydrotreater we would normally o$erate with tem$erature $rofile ascending in order to s$read out the metals de$osition and guard against e<cessi%e metals laid down on the lead reactor" The only situation from our $ers$ecti%e that we would recommend a descending tem$erature $rofile is where aromatic saturation is e/uili!rium limited" JO>CCM# There is no single answer" How you set the tem$erature $rofile de$ends on the $rocess o!@ecti%es and whether multi$le catalysts are in the unit" .n general our e<$erience is to run as close to -isothermal- as $ossi!le" (e try to kee$ the same -load- across each !ed same weighted a%erage !ed inlet tem$erature or to control $eak !ed tem$eratures where the most side reactions occur" .f there is a $rofile it is usually ascending" T&>MCR# . ha%e a fairly similar res$onse" Cach $rocess should !e treated according to the feed and $rocessing o!@ecti%es" >o there really is not a set answer to this /uestion" Ty$ically we use the classical a$$roach de$ending on the actual $rocess and we ad%ise e/ual outlet tem$eratures from each !ed for distillate hydrotreaters" >imilarly for $yrolysis feeds we try to maintain e/ual outlet tem$eratures and a lower inlet tem$erature" Howe%er you can only go so far on that" For residing feeds in fi<ed !ed $rocessors we do use different (&ATs for demetali1ation and desulfuri1ation in order to ma<imi1e the cycle length at as low a tem$erature as $ossi!le" (e like to use multiF!eds within reason of course to minimi1e the delta T $er !ed as $art of the design criteria" For H=> o$erations with hea%ier feeds we also use e/ual (&AT for multiF!ed o$eration" For hea%ier feedstocks including $artial residue and full residue feeds we ha%e achie%ed two year run lengths for the lighter deed and o%er one year for the hea%ier feeds" .t may !e necessary to rela< your $rocessing o!@ecti%e to !e a!le to e<tend the run length" For one of our units running atmos$heric residue we ha%e achie%ed o%er one year run when reducing the sulfur le%el from *"3 $ercent to 3"+ $ercent"

%uestion 38 1(at (as "een t(e eA/erience &it( using li5uid nitrogen for accelerated reactor cool do&n) Ho& is t(is normally done- and &(at are t(e "enefits- /otential /ro"lems and ris+s) Ho& &ides/read is t(is /ractice) C&.G# &s mentioned in Question 15 normally we hook u$ a li/uid nitrogen truck to %a$ori1e the nitrogen to 3LF for a once through $ass and %ent to the flare" From the time nitrogen is introduced the reactor tem$erature decreases from 173F 233LF to 13+LF in 12 to 17 hours" The $otential $ro!lems or risks are a%oided if the nitrogen is %a$ori1ed with the $ro$er tem$erature and $ressure s$ecification for your $articular o$eration" The cost of cooling down a reactor with o%er 1+3 333 $ounds of catalyst is less than Z23 333" (ithout nitrogen you could tri$le your time to cool the reactor down" F;CTCHCR# (e see li/uid nitrogen cool down !ecoming standard $ractice for large units with significant cost of down time e<ce$t during cold weather shutdowns" The economic !enefit de$ends on the si1e of the unit and the $roduct u$grade %alue of ha%ing the unit onstream" .t is definitely im$ortant to stay within the metallurgical cooling limitations for the e/ui$ment" :sually it is !eneficial to add the nitrogen through the furnace to moderate tem$erature fluctuations" .f inert entry is re/uired following the cool down further tem$erature restrictions may !e re/uired for the comfort of catalyst handling $ersonnel" .t is actually $ossi!le to get the reactor too cold for inert entry" FO>TCR# (e ha%e !een using this $ractice for 1+ years with im$ro%ement of 2 days or more on T?& length" (e also !enefit from im$ro%ed safety for the reactor crew F much less heatFrelated stress !ecause it)s $retty cool in there when we get done" The $otential $ro!lems are com$ressor damage due to o$erating a gas for which it is not designed and heater outlet $i$ing em!rittlement due to !ringing the tem$erature too low at the $oint of li/uid nitrogen in@ection" Aut with good management of change $rocesses good o$erating $rocedures and a $ro$erly designed diffusion 1one these risks can !e reduced to near 1ero" . recommend you work with your com$ressor e<$erts with $articular attention to the limits on com$ressor suction and discharge conditions com$ressor s$eed and load limitations" &lso consult with your metallurgy grou$ as to the minimum tem$erature your $articular $i$ing can sustain at the $oint of in@ection" . highly recommend the thorough use of thermocou$les 2encircling the $i$ing at the $oint of diffusion4" (e use a stainless steel diffuser on the heater outlet that is es$ecially designed @ust for this $ur$ose and is uni/ue for each a$$lication" Once you ha%e made the $ro$er $recautions and ha%e done this a few times you can !e /uite aggressi%e" .n our case downtime is always more e<$ensi%e than nitrogen so we raise the system to ma<imum mass circulation and minimum tem$erature on the heater outlet as /uickly as we can e%en if we consume a few e<tra $ounds of nitrogen" .t is a good idea to kee$ G2 $um$er truck a%aila!le all during catalyst unloading" .t kee$s the tem$erature down in the %essel which the workers a$$reciate and is more %ersatile in tem$erature and flow rate when %acuuming or dealing with hot s$ots" H&HG# . think the other $anelists ha%e co%ered most e%erything" (e also use nitrogen cool down as a routine $rocess and we would also caution that monitoring the tem$eratures of the $i$ing at the inlet where your nitrogen goes in is %ery im$ortant" (e cool down to at least 123LF !efore inert entry" JO>CCM# (e ha%e standardi1ed on using li/uid nitrogen cooling for rate limiting units" The time sa%ings greatly outweigh the li/uid nitrogen costs and the additional down time to cool the reactor" (e ha%e also incor$orated nitrogen cooling into the shutdown $lanning time line" (e ha%e !een using li/uid nitrogen since the O73s" >&0:C;># :>.>CO)s G.COO; $rocess was used for the first time on the :nicracker in our 0arch 1996 Turnaround" For the first time ;C;)s were low enough to get an immediate entry $ermit" Historically nitrogen would !e $urged u$flow through the reactors for a$$ro<imately one day !efore an entry $ermit could !e issued" &s far as accelerating the cooldown it is difficult to $ro%ide an e<act time" &t the $re%ious turnaround we installed 12 additional thermocou$le 2G&HC>CO4 which $ro%ided skin tem$erature in the HFC reactor" This additional tem$erature monitoring showed that the catalyst and reactor walls were not cooled com$letely when the middle of the catalyst !eds were D133LF" (e may ha%e reali1ed a$$ro<imately *F7 hour reduction in time !ut achie%ed a more com$lete cooling com$ared to historical cooldowns and an ;C; free reactor" =uring the accelerated cooldown the reactor wall tem$eratures should also !e monitored as well as the catalyst !ed tem$eratures" Once we started dum$ing the HFT reactor we found that the catalyst near the reactor wall was still in

the 1+3LF range when the !ulk catalyst tem$erature was D133LF" .n the Hydrocracking reactor the thermocou$les near the reactor wall cool much slower than the middle of the !ed" To sufficiently cool all the catalyst the reactor walls must also !e cooled" (e in@ected the li/uid nitrogen through a 1- %al%e at the outlet of the HFT reactor heater and the HFC reactor heater" The in@ection $oint was at grade le%el @ust u$stream of the check %al%es on the heater outlets" ;i/uid nitrogen was in@ected into the recycle gas to achie%e a com!ined gas tem$erature of *3LF" Thermocou$les were $ositioned on the down stream $i$ing to monitor the tem$eratures" Bisual and &udi!le alarms acti%ated if the tem$erature dro$$ed 13LF !elow target and the in@ection automatically shutdown at 23LF !elow target" Tem$erature control was not a $ro!lem" &s long as the in@ection is in stainless steel $i$ing no in@ection /uill is needed" Howe%er a /uill is needed if in@ecting into car!on steel $i$ing" The recycle gas com$ressor needs to !e checked to make sure it was designed for or can handle 133, nitrogen" .n $articular consider the higher discharge tem$erature and motor am$s" For the cooldown we dro$$ed $ressure to 533 $si initially 2due to reactor 08T4 and continued to dro$ $ressure as the motor am$s increase as the recycle gas neared 133, nitrogen" One additional $recaution we took was to ha%e the :ltraformer %ent H2 to flare during our cooldown to ensure that the flare was not $ut out with the large %olume of nitrogen !eing $urged from the unit" Our in@ection rate ranged from *33 333 to 733 333 scfh" :=&H 8&RCMH 2&ir 8roducts4# &ir 8roducts $ioneered the technology for li/uid nitrogen assisted reactor cool down in 1967 at &mocoOs Te<as City refinery" >ince then &ir 8roducts has done more than 2+ such cool downs in :">" and Curo$e safely and with significant economic !enefits as se%eral mem!ers of the $anel ha%e attested to" To ensure integrity of the metallurgy the nitrogen in@ection rate is controlled so that tem$eratures remain a!o%e a $redetermined set $oint" The nitrogen is in@ected using a custom designed coil or diffuser for each a$$lication" Ty$ically a refinery can e<$ect to reduce cool down times !y a factor of three or more using li/uid nitrogen" .n a recent case two reactors weighing in e<cess of 1"2+ million $ounds that is reactor $lus catalyst $lus su$$ort weight were cooled down from 273LF to less than 133LF in less than eight hours" ACG GR.CA 2Gay Cngineering and >ales Co" .nc"4# (hen analy1ing guidelines for setting !ed tem$erature $rofiles in multiF!ed hydro$rocessing reactors a fundamental /uestion should !e e<amined" -.s our current tem$erature measurement system ca$a!le of $ro%iding us with the data $oints necessary for making these o$erating decisions?.n many cases traditional tem$erature measurement technology limits !oth the num!er and location of the sensors" &dditionally the use of the traditional systems can detrimentally im$act res$onse time and accuracy" &n increasing num!er of refiners and $rocess licensors are now utili1ing the -Fle<FR- radial tem$erature measurement system to $ro%ide a solution to these limitations" The -Fle<FR- technology offers many attracti%e !enefits for tem$erature $rofiling in reactors" &ttri!utes such as faster res$onse time greater $oint density com$lete reactor co%erage and im$ro%ed accuracy $ro%ide the o$erator with a %alua!le tool for setting !ed $rofile o$erating $arameters" For a full discussion of the !enefits of this technology including user e<$eriences O refer you to G8R& 8a$er &0F 95F5' or contact Gay Cngineering and >ales Co" 8asadena TV" 0.MC H:GTCR 20"(" Mellogg Com$any4# . ha%e a followu$ /uestion" >e%eral of the $anelists mentioned the tem$eratures at which they sto$$ed the li/uid nitrogen cool down" . would like to ask if that is a $rocess tem$erature or a %essel wall tem$erature" &lso at what $rocess tem$erature do you start the $rocedure? C&.G# &s mentioned earlier we started at 173 to 233LF $rocess tem$erature in the reactor" (e sto$ it at 13+LF" JO>CCM# On some of our hea%y wall reactors we usually go to a skin tem$erature and an outlet tem$erature due to the reactor %essel metal mass" H&HG# The 123LF that . referred to was the $rocess tem$erature 2reactor inside tem$erature4" >&0:C;># (e would start the in@ection at *3LF $rocess tem$erature and sto$ the $rocess at 23LF $rocess tem$erature" %uestion 31 1(at cleaning met(ods are used for multi-"ed (ydro/rocessing reactors after unloading) If &ater is used(o& is it remo0ed from t(e reactor "efore loading) 1(at s/ecial met(ods are used to clean inter"ed internals and t(e mes( su//ort for t(e catalyst)

F;CTCHCR# 6" &lkaline wash solution is used to $rotect austenetic stainless steel and other austenetic alloys from $olythionic acid stress corrosion cracking" >olution $H should !e greater than nine for ade/uate neutrali1ation" These solutions may also contain an alkaline surfactant and corrosion inhi!itor" 7" The recommended wash solution is a 2 wt, soda ash" & 1"* to 2"3 wt, soda ash solution will $ro%ide a sufficient le%el of residual alkalinity on metal surface after the solution drains from the e/ui$ment" Higher soda ash concentrations 2+ wt,4 are desira!le when the catalyst itself has wedded" There is a $a$er from G&CC 2R83163F9'4 that $ro%ides more details on the $rotection of austenetic alloys from stress corrosion cracking" The reference will !e $ut into the transcri$ts" C&.G# Gormally we %acuum and neutrali1e with the soda ash solution" &lthough in some cases after unloading the catalyst through the dum$ chute the catalyst handling s$ecialists under fresh air clean out the catalyst $ockets" (e then use high $ressure wash with s$ecial s$ray no11les to clean and neutrali1e the %essel walls and hardware traces !eams etc" The s$ray no11le s$ins '53 degrees and s$rays soda ash solution at 13 333 to 1+ 333 $sig" Once finished we then lower a $erson inside and clean out any hard to reach $laces with a handFheld high $ressure lance" The %essel is then allowed to dri$ dry" (e then discontinue the nitrogen $urge" &fter checking for the o<ygen content it is ready to !e entered !y maintenance $ersonnel" H&HG# (e do not water wash our hydrotreaters " (e @ust dum$ using an inert atmos$here !y s$ecialty contractors" They also %acuum out any remaining dust or $articles from the reactor while under inert atmos$here" (e get a satisfactory cleaning using this mode" FO>TCR# (e us a high $ressure or!ital no11le to s$ray all internal $arts with a sodaFash solution" This is to $assi%ate '33 series stainless steel $arts from $olythionic acid attack of course !ut also $ro%ides initial remo%al of residual coke and scale" Once this $hase is com$leted contractors enter with high $ressure hydro!lasting e/ui$ment for a thorough cleaning of all internal $arts F again we use sodaFash solution here as well" Then the li/uid that remains is remo%ed !y %acuum or rags" (e do a final dry out with a high %olume fan $laced at the R< outlet" #. $eneral Process %uestion 32 Is anyone feeding H $' 7, cycle oil or (ea0y co+er gas oil9 to a (ydrotreated gas oils (ydrocrac+er@(ydrotreater) If so- &(at are t(e o/erating conditions 71AB*- H2 /artial /ressure- ?HSE9 and yields) Are t(ere any /ro"lems &it( , catalyst or co+er fines) Ho& are t(ese (ydrotreated gas oils used) RO0&G# (e hydrotreat RCC hea%y cycle oil along with %irgin %acuum gas oil in a %acuum gas oil desulfuri1er $rior to feeding it into a con%entional FCC unit" & ma<imum gasoline yield o!tained from hydrotreated hea%y cycle oil is 53 $ercent com$ared to only *' $ercent for nonFhydrotreated hea%y cycle oil" (e occasionally will feed either RCC or FCC light cycle oil into the BGO unit and recrack it in the FCC if the gasoline distillate s$read is high enough" The ma<imum gasoline yield from desulfuri1ed RCC light cycle oil was somewhat higher at 5+ $ercent" &s would !e e<$ected the sulfur in the gasoline deri%ed from hea%y cycle oil is dramatically lowered from 1 +73 $$m to 67 $$m !y desulfuri1ing this cut" The economics for either mode of o$eration are not straight forward and highly de$endent u$on $ricing hydrogen a%aila!ility and desulfuri1er ca$acity" Hou need to ha%e a high degree of confidence in your linear $rogram yield %ectors" (e ha%e had no $ro!lems with FCC catalyst $articles" T&>MCR# . hate to steal 0r" Cain)s thunder on this one" The con%ent HFOil unit o$eration does include FCC hea%y cycle gas oil in the feed" O!%iously there would !e some aromatic saturation taking $lace" Aut all of the reco%ered gas oils treated gas oils are recycled !ack to the FCC and effecti%ely therefore we are recycling the hea%y cycle gas oil to e<tinction" The ad%antages of doing this $articular o$eration are that we im$ro%e the as$haltene sol%ency e%en though there is some $artial aromatic saturation" &lso when we are heat in$ut limited the hydrogen consumed !y the hea%y cycle gas oil does hel$ us to ad@ust our reactor tem$eratures and assist in getting the $articular target reactor tem$erature"

There ha%e !een $ro!lems with FCC fines on occasion when the filters ha%e not functioned correctly in the FCC:" .m$eller wear on the feed $um$ has !een e<$erienced as catalyst fines lay down in some of the !ottoms e<changers" 8ro$er and good filtration therefore in the FCC will a%oid those $ro!lems" The gas oils can !e in@ected u$stream of the reactors where the !lack oil feed can !e used as /uench oil in the downstream %essel" Gow for se$arate $rocessing the hea%y cycle gas oil is relati%ely refracti%e and $ilot testing has shown that the aeromatics saturate first" .t is $ossi!le to crack !ut this re/uires /uite se%ere conditions" The conditions will !e a!out or 1+3 atmos$heres of hydrogen $artial $ressure at a 3"2 to 3"' li/uid hourly s$ace %elocity and a tem$erature of around '53LC" For H=> and hydrocracking o$erations we do not ha%e any commercial e<$erience on this material !ut we think that a 1eolite ty$e catalyst would !e the !etter choice of catalysts for the $retreatment that would !e re/uired" O!%iously the fines would !e !ad news and there would !e an im$act on the o$eration" Therefore it might !e necessary as we ha%e $re%iously mentioned to design a guard !ed and there!y increase the o%erall cost" 8CTCR>OG# (e treat our ;CO in either the =H=> unit or the CFH unit as economics and a%aila!le ca$acities allow" One of our refineries hydrotreats FCC slurrry in a *33 $sig four !ed hydrotreater" O$erating conditions are as follows# Feed >ulfur wt, 1" 63 8roduct >ulfur wt, 3" 9+ ;H>B HrF1 1" 3 H2?HC recycle >CFA 1 33 3 H2 Consum$tion >CFA '+ 3 H2 8artial 8ressure $sia '6 + Cycle ;ength months 2* >OR (&AT F 5' 3 COR (&AT F 62 + .n the $ast cycle length had !een acti%ity limited" Howe%er since a $ortion of the reduced crude feed to the FCC is ty$ically now !eing hydrotreated cycle length has greatly im$ro%ed" Feed sulfur used to !e in the 2"+ to '"3 wt, range with target $roduct sulfur content at 1"3 wt," The current cycle has nearly reached 2 years with another year to year and a half $ro@ected !efore a com$lete catalyst changeout is needed" & $ortion of the $roduct can !e recycled to control se%erity with a lower con%ersion $er $ass" (e do not ha%e any trou!le with $ressure dro$ as it seems that the FCC catalyst fines largely $ass through the reactor" The feed is not filtered" =ense loading is critical to e<tending the life as sock loads suffer from regions of coke formation from $oor retention of feed distri!ution" Catalyst $ore si1e must also !e consistent with slurry molecule si1e as a load of small $ore si1e catalyst had a %ery short life" The dedulfuri1ed slurry is sold as Go"5 fuel oil" A&R;OC(CG# There are a num!er of refineries that feed FCC cycle oils or hea%y coker gas oils to hydrocrackers" These feeds as has !een discussed are %ery refracti%e" They are difficult to treat" They $ut a $remium on ha%ing a %ery high acti%ity denitrogenation catalyst and the higher the $artial $ressure the !etter" &s we discussed early today there are a num!er of $ro!lems associated with them dealing with solids handling filtration" >o the use of a graded !ed is a !ig assistance in $rocessing them on the long term !asis" C&.G# (e feed the FCC hea%y cycle gas oil and hea%y and light coker gas oil to a hydrocracker" (e o$erate at 2 *33 $si with the hydrogen $urity of greater than 73 $ercent and we target our weight a%erage !ed tem$erature to achie%e a 5+ $ercent con%ersion" F;CTCHCR# Aoth HCGO 2FCC cycle oil4 and HMGO 2hea%y coker gas oil4 are $rocessed !y refiners in

hydrocracker?hydrotreater units" (e will let the indi%idual refienrs comment on conditions and yields" >uffice it to say that these oils are %ery aromatic and re/uire high $ressure and low ;H>B relati%e to %irgin streams" (e ha%e three such hydrotreaters in Ja$an feeding hea%y coker gas oil" O$erating conditions are as follows# om/any MO& TO& F.J. O.; O.; O.; Refinery 0arifu Mawas >odeg aki aura >nit *y/e FCC FCC FCC 8retrea 8retrea 8retrea tment tment tment ,eedstoc+ >R BGO 63F 63, 93, Coker ;GOTHGO 73, '3, 13, 23F '3, ,eedstoc+ Pro/erties =ensity 2*"+ 22"3 23"6 >ulfur 2wt,4 1"9 2"+ '"3 93, A82LF4 1393 1323 1313 '/erating onditions ;H>B 21?hr4 1"32 3"*+ 2"3 H2?O.; Ratio 2>CFA4 '533 1233 '333 $$H2 2$sia4 1533 563 62+ Cycle ;ength 2month4 2' 2' 11 Bottom Product Sulfur 3"31 3"1 3"37F 7&t39 3"1+ atalyst MF931 MF931 MF931 H H H %uestion 33 Hield estimates from (ydrocrac+ing catalyst 0endors s(o& a decreasing trend in formation of crac+ed gases. Bo actual commercial /erformance data 0erify t(is trend) T&>MCR# Choice of 1eolite ty$e catalyst o%er amor$hous catalyst will result in lower formation of cracked gases" (e ha%e o!ser%ed that the recycled gas $urity has remained fairly constant from start of run to end of run o%er a two to three year cycle and relati%e little $urging was done" This was for a middle distillate a$$lication" For na$htha cracking though we ha%e o!ser%ed an increase from start of run to end of run" .n one of our units we ha%e reached 17 months into the cycle and the deacti%ation has !een !etween *L to +LC or 6L and 13LF" This re$resents a high degree of sta!ility in the o$eration" Gas $roduction from the start of run condition to the $resent endFofFrun condition is %ery similar" F;CTCHCR# The yield estimates are accurate" Commercial o$erating data %erifies the im$ro%ement" The reasons for these yield im$ro%ements are a com!ination of what we !elie%e to !e three fundamental shifts" 1" & shift from Gi0o to Gi( catalysts" The Gi( catalysts offer greater hydrogenation acti%ity with less o%erF cracking" Hence there is also a lower and more sta!le gas make o%er the course of the catalyst cycle" 2" 0ore acti%e catalysts are !eing used" O$eration at lower tem$erature reduces gas formation" .n addition yield decline 2>OR to COR difference4 is reduced significantly" '" .m$ro%ed 1eolites" H&HG# (e re$laced catalysts in two of our hydrocrackers and in each case we found su!stantial reductions in our gas make" (hen we switched out one unit that had a!out a four year old catalyst in it we reduced gas make !y almost half" .n the other one that had eight year old catalyst gas $roduction was reduced more than half" GCORGC H&=J.;O.QO: 2Qeolyst .nternational4# (e ha%e o!ser%ed !oth commercially and in $ilot $lant studies re$eatedly less total gas make with our !ase metal nickel tungsten and no!el metal hydrocracking catalyst %s" com$etition $roducts" Ty$ically we ha%e seen at least

one to two $ercent less gas make de$ending on feed and $rocess conditions" (e !elie%e this is due to the ty$e of 1eolite technology and catalyst formulation techni/ues that we em$loy in all of our hydrocracking catalyst $roducts" %uestion 3! ,or (ydrotreaters configured &it( se/arate li5uid and gas /re(eat- it (as "een suggested t(at a small amount of (ydrogen "e inCected &it( t(e li5uid feed to reduce fouling on t(e eAc(anger train. Boes anyone do t(isand if so- &(at is t(e ratio of (ydrogen to feed c(arge) 1(at ot(er issues s(ould "e considered) A&R;OC(CG# >ome of the hydrocracking units and resid hydrotreating units designed !y :nocal in the $ast had se$arate heat e<changer trains to $reheat the oil and the recycled gas to the hydrotreating reactor" For these units it was common to add a small amount of recycled gas to the oil feed u$stream of the feedFeffluent e<changer increasing the hydrogen $artial $ressure" The theory is to inhi!it coking against the hot tu!e wall and also incrementally increase the %a$or %elocity through the e<changer" A.GFOR=# Hes we ha%e seen se%eral refiners in@ect hydrogen into the li/uid feed to reduce fouling in the e<changer train" The $rimary !enefit as 0r" Aarloewen said is the increased hydrogen $artial $ressure and the increased %elocity through the e<changers there!y reducing the de$osition $otential of material inside the e<changer tu!es" Hou need to make sure that the hydrogen does not result in some o%erall hydraulic limit or significant change in heat transfer through the $reheat e<changers that may limit your heat duty" >ome units were initially designed for hydrogen in@ection" >o these factors ha%e already !een considered in the design of the unit" .t is also our o!ser%ation through feedstock characteri1ation !efore and after hydrogen addition that the hydrogen in the $reheat e<changers does not decrease hydrocar!on $olymeri1ation in many reacti%e feedstocks" This confirms that hydrogen is not a!le to saturate any of the olefinic materials in the feed until it reaches the reactor catalyst" &s a result understanding the cause of fouling is e<tremely im$ortant !efore in%esting in ca$ital to make this o$erational change if you do not already ha%e the ca$a!ility" 8olymeri1ation reactions may !e decreased with the addition of hydrogen !ut only if the reactions are !eing caused !y high film surface tem$eratures on the e<changer tu!e wall" .f inorganic $articulates are causing the fouling adding hydrogen ahead of the e<changers to increase the %elocity may sim$ly $ush the $ro!lem downstream to the reactor !ed" &s a result if the fouling mechanism is not $ro$erly identified hydrogen addition may accelerate reactor !ed fouling resulting in $remature catalyst changeouts or more fre/uent skimming of the to$ of the !ed" C&.G# (e ha%e !een successful at =elaware City adding hydrogen to our hydrocracker feed to reduce feed side fouling of e<changers" (e do fi< the hydrogen flow rate at a small rate inde$endent of the feed rate" F:>>C;;# (e ha%e a distillate hydrotreater in 8ort &rthur that we tried this on and it did not work" Aasically what ha$$ened was e<actly what 0r" Ainford descri!ed" (e $ushed the $ro!lem into the reactor" .nstead of ha%ing a down time after nine months @ust to clean some heat e<changers we had a down time after nine months to dum$ the reactor and clean the heat e<changers" >o we are no longer in@ecting hydrogen into these heat e<changers and we are continuing to trou!leshoot the $ro!lem" HCGMC# (e in@ect hydrogen into the li/uid feed of one our diesel hydrotreaters at a rate of +33 standard cu!ic feet $er !arrel" The feed to this unit is %ery reacti%e com$rised of light cycle oil and light coker gas oil" =esign issues that we consider when in@ecting hydrogen into li/uid feed include total recycled gas rate thermal design and heat transfer e/ui$ment the metallurgy of the feed effluent e<changers the heaters and the associated $i$ing the reacti%ity and sta!ility of the li/uid feed and finally the sta!ility of the flow regime" . refer you to the 199' G8R& QE& transcri$t $age 96 Question 23" >yncrude Canada re$orted some work that their research de$artment had done concerning the chemistry of free radical saturation and other items there" 0&;CM# Just to reinforce some of the things that 0r" Henke has said we !elie%e that the !enefits of in@ecting hydrogen are $rimarily related to %elocity effects and !etter heat transfer coefficients $erha$s $re%enting some fouling in these e<changers" Howe%er a word of caution has !een already $ointed out" Hydrotreaters that are configured with se$arate li/uid and gas $reheat systems will sometimes ha%e metallurgy that is inca$a!le of handling H2> that may !e in the recycle gas" >o !e careful where you in@ect it" .f there is no recycle gas scru!!er or if it is only $artially effecti%e the hot H2> corrosion can occur in some of the e<changer e/ui$ment if it is not '33 series stainless steels"

&lso $otential flow distri!ution $ro!lems will de%elo$ in the multi$ass heaters if some of you ha%e designs that do not ha%e $ositi%e flow control and are relying on symmetrical flow distri!ution" Two $hase flow may gi%e you flow distri!ution $ro!lems across those heaters" T&>MCR# 8ushing it one stage further we do ha%e the ca$a!ility in !lack oil $rocessing of in@ecting hydrogen into the heater the oil heater" (e do ha%e se$arate gas and oil heaters" Howe%er the idea here was to im$ro%e the o%erall heat transfer coefficient or the heat flu< when you are really $ushing the unit" .t was also there to minimi1e the $ossi!ility of coking in the heater" Howe%er we o$erate the heaters at low enough tem$erature that we %ery seldom see any coking $otential occurring in that heater" (hat we ha%e seen is as already mentioned a tendency to cause flow insta!ility of the oil when hydrogen is in@ected" This facet has to !e done carefully" (e ha%e tried it !ut ha%e really not seen the !enefit in reality" %uestion 3# Is "iodesulfuri6ation tec(nology nearing commerciali6ation) 1(en do /eo/le t(in+ t(is mig(t actually reac( t(e refiner) HCGMC# (e are o$timistic a!out the commerciali1ation of !iodesulfuri1ation technology" (e are working closely with Cnergy Aio>ystems to incor$orate Moch mi<er technology into the design of the !iodesulfuri1ation reactor" Moch also is working closely with Cnergy Aiosystems to de%elo$ a !iodesulfuri1ation $rocess for na$htha streams" (e ha%e !een told !y Cnergy Aiosystems that they are a$$ro<imately 5 to 17 months away from commercial commitment to !uild the first diesel !iodesulfuri1ation unit" >&0:C;># . ha%e similar information" 0arathon !elie%es that this technology will !e a$$lica!le for na$htha desulfuri1ation" (e are currently com$leting a @oint research de%elo$ment agreement with a leading !iodesulfuri1ation concern in%ol%ing a colla!orati%e research effort and a$$lication of 0arathonOs technology to the !iodesulfuri1ation $rocess" (e estimate commerciali1ation for na$htha desulfuri1ation within three to fi%e years and diesel !iodesulfuri1ation in as soon as 5 to 12 months" >&0.R 0OH&00C= H&;&(&G. 2>audi &ramco4# Could we ha%e a !rief descri$tion of the !iodesulfuri1ation $rocess? H.GG.G># There is a $a$er that was $resented a cou$le of years ago that had some of the introductory material on it" 0.MC 8&CHCCO 2Cnergy Aiosystems Cor$"4# &s the two s$eakers ha%e already stated !iodesulfuri1ation is %ery near commerciali1ation" &t Cnergy Aiosystems in (oodlands Te<as we are working on a $rocess with se%eral refiners to desulfuri1e $etroleum streams with genetically engineered micro!es and air at am!ient tem$erature and $ressure" Our current focus is on the commerciali1ation of diesel !iodesulfuri1ation" (e ho$e to ha%e a commitment within the ne<t 5 to 17 months to announce the worldOs first !iodesulfuri1ation $rocess" Aiotechnology for na$htha and crude oil as well as decanted oil desulfuri1ation will ho$efully follow shortly thereafter" (e are not aware of any other com$any that is acti%ely $ursuing the de%elo$ment of a !iological $rocess for remo%ing sulfur from $etroleum streams" C=(&R= >0.TH 2:O84# :O8 also considers !iodesulfuri1ation a %ery e<citing and interesting area with significant ad%antages and o$$ortunities if a$$lied correctly in the refining and $etrochemical industries" (e ha%e !egun an acti%e and aggressi%e $roof of $rinci$le in%estigation with a $artner to determine $rocess feasi!ility and to /uantify some of the !enefits and technical challenges" The conce$t is truly in its infancy and realistically we !elie%e it will !e at least a few more years !efore -true !reakthrough- is achie%ed such that !ulk desulfuri1ation can !e offered commercially" :O8 will !e working on s$ecific $ro@ects in this area and we will seek refinersO feed!ack during the de%elo$ment of this technology" B"M" M&8OOR 2.ndian .nstitute of 8etroleum4# (hat le%el of diesel sulfuri1ation is e<$ected for the na$htha and diesel $roducts $articularly the diesel !iodesulfuri1ation $rocess coming u$ in a!out a year? HCGMC# For diesel it is a strong function of the residence time" Hou can get $roduct sulfur down to the lower $$mw le%els with enough time in the !ioreactor" &s far as na$htha desulfuri1ation is concerned it is too early to tell what it will !e !ut . assume that they will get it down to $$mw le%el" &gain it will !e a function of residence time" O!taining %ery low $roduct sulfur le%els may not !e economically %ia!le" One of the things we are o$timistic a!out is the com!ination of !iodesulfuri1ation with con%entional hydro$rocessing" .n this case we would !e asking the

!iodesulfuri1ation reactor to take out the more refractory com$ounds that con%entional hydro$rocessing currently has difficulty remo%ing" %uestion 3: In start-u/ of (ydrocrac+ing catalyst- is anyone /racticing simultaneous /resulfiding and ammonia /assi0ation) Are t(ere any /ro"lems controlling DH2HS formation in t(e effluent /i/ing) A&R;OC(CG# (e know of one hydrocracker that used e< situ sulfided catalyst to which a nitrogen containing com$ound had !een added !efore the catalyst was loaded" This did not com$letely $assi%ate the catalystOs cracking function since most of the ammonia was desor!ed during the startu$ and lost from the system" (e would recommend se$arate sulfiding and $assi%ation" The ty$ical a$$roach is to sulfide first and then $roceed with $assi%ation" (ash water should !e started !efore the ammonia or nitrogen containing com$ound is introduced for the $assi%ation" GCORGC H&=J.;O.QO: 2Qeolyst .nternational4# (e offer !oth !ase metal and no!le metal hydrocracking catalysts" (e do not ty$ically re/uire ammonia $assi%ation during startu$ or during normal o$eration" (e ha%e found in our +3 $lus startu$s that through o$timi1ed startu$ $rocedures we can effecti%ely acti%ate and startu$ our hydrocracking catalyst without the need to $assi%ate" %uestion 3; 1(at routes does t(e industry utili6e to (ydro/rocess BA' or "lends including BA') Please /ro0ide s/ecific details. RO0&G# (e used to hydrotreat =&O in a %acuum gas oil desulfuri1er and we were limited to a +3 to ++ $ercent lift on the >=& unit to kee$ the concar!on down to an acce$ta!le le%el" (e su!se/uently con%erted the >=& unit from a mi<ed sol%ent e<traction o$eration to straight !utane sol%ent o$eration with the goal of achie%ing a ma<imum lift of a!out 63 $ercent" O$eration at high lift forced us to discontinue hydrotreating the =&O due to unacce$ta!le catalyst life on the BGO unit" >ome $reliminary ;8 work as indicated that we may ha%e an incenti%e to reduce this lift and hydrotreat =&O during the summer months if as$halt $rices are high enough" T&>MCR# (e do ha%e some e<$erience with =&O in hydrocracking o$erations" For $ro$ane =&O we find that it is easier to crack than HBGO" The =&O should !e a $urer hydrocar!on with the resins and as$haltenes remo%ed" Aut if some resins are left in the =&O then it !ecomes more difficult to crack and effects catalyst life" Therefore the ease or otherwise to $rocess =&O will strongly de$end on the /uality of the deas$halting o$eration" (ith the units cou$led it is $ossi!le to control the relationshi$ !etween hydrocracking and deas$halting" >&0:C;># The 0arathon Garry%ille refinery currently $rocesses ;BGO HBGO and u$ to 23 %ol, =&O in a 933 $sig 75 333 !arrel a day FCC feed hydrotreater" Rose unit o$eration the charge rate sol%ent com$osition and the lift $ro%ide the desired through$ut of =&O according to o$erating targets esta!lished for the hydrotreater" These are defined !y $ast history current o$erating conditions and e<$ected catalyst $erformance which is closely monitored !y a daily sam$ling of the feed and $roduct" Catalyst deacti%ation rates are calculated from these data and com$ared to reference cur%es de%elo$ed through $ilot $lant studies conducted at our research center" The =&O /uality and /uantity is controlled to target around a 1"6 to 2 wt , com!ined feed concar!on" The hydrotreater $roduct is ty$ically "' to "* wt , concar!on" 0etals o!%iously as well as concar!on deacti%ate the catalyst" (e do not routinely test for metals !ut correlate those to concar!on" (e achie%e 1+ month runs !ut the se%erity is dictated !y economics" The unit has four reactors in $arallel with a 1"*+ s$ace %elocity a 563LF startFofF run weighted a%erage !ed tem$erature and a 663LF endFofFrun weighted a%erage !ed tem$erature" A&R;OC(CG# =&O is ty$ically fed to FCC $retreaters" One /uestion to really kee$ in mind is the dee$er you dig in your deas$halting unit the more metals will come with it" Those metals are going to !e /uantitati%ely laid down on your hydrotreating catalyst" >o the dee$er you lift or the more you lift the more you ha%e to $ro%ide metals remo%al ca$acity at the front end of that hydrotreating unit ty$ically through the use of demet catalysts" There also has !een deas$halted oil fed to hydrocrackers" Howe%er on the $articular unit that this occurred as they tried to raise the con%ersion on the =&O $ortion they found significant rate of deacti%ation and they !acked off" F;CTCHCR# =&O hydro$rocessing resem!les resid hydro$rocessing e<ce$t that the metals remo%al load is lower and the

Conradson car!on content is lower" Hydrotreating deacti%ation rates are high relati%e to gas oil $rocessing" Catalysts are selected !ased u$on the com!ination of high acti%ity and high metals $icku$ ca$acity" One e<am$le#

Catalyst# MF931HF1">C $$H2# 523 8>.G Feed# BGOT+F13, =&O H2?Oil# 162+ 2CFA ;H>B# 2"5 1?H 8roduct >ulfur# 3"' wt, Cycle# 2' months
F:>>C;;# .n 8ort &rthur we ha%e a :O8 =eme< unit" Our colleagues at =iamond >hamrock at Three Ri%ers are $ro!a!ly the only one that can relate to that statement" Aut !asically it is a sol%ent e<traction unit which uses normal !utane" (e actually make three cuts off of the =eme< unit" (e make a =0O a resin cut and an as$halt cut" (e run the unit at a$$ro<imately 223LF softening $oint on the as$halt" &$$ro<imately fi%e years ago we started feeding the resin and the =0O to our :ni!on unit" 8rior to that we were only feeding the =0O along with hea%y %acuum gas oil" (e are a!le to get a$$ro<imately 73 $ercent sulfur remo%al +3 $ercent concar!on remo%al and 63 $ercent metals remo%al across our :ni!on unit" (e do ha%e a $ro!lem on the :ni!on though as a result of running this higher as$haltene containing material" That is foaming in our high $ressure se$arator" The foaming has !een a $ro!lem e%er since we started running the resin mostly at endFofFrun" On this $articular catalyst run that we are into right now we seem to ha%e a continuous foaming $ro!lem in the se$arator and we are currently working on installing an antifoam in@ection system" (e ha%e done a cou$le of things to change the system" (e made some modifications in our =eme< unit in Go%em!er" (e also changed from a Criterion catalyst system to an &k1o catalyst system on the :ni!on" Gow Criterion would $ro!a!ly say that it is that &k1o catalyst system that is causing the foaming !ut we really do not know" (e do know that something has changed" . @ust want to warn e%eryone that you may ha%e that $ro!lem" (e ha%e discussed it with :O8" They ha%e recommended that we install a larger high $ressure se$arator" &s you might imagine that has !een %ery difficult to @ustify to management" 0.MC H:GTCR 20"(" Mellogg Co"4# (ithin our technology alliance with 0o!il &k1o Go!el and Fina we ha%e recently com$leted a large series of $ilot $lant tests looking at hydrocracking deas$halted oil from a Rose unit in com!ination with %acuum gas oil" (e ha%e looked at !lends consisting of 23 to *3 $ercent =&O at con%ersion le%els ranging from 23 to 63 $ercent in a single $ass configuration" (e ha%e $u!lished the early results of this at the 1996 G8R& &nnual 0eeting" >u!se/uent to that we ha%e done long term sta!ility testing where we ha%e demonstrated +3 $ercent con%ersion of a !lend of *3 $ercent =&O and BGO" The $ressure le%el in that test was 2333 $si" . think what we ha%e learned is that it is %ery im$ortant to !e a!le to a$$ly s$eciali1ed indi%idual catalysts to address the metals content and car!on residue content of the =&O ty$e feedstocks" %uestion 3= Brastic reductions in sulfur are re5uired to meet Euro/ean diesel fuel s/ecifications or alifornia clean air regulations. *(ese reductions- as &ell as seasonal c(anges in diesel /ool "lend com/onents- are ma+ing it difficult to meet cloud- /our- lu"ricity- and ot(er /roduct s/ecifications. 1(at /rocessing- c(emical treatment- and "lending o/tions can "e used to maAimi6e diesel /ool economics in t(is en0ironment) F;CTCHCR# The sim$le a$$roach is to use kerosene !lending and?or additi%es in the diesel $ool to im$ro%e the cold flow $ro$erties" The $ro!lem is using high %alued kerosene or e<$ensi%e additi%es in the winter diesel season" .n Curo$e se%eral refineries ha%e selected the &k1oFFina CF. Technology and 0o!il 0idF=istillate =ewa<ing Technology to !ring the cold flow $ro$erties of their diesel and heating oil into s$ecs" The following $rocess o$tions are !eing a$$lied# 214 diesel dewa<ing o$erating in H=> mode during the summer and in dewa<ing mode during the winter $roducing low cloud $oint or $our $oint diesels with e<tremely low $roduct sulfurI 224 high con%ersion dewa<ing" =ewa<ing com!ined with a hydrocracking functionality which allows the con%ersion of ;BGO HBGO to low sulfur low $our $oint $roducts" These can !e !lended directly into the diesel $oolI 2'4 0&MF;CO a $rocess that con%erts ;CO into high octane gasoline and low sulfur high cetane diesel" .n many cases these $rocesses can !e a$$lied to e<isting units with only minor hardware changes" &s you may ha%e heard 0o!il &k1o Go!el Mellogg and Fina ha%e merged their 0&M CF. and 0idF=istillate =ewa<ing Technologies into one technology $artnershi$ offering the !est and most fle<i!le technology a$$roach to $roducing high /uality diesel"

A.GFOR=# . am going to focus on the lu!ricity $ortion of this /uestion" 0r" Fletcher effecti%ely co%ered a lot of the other issues" >e%ere hydro$rocessing to meet sulfur and aromatic s$ecifications can result in low lu!ricity fuels" This is certainly the case with >wedish diesels and C&RA diesels $roduced to meet the ultra low sulfur and ten $ercent aromatic s$ecification" Gewly de%elo$ed nonFacidic lu!ricity im$ro%ers are one o$tion to im$ro%e the lu!ricity of these fuels" =iesel lu!ricity can also !e ad%ersely affected !y e<cessi%e kerosene !lending to meet winter cloud or low tem$erature o$era!ility s$ecifications $rimarily due to low %iscosity" The lu!ricity of these fuels can also safely !e im$ro%ed with nonFacidic lu!ricity im$ro%ers" &nother o$tion is to use a cloud $oint de$ressant and?or low tem$erature o$era!ility additi%e to !ack out the kerosene" This may safely meet !oth lu!ricity and low tem$erature s$ecifications" The resulting hea%ier fuels also ty$ically ha%e a higher cetane num!er and are more dense resulting in !etter ignition $ro$erties !etter cold starts and sometimes im$ro%ed fuel economy" (e introduced a new cloud $oint de$ressant last year and are currently field trialing se%eral more new chemistries this fall to offer the refiner more choice in cloud additi%es that can !e tailored to meet the o%erall C&RA diesel !lend $ool o!@ecti%es" .n reference to diesel $ool economics my res$onse in >ession * Question *2 will co%er this issue" ;.G&> JOM:A&.T.> 2;u!ri1ol4# The ;u!ri1ol Cor$oration offers the refiners chemical treatment o$tions to meet cloud $oint $our $oint lu!ricity and o$era!ility re/uirements" For e<am$le there are now chemistries a%aila!le to thermodynamically lower cloud $oint" =&B.= =.C&0.;;O 2Criterion Catalyst Com$any4# Criterion and &AA ;umus offers >ynflow as one of its >yn technologies" . will gi%e you an e<am$le of how it can reduce cloud $oint" .n one s$ecific customer test we reduced cloud $oint from '* to 15LF and maintained 133 $ercent distillate yield in the $roduct" (hen we reduced distillate yield to 97 $ercent the cloud $oint reduced further to 5LF" On this same feed if the customer cut the ten $ercent hea%iest material out he could ha%e reduced the cloud $oint to 13LF" %uestion !8 1(at eA/erience (a0e refiners (ad in /rocessing atmos/(eric reduced crude &it( E$' in lo& /ressure (ydrotreaters to /roduce , feed) 1(at /ercentage of reduced crude (as "een /rocessed) 1(at le0els of desulfuri6ation and R reduction are reali6ed) 8CTCR>OG# One of our refineries $rocesses reduced crude deri%ed from fairly sweet light crude through a low $ressure distillate desulfuri1er" &!out *+, of the reduced crude is hydrotreated along with ;CO and straight run distillates" FCC flue gas >o< reduction is the main $ur$ose for the hydrotreating although FCC $erformance has im$ro%ed as well" The o$erating conditions are as follows# Feed >ulfure wt , 3"53 Reduced Crude >ulfuer wt , 1"33 8roduct >ulfur 2Frac Atms4 wt , 3"'+ ;H>B HrF1 1"2+ 8ressure $sig 733 Recycle H2?HC >CFA 1 563 H2 8artial 8ressure $sia 6'3 Cycle ;ength months 12 >OR (&AT F 5+3 COR (&AT F 6'3 Reduced Crude Rams!ottom wt , 2"+3 Frac Atms Rams!ottom wt , 1"+1 to 1"77 Reduced crude as feed , *+ The unit has $erformed !etter than initially e<$ected achie%ing 5+, reduction in sulfur and 2+ to *3, reduction in Rams!ottom car!on" Trimetallic catalyst from &k1oFGo!el is used" The feed is not filtered and most recent cycle was cut short due to $ressure dro$ after an u$set when the recycle com$ressor shut down" The $ressure dro$ across the first !ed increased from 63 $si to 1'3 $si" Reduced crude was taken out of the feed and the recycle hydrogen was

reduced to get the $ressure dro$ !elow the ma<imum allowed 133 $si until re$lacement catalyst could !e installed" Com$ressor u$sets in na$tha hydrotreaters ha%e also resulted in sudden increases in $ressure dro$" Our e<$erience on our other FCC feed hydrotreater shows filtration is /uite im$ortant" A&R;OC(CG# One refiner that we worked with has !een $rocessing atmos$heric resid in BGO hydrotreating unit" The unit o$erates at a!out 633 or 733 $ounds $artial $ressure" They are a!le to achie%e ty$ically a!out 63 $ercent desulfuri1ation and 23 to 2+ $ercent CCR reduction" The le%el of CCR reduction is %ery much a function of the hydrogen $artial $ressure of the unit and if this unit were to try to dramatically im$ro%e on that CCR reduction we !elie%e that they would run into $ro!lems due to the lack of hydrogen $artial $ressure" (hat they are really con%erting are the sulfur com$ounds and the as$haltene com$ounds that are left in the BGO and as they try to get to higher con%ersions they ha%e a hard time in that low system $ressure to achie%e %ery much con%ersion on the as$haltene $ortion" F;CTCHCR# (e are familiar with a num!er of units that are $rocessing reduced crude in hydro$rocessing units with low o$erating $ressure relati%e to units designed for atmos$heric tower !ottoms" .n general the cycle lengths are low relati%e to gas oil in the same unit" &k1o Go!el is familiar with se%eral cases in which the reduced crude is o$erated in 533 to 733 $sia $artial $ressure hydrogen hydrotreaters" The concentration of reduced crude is less than +3, in all cases" :$ to 73, desulfuri1ation and '+, CCR remo%al has !een achie%ed" This ty$e of o$eration is usually only $ractical when reduced crude sulfur CCR and metals 2Gi and B4 are relati%ely low 2>D1 wt, CCRD2 wt, GiTBD+ $$m4" C%en in these cases cycle lengths of less than 12 months are ty$ical" Cycle length is $rimarily de$endent u$on o$erating se%erity 2,H=> ,H=CCR and ;H>B4 since this determines the deacti%ation rate due to coking" The ma@or !enefit from this treatment is %anadium remo%al and the resulting reduction in re/uired FCC catalyst $urchase" .n some cases the FCC gasoline and?or GO< emission limits also @ustify the shortened cycles" C;.Q&ACTH &;;CG 2Criterion Catalyst Com$any4# & num!er of CriterionOs customers are $rocessing reduced crudes at low $ressures in BGO units" Ty$ically these units are $rocessing a!out 2+ $ercent resid in a !lend of BGO although there are also a num!er of customers who are $rocessing with straight run distillates" Ty$ical desulfuri1ation le%els are a!out 73 $ercent and CCR remo%als u$ to 5+ $ercent" &t %ery low $ressure let us say at around less than 1 333 $ounds the significant deacti%ation of the catalyst system from coking due to the high CCR will !e o!ser%ed e%en at the low s$ace %elocities" %uestion !1 Is anyone successfully (ydrotreating full range , gasoline to reduce sulfur) 1(at are t(e /roduct sulfur le0els and corres/onding M'D and R'D octane losses. 1(at &ere t(e initial sulfur- M'D and R'D le0els) RO0&G# (e ha%e done e<tensi%e work in this area" (e used commercially a%aila!le co!alt moly catalysts to minimi1e olefin loss and targeted a $roduct sulfur le%el of a!out 2+3 $$m" The FCC na$htha e<$erienced an octane loss of 12 octane num!ers" (e also $erformed the same test on our light RCC gasoline and e<$erienced the loss of 19 octane num!ers due to its higher olefinicity" 0ost of the sulfur in cracked gasoline is in the '53 degree $lus cut" The way to minimi1e the se%ere octane loss is to desulfuri1e the '53 degree $lus gasoline only" This hea%y na$htha can either !e desulfuri1ed in a stand alone unit or it can !e dro$$ed down into the light cycle draw in desulfuri1ed and middle distillate desulfuri1er or ==> unit" There is a three or four $ercent loss in total gasoline yield to distillate which results from commingling hea%y na$htha with the much larger middle distillate stream" T&>MCR# .F8 and HR. ha%e licensed se%eral units to hydrotreat full range FCC gasoline to reduce sulfur" Ty$ically when the unit reduces the feed sulfur from a!out 26+ to a!out +3 weight $$m and the feed olefin is '1 weight $ercent the road octane loss has !een less than a!out fi%e num!ers" .f the feed sulfur was lowered from a le%el of say * 233 $$m to *23 and the feed olefin content is 2* $ercent the road octane loss is less than '"+ num!ers" C&.G# (e conducted a week long test at our =elaware City $lant" The inlet sulfur was reduced from 1955 $$m to 3"1 $$m" The ROG was reduced from 77"7 to 66"5 and the 0OG was reduced from 67"2 to 63"'" R.CH&R= FO;CH 2C=TCCH4# C=TCCH licenses a C=HES $rocess for reducing the sulfur content in full range FCC gasoline" Cight or ten different customer feed stocks containing 2+33 to 1333 $$m sulfur ha%e !een tested in the commercial

demonstration unit at C=TCCH" (e ha%e !een a!le to reduce the sulfur contents to +3 to 133 $$m le%el 29+, desulfuri1ation4 with octane loss 2RT04?2 of less than 1 to 2" Catalytic distillation $ro%ides the o$$ortunity to treat the high sulfur and high olefin fractions of full range gasoline from the FCC unit se$arately at o$timum conditions with lower octane loss and lower total installed cost than fi<ed !ed $rocesses" R.CH&R= RO>>. 2Criterion Catalyst Co"4# There are some refiners on the (est Coast and a cou$le in the midwest who are !elie%ed to !e successfully hydrotreating FCC gasoline or ha%e done so in the recent $ast %ia se%eral different o$tions" (hile one can achie%e a!out 93 $lus $ercent H=> on full range FCC gasoline %ia con%entional hydrotreatment there will !e significant loss of ROG and 0OG due to saturation of olefins in the front end of the stream" (ith s$ace %elocities in the range of + to 7 and 92 to 97 $ercent H=> a * to 7 num!er loss in ROG and a!out a 1 to ' num!er loss in 0OG are likely with the octane loss !eing more se%ere at the higher desulfuri1ation rates" Aecause of this many refiners ha%e considered $referentially hydrofeeding @ust the hea%y FCC gasoline as was mentioned !efore which is relati%ely sulfur rich and olefin $oor and thus minimi1es the octane loss" .n this case one can target relati%ely high H=> rates and hold ROG and 0OG losses down to $erha$s 1 to 2 num!ers"