Session IV - Light Oil Catalytic Processing

A. Alkylation-Sulfuric Acid 1. Feed Question 1 Does anyone have problems with ice formation in the contactor feed nozzle piping where the "wet" iso recycle joins the cold effluent recycle? Question 2 What instruments have refiners used for the custody transfer of spent and fresh sulfuric acid for the al ylation unit? Question ! What levels of light ends "hydrogen through ethane# in the al ylation feed have refiners been able to tolerate? Do refiners with feed selective hydrogenation units have product strippers$ or flash separators only? 2. Process Question % What is the recommended water content of circulating acid in &' and & 2()% al ylation units? What are the best ways to control this? Question * +s anyone using al ylation co,catalysts? What are the benefits? Question What e.periences$ if any$ have people had using capacitance probes to determine the settler acid level and the acid, to,hydrocarbon ratio in the reactor? Question / We have had occasional foaming in our al aline water wash system0 1ould it be caused by poor ma e,up water 2uality "3D(# or aromatics in the feed or something else? What type of ma eup water do you use "4'W$ condensate$ process water#$ and what is the 2uality? +f the problem is aromatics$ at what level does it occur? Question 5 What effects are seen in the D+4 operation when chlorides come in with ma e,up isobutane? &as anyone e.perienced severe tray fouling in the D+4 and6or pluggage in the feed6isobutane recycle coalescer as a result of it? Question 7 What are your e.periences with$ and the causes of$ foaming in spent acid tan s or acid truc s6railcars? Question 18 &ow do you troubleshoot the acid wash electrostatic precipitator to ensure that it is wor ing efficiently? Does anyone test for acid in the effluent? What procedure is used? Question 11 Discuss e.perience with running above 80- olefin space velocity in sulfuric acid al ylation units0 (pecifically comment on reaction zone temperature limitations$ corrosion problems$ al ylate yields and acid consumption effects0 Question 12 +s there much industry e.perience with using bau.ite for effluent treating? What benefits and costs can be e.pected from switching to bau.ite? (ince our refinery is short on isobutane$ can anything else be used for dry,out during bau.ite regeneration? Question 1! Discuss what corrosion has been e.perienced in sulfuric acid or &' al ylation al ylate splitter tower overhead systems0 Question 1% &as anyone e.perienced plugging problems on the flash drum side of the suction trap6flash drum? +f so$ what was the cause and6or solution? &as anyone documented a case of hydrate formation? Question 1* &as anyone e.perienced fouling or plugging in the al aline water wash heater or depropanizer feed heater? +f so$ what was the cause and6or solution? Was any of the material that fouled the e.changer collected and analyzed? +f so$ what was the composition? . !echanical Question 1What is the e.perience on erosion6corrosion of nozzle tips and candles in olefin feed distributors of al ylation units? What materials and6or coatings have refiners used to prevent this damage? )ur unit is e2uipped with an 9lloy 28

spray nozzle on each candle with a tungsten carbide insert0 3he candle is a carbon steel pipe nipple with a "greycoat" applied0 )ur unit is fitted with ":ightning" turbine type mi.ers0 ". #eneral Question 1/ What are the panelists; thoughts on preneutralizing the spray mitigation water? &as anyone used sodium silicate in this service? Question 15 What is the current "best" practice for washing the residual &2()% from an al ylation unit after draining for turnaround? +s a neutralizing circulation used$ or is deluging with water to the sewer a common practice? +f a circulating basic water wash is used$ what is the typical flow diagram for it$ and how is the p& of the water monitored and controlled? $. Alkylation-%ydrofluoric Acid Feed Question 17 What problems are caused by al ylating amylenes? What contaminants cause the different problems$ and how can the problems be mitigated? Process Question 28 What has been your e.perience with &' and &1 sensors for vapor detection? <lease give your overall philosophy of selecting different technologies and e.tent of success6reliability with each type and ma e of sensor0 Question 21 =ow that some of the new vapor suppression additive systems have started up$ what has been the e.perience with their performance? Question 22 'or &' al ylation systems$ what instruments are refiners using to indicate acid regenerator column bottoms levels? We currently use a temperature indicator with some success0 Question 2! 'or &' al ylation systems$ what instruments are refiners using to indicate acid settler levels other than sight glasses and D< cells? !echanical Question 2% &ow successful have magnetic drive pumps been in &' service? &ow do they compare with other sealless pumps? C. &efor'ing Process Question 2* What is the operating e.perience of reforming units being controlled by advanced controls and optimizers? What operating parameters are utilized for control to optimize performance? Question 2What has been the industry e.perience using density grading to recover 11> catalyst that was contaminated with "heel" catalyst? &as anyone attempted to e. situ regenerate "heel" catalyst for reuse? Question 2/ What process variables can improve the hydrogen purity from a 11> reformer contactor? What process add,ons have been used to further increase purity for high purity uses$ such as hydrocrac ers and resid hydrotreaters? Question 25 What are typical targets for moisture and chloride in the recycle gas for semiregenerative$ cyclic$ and 11> units? 9re these targets dependent on catalyst type or age? &ow are chloride6water levels controlled$ and what is the typical variability? Question 27 Do operators wait until brea through on their sulfur and chloride guard beds to decide when to change out the beds? +s there a better method? Question !8 +n the reformer recycle hydrogen gas there is a fairly high 2uantity of heavy hydrocarbons "we have measured over 2?#0 &ow does this affect the reformer catalyst in terms of co ing and conversion? Question !1

Where in the reforming process is the precipitation of ammonium chloride a problem? What effect does the reactor section operating pressure have on the chloride deposition problem? Question !2 &ave the high yield catalysts lived up to their e.pectations? What yield improvements have been realized? Does the yield improvement decrease at lower pressures? Question !! What are the problems associated with reducing the pressure in either a 11> or cyclic reformer$ and do the yield benefits justify the lower pressure operation for a gasoline or an aromatics unit? !echanical Question !% What methods have been used to control salt build,up in the recycle compressor$ other than washing it? &ow effective have they been? Question !*0 'or continuous catalyst regeneration systems using stainless steel instead of +nconel$ have there been problems with stress corrosion crac ing? What precautions need to be ta en? Question !What is the typical life of the vertical combined feed e.changer "not <ac ino.# in reforming service? What type and fre2uency of inspections and maintenance are recommended? (. Aro'atic )*traction Question !/ What methods are available for removing chloride from a solvent system? ). Poly'eri+ation Question !5 Where is Dimersol catalyst injected$ and what ratio of alumina to nic el do you maintain? Question !7 &as anyone had problems with forming sludge in Dimersol pumparound coolers? +f so$ how have you controlled it? Question %8 &ow fre2uently do you chec for contaminants "ammonia$ water$ diolefins# in Dimersol feed? What test methods are used? F. Iso'eri+ation Question %1 &ave the new high activity zeolite and chlorided isomerization catalysts proven to be a significant improvement over their predecessors? Question %2 &ave any refiners e.perienced e.cessive yield loss in isomerization units? 3o what has this loss been attributed? Question %! &ow are refiners addressing salt deposition and corrosion in their isomerization units? #. )therification Question %% What are the e.periences with advanced controls on ether units? What are the ey control parameters? Question %* What impact does feed sulfur content "particularly dimethyl sulfide# have on @34A catalyst life? What solutions e.ist for reducing the impact of sulfur in the feed? %. )n,iron'ental Control Question %What has the e.perience been with scrubbing the 11> regeneration vent gas? 9re many refiners scrubbing this stream?

Session IV - Light Oil Catalytic Processing

A. Alkylation-Sulfuric Acid 1. Feed -uestion 1 (oes anyone ha,e .ro/le's 0ith ice for'ation in the contactor feed no++le .i.ing 0here the 10et1 iso recycle 2oins the cold effluent recycle3 @9:ABC We are aware of people who have had freeze problems with their recycle iso,olefin feed control valve or their refrigerant recycle control valve0 3he cause has usually been traced bac to poor coalescing of the recycle isobutane and the olefin feed0 Dou can chec the effectiveness of your coalescer by analyzing the water content on the inlet versus the outlet0 + believe that (3>931) designs for 75? removal of free water in their coalescer designs0 Dou should also chec your olefin feed$ ma eup isobutane$ and recycle isobutane for water content0 Dou may be getting large amounts of water that impact the feed coalescer and overwhelm its ability to withdraw water away fast enough0 3he isobutane recycle can be a problem if you have low residence time in your overhead accumulator$ which can impact effectiveness of the water boot0 4+=')>DC 'irst$ + would li e to than (3>931) for helping provide answers to several of these 2uestions$ especially those that dealt with the design and operation issues$ and 9llen @oser of (3>931) deserves special recognition for his help here0 +ce formation in the (3>931) contactor reactor feed nozzle piping can occur when the temperature of the combined wet isobutane recycle and the cold effluent recycle is less than !2 '0 3ypically$ this condition results only when the propane content in the refrigeration loop is about 28?0 'or this to occur$ the refrigeration compressor is usually oversized to allow higher discharge pressures for total condensing0 ')(3A>C + agree with what @r0 @ale and @r0 4inford said0 We are planning to replace our coalescer in the ne.t year0 Entil that time$ we are wor ing around the problem that we are having0 We do not have a temperature indicator here$ but a calculation e.ists for the operator group so that they can appro.imate this temperature on the run0 3hey use this calculation to maintain the feed nozzle at around !% by bypassing a slipstream around the feed and effluent e.changer to heat the stream0 9 better solution$ of course$ is to replace the coalescer$ which we are planning on doing ne.t year0 3&+A>>D D9>DA "<all 1orporation#C (ince it has been mentioned that there is a need for a good li2uid,li2uid coalescer upstream of the al ylation plant$ + would li e to mention that <all 1orporation has a viable li2uid,li2uid coalescer which can deliver below 1* ppm free water downstream$ which in this case would protect the al ylation plant very efficiently0 (3AFA @93&E> "1hevron#C Dou could actually see freezing in the lines if you are water washing the D+4 a lot$ because the water tends to carry with the iso recycle when it meets the feed junction of the refrigerant recycle$ which could be at 1/ ' or 28 '0 3he situation is worsened if the coaleser is not functioning well0 3he actual freeze point happens right where the cold refrigerant recycle meets the isobutane recycle "including the feed#0 3his can cause the flow control valve in the iso plus feed line to fully open to compensate for the loss of flow due to partial freezing0 -uestion 2 4hat instru'ents ha,e refiners used for the custody transfer of s.ent and fresh sulfuric acid for the alkylation unit3 19+=C We have our acid regenerated by Dupont$ which has a plant adjacent to our :ouisiana plant0 3hey have an in,line magnetic type flow meter manufactured by 'o.boro$ and we agree with them that it is highly accurate and very reliable0

&9&=C 9lthough we do not use them$ we now of several refiners that do use mass meters for acid transfers0 @ore common for us is to use tan gauges or traditional meters0 (3>931) does recommend mass meters for custody transfers0 @9:ABC 3he bul of the installations that we have seen use weigh scales$ either truc weigh scales or rail weigh scales0 Esually$ the refinery will have truc weigh scales0 3he rail weigh scales are a little bit less common$ but they are readily available0 +t is probably the most effective way to reliably measure this material0 'E((A::C 9t our <ort 9rthur refinery$ we bring our sulfuric acid into the plant$ as well as out of the plant$ in rail cars to )lin0 With the spent acid$ we test the concentration$ we find out what the concentration is in the acid$ and then we ta e a strapping on the rail car0 )n the fresh acid$ we use the bill of lading and we strap the rail car0 G>AG &9::9EA> "@icro @otion$ +nc0#C @icro @otion;s mass flow meters are successfully being used for custody transfer of spent and fresh sulfuric acid0 @eter sizing and material selection are critical to ensure the safety and longevity of the system0 9cid velocity should be maintained below 2 fps to ! fps0 Farious metallurgies are available$ including 3efzelH lined meters0 Density and temperature$ measured by the same meter$ are used to monitor concentration during transfer0 -uestion 4hat le,els of light ends 5hydrogen through ethane6 in the alkylation feed ha,e refiners /een a/le to tolerate3 (o refiners 0ith feed selecti,e hydrogenation units ha,e .roduct stri..ers7 or flash se.arators only3 @9:ABC @ost sulfuric acid units can handle small amounts of 1 2 and lighter material0 We have reviewed units that have run as high as ! li2uid vol? and % li2uid vol?0 3his material will get purged via the refrigerant compressor receiver pressure control valve0 @any selective hydrogenation units only have flash separators$ which is a potential source of light ends into the sulfuric acid units0 9 typical unit that is using real high 2uality or high purity hydrogen will have very little inerts coming through with the treated material$ because the hydrogen consumption is very near stoichiometric in this unit0 We would recommend sending the vent stream from the flash separator of these hydrogenation units to the '11 wet gas compressor rather than the fuel system0 3his will recover the olefins in this stream0 3his stream is very small compared to the total flow of the wet gas compressor0 Dou may consider sending the refrigerant compressor receiver pressure,controlled vent to the '11E$ as well0 3his stream will contain some trace amounts of ()2 and ()!0 39(BA>C +n general$ dealing with the second part of the 2uestion$ +'< and &>+ design the selective hydrogenation units$ which we refer to as (&E;s0 We design them to avoid e.cess hydrogen in the reactor0 With no e.cess$ the production of light ends is minimized0 +f the hydrogen stream$ as @r0 @ale indicates$ is pure enough$ then it is conceivably possible to have zero gas at the reactor outlet$ and hence$ zero going to the al ylation unit0 4ut in the real world$ we do approach almost stoichiometric proportion of gas0 4ut$ there is always a little bit there0 @ost of the units re2uire only a flash separator0 Ese of a stripper$ of course$ will ensure that the ma.imum amount of light ends are stripped out$ and that will be a function of your incoming hydrogen0 Dou need to try to ensure that as much of the light ends as possible is stripped before the feed goes to the al ylation unit0 &A=BAC 3he amount of 12 that can be tolerated in the al ylation feed depends on the design of your particular al ylation unit$ and how much propane6propylene is in the feed0 3he light ends will eventually end up in the depropanizer section0 +f there is not much propane6propylene in the feed$ the 1 2 will significantly pressure up the depropanizer section0 We operate two E)< &' units with selective hydrotreaters0 4oth units are e2uipped with product strippers0 4oth units operate on butane6butylene feed0 3he only propane6propylene that enters the unit is through variation in

upstream fractionation0 3he 12, in the al ylate feed must be ept very low0 We target less than 8082 li2uid vol? in order to avoid venting from the depropanizer overhead receiver0 We also operate a (3>931) sulfuric acid unit0 3his unit operates with 1*? propane6propylene in the feed0 (everal years ago$ we ran for a short period of time with a selective hydrotreater upstream of the sulfuric acid unit0 3he only light ends removal was through two simple flashes0 3he operation was runnable$ but the light ends did result in high pressures on the compressor discharge receivers$ which restricted compressor capacity0 3he selective hydrotreater operation was discontinued for numerous reasons0 +f we had continued with that operation$ the economics would have justified the additional provisions for light ends removal0 (3AFA @93&E> "1hevron#C )ne of the things that we have found necessary in &' al ylation units is to have a condenser in the vent line on top of the depropanizer overhead drum$ because if you do not condense the &' out of there$ you are going to blow a lot of acid out with the noncondensables$ and that could actually increase the acid consumption rate substantially0 3he situation gets a lot worse if you have a lot of noncondensables "1 2$ etc0#$ and also$ if you are not operating the &' stripper correctly so that the ethane$ instead of coming out with the propane product$ goes overhead and pressures up the unit0 2. Process -uestion " 4hat is the reco''ended 0ater content of circulating acid in %F and % 2SO" alkylation units3 4hat are the /est 0ays to control this3 >)@9=C 9t 9shland$ we operate three &' al ylation units0 +n all of them$ we try to maintain 80*? to 805? water in the circulating acid0 We try to maintain the olefin feed moisture at less than * ppm0 &igher moisture levels can cause problems via two different mechanisms0 1arbon steel in the unit is normally protected by dense$ hard$ adherent iron fluoride scale0 Dilute acid will convert this iron to iron fluoride tetrahydrate$ which has a specific volume of !0* times the original scale0 3his e.pansion causes the scale to fall off the underlying metal0 1ontinued e.posure will convert the scale to iron fluoride octahydrate$ which is actually soluble in hydrofluoric acid0 9nother problem is the formation of azeotropes in the stripper0 3he settler effluent contains several hundred ppm of dissolved$ concentrated &' acid0 3his acid will be driven off as it flows down the stripper$ until a ma.imum boiling azeotrope forms at !-? &' in water0 3his azeotrope is e.tremely corrosive$ and if the concentration is high enough$ it will enter the side reboilers and cause failure0 We have recently begun to use seamless tubes on our side reboilers to avoid the possibility of this type of corrosion at the tube seam welds where there is always some residual hardness0 @9:ABC 9s a general guideline for operating &' units$ you need to eep the water content in an &' acid below 1 wt?0 3his is done by e.ternal acid regeneration0 'or a sulfuric acid unit$ a good operation will be ! wt? to % wt? ma.imum water0 9s discussed previously$ proper coalescing of the feed has a major impact on the water content in the circulating acid0 <A3A>()=C +n one of our refineries$ we have a dimersol unit that processes most of the propylene0 4ut$ at times$ we can put propylene$ or the rest of the propylene$ to the al ylation unit$ so we have a common feed drier for the propylene0 +n another refinery$ we have a fractionation dehydrator downstream of the @DA9 and @ero. treating system which dries propylene along with the butylene0 When only al ylating butylene$ we may not need to run this dehydrator tower in front of the system0 4ut$ because of the severely hydrotreated feed to the '11E$ we do not have to run the @ero. system0 @DA9 is not perfect at getting all of the &2($ so this partially condensing tower acts as an & 2( bac end stripper to help prevent sulfur consumption of the &'0 4+=')>DC 'or units operating with full mi.ed butylene feedstoc s$ (3>931) recommends typical water content of 2? to !?0 3ypical water content is !? to *? for units with an @34A raffinate feed0 Water content of the feed is controlled by

monitoring the efficiency of the feed coalescer through trac ing the water noc out rate0 )therwise$ water content is controlled by reducing water in the fresh acid or in the olefin feed0 Water precursors$ such as methanol$ need to be controlled as well0 4esides decomposing and forming water in the reaction zone$ methanol is a cosolvent which allows more water to get past the feed coalescer0 -uestion 8 Is anyone using alkylation co-catalysts3 4hat are the /enefits3 'E((A::C +n our (3>931) al ylation unit$ we have been using the 4etz 9l at product for appro.imately 2 years0 We have seen a 18? to 1*? decrease in our sulfuric acid consumption0 We new we were ma ing progress there when )lin gave us a call0 We have also seen a 2? to *? increase in the al ylate production off of the unit0 We have not seen any significant octane gain that we have been able to 2uantify0 3hat is part of what is advertised$ but we were not able to see that0 We have calculated about a 288? return on investment with the use of the 9l at0 We have also noticed that it has made our operation a lot more stable than the operation was before0 We receive our feed to our al ylation unit from &untsman$ and it varies 2uite a bit$ and we used to have a lot of operational problems0 3he 9l at seems to have stabilized the unit for us0 We are getting ready to do a trial using the =alco6A..on product0 We are not doing this because we have a problem with the 4etz productI we just feel li e doing some e.perimenting0 4+=')>DC 3he numbers that @s0 'ussell 2uoted are pretty typical of what we see with our co,catalyst product0 We have evaluated it in 21 commercial al ylation units$ which e2uates to about half of the al ylation units in the Enited (tates0 3ypical performance improvements 2uantified are !? to /? improvement in unit yieldI 18? to 2/? reduction in unit acid consumptionI and a 80! to 80/ number increase in al ylate octanes0 3hat small value octane increase can be very valuable$ but as @s0 'ussell mentioned$ it may be very hard to see in the unit$ and hard to 2uantify0 >eduction of undesirable side reactions in the unit$ as a result of using the co,catalyst$ has also reduced corrosion in the downstream D+4 tower and reduced al ylate end point0 Enits al ylating higher levels of propylene in their feedstoc s or mi.ed propylene,butylene,amylene feeds$ and generally those units operating at more severe conditions$ e.hibit the upper end of the improvements + 2uoted before0 We are evaluating a new product that is specifically targeted at higher acid reduction numbers0 +n our pilot plant$ we have seen acid reduction in the 2*? to !*? range0 We do have a commercial test on,going$ and another just about ready to start0 19+=C We have conducted several trials in two of our plants with al ylation aids0 We have been unable to 2uantify the benefits0 (o$ we are still wor ing with them$ and we will try to get those 2uantified0 ')(3A>C We have done several trials of 4etzDearborn;s 9l at J:0 We have seen a reduction in acid consumption of about 7?$ and an increase in al ylate yield of !?0 We are not sure that these results are 188? statistically significant$ however0 9fter the final 9l at J: trial$ we intend to conduct a trial of the 9l at 9>0 + thin that @r0 4inford was tal ing about 9l at 9> with the higher reduction in acid consumption$ somewhere between 2*? and !8?0 @9:ABC 3he data that + have reviewed on the various catalyst systems do indicate that there is some improvement0 )ne refiner told me that he thought that a lot of it might have been attributable to the fact that his engineers were loo ing at the unit a lot closer while they were evaluating the use of the catalyst0 4ut + really do believe there is an improvement0 +t is probably justified when you weigh the additional cost of more isobutane versus the catalyst cost0 3he numbers that + have reviewed indicate that the use of these catalysts is cost,effective0 -uestion 9 4hat e*.eriences7 if any7 ha,e .eo.le had using ca.acitance .ro/es to deter'ine the settler acid le,el and the acid-to-hydrocar/on ratio in the reactor3

')(3A>C We currently have capacitance probes on four settlers and D< cells on two others0 We have had good e.perience with the capacitance probes0 3hey more accurately identify where the top layer of foam e.ists$ and they show a good trend of the acid level0 -uestion : 4e ha,e had occasional foa'ing in our alkaline 0ater 0ash syste'. Could it /e caused /y .oor 'ake-u. 0ater ;uality 5<(S6 or aro'atics in the feed or so'ething else3 4hat ty.e of 'akeu. 0ater do you use 5$F47 condensate7 .rocess 0ater67 and 0hat is the ;uality3 If the .ro/le' is aro'atics7 at 0hat le,el does it occur3 4+=')>DC (3>931) has noted$ in their e.perience$ that the al aline water wash will have a tight emulsion when a surfactant enters the water wash with the olefin feed0 (eal oil and lube oil lea s into the process can also cause tight emulsions0 9romatics$ ethylene$ or ethyl mercaptan can all cause a detergent or soap formation in the al aline water wash at levels as low as *8 ppm in the olefin feed stream0 3o prevent the formation of solids in the al aline water wash$ they recommend that the ma eup water contain less than 28 ppm hardness as magnesium plus calcium carbonate0 1ontinuous water ma eup is re2uired to maintain a conductivity in the circulating water in the range of *888 to 5888 micro moles per centimeter0 19+=C We use clarified water as ma eup water$ with a total hardness of less than 58 ppm in two plants0 ')(3A>C @r0 4inford mentioned the *888 ppm to 5888 ppm range for 3D(0 )ur utility water happens to run about %888 ppm$ so it is a very good 2uality and we use utility water0 1ondensate can also be used as ma eup water$ but the hotter it is$ the more it tends to absorb hydrocarbon$ so it causes the 3)1 to go up in the water purge stream0 We also use an antifoam by 4a er <etrolite$ it is +<1 *1280 We use it at about 2 ppm in the caustic wash drum in order to control the amount of foaming in the neutralization section0 &A=BAC We have not e.perienced foaming problems due to ma eup water 2uality or aromatics in the feed0 We did have a foaming event that we attributed to high caustic concentration in the al aline water wash vessel0 3his condition was corrected by repairing the ma eup water flow meter and reestablishing an ade2uate ma eup water flow rate0 We use softened well water as ma eup water to the al aline water wash0 3he 3D( of this stream is appro.imately 18880 @9:ABC Dou would have to have a fairly large amount of aromatics in your feed$ probably greater than 2? to !?$ to see a foaming problem0 +f you are using reformate to start up your unit$ or as a seal flush$ you may have a problem during those times0 &owever$ you should also see emulsion problems in your acid settler emulsion level gauges0 &A>4A>3 W0 W+K+G "@erichem 1ompany#C 'or over 18 years$ @erichem has operated a 'iber 'ilmL water wash system in 92uafining service which is downstream of a conventional caustic wash on the al ylation reactor product0 We have seen e.tremely good results with this service0 @erichem recommends that the ma eup water to the water wash be steam condensate$ boiler feed water$ demineralized water or e2uivalent0 3he total dissolved solids not e.ceed 188 ppm weight as calcium carbonate0 (3AFA @93&E> "1hevron#C We have found that if you have high 3D( in the overall al aline water wash$ higher than 18$888 ppm$ you will tend to carry the al aline water with the reactor effluent to the D+40 &ardness is another matter$ however0 With hardness$ what you do is foul up your al aline water e.changer0 +f the hardness is very high$ within three wee s you will end up cleaning that e.changer on a continual basis0 3he only long term solution is to use either condensate or soft water as ma eup water to the al aline water wash0 -uestion =

4hat effects are seen in the (I$ o.eration 0hen chlorides co'e in 0ith 'ake-u. iso/utane3 %as anyone e*.erienced se,ere tray fouling in the (I$ and>or .luggage in the feed>iso/utane recycle coalescer as a result of it3 @9:ABC +f chlorides are present in your isobutane$ you can be assured you are going to have problems in the D+4 column0 +n order to ma e sure that you do not have chlorides$ chec the source of your isobutane0 +t is probably coming from the butane isomerization unit stabilizer0 3his problem is usually due to an over,injection of chloride in the butane isomerization unit$ and to improper stabilizer operation0 Get the licenser to review your chloride injection rate and ma e sure that you are reflu.ing the stabilizer ade2uately$ and thereby reboiling and stripping this tower properly0 3his tower is not an area where you should be trying to save reflu. energy0 4+=')>DC + agree with all of @r0 @ale ;s comments on the chloride issue0 While + was researching this$ + did gather a lot of information on corrosion in the overhead of the depropanizer and in the debutanizer0 1orrosion in fractionators of al ylation units is becoming a more prevalent problem for most refineries0 @any E0(0 al ylation units are running above 118 ? of design capacity to meet the refinerMs need for al ylate in the gasoline pool0 3he increased loading on the reaction section creates more side reaction products$ acids and neutral esters$ and acid carryover0 9cids and esters carrying through from the reactor are the most common cause of corrosion in the fractionators0 <oor mi.ing and lower residence times in the reactor effluent treating section allow more of these components to enter the fractionation section0 1orrosion in the D+4 comes from not sufficiently neutralizing the al yl sulfates in the water6caustic wash upstream0 3he al yl sulfates may brea down to form tars and () 20 3he wash needs to be at least 128N' to thermally decompose the dial yl sulfates0 1orrosion in the depropanizer on the al ylation unit is the result of () 2 and ()! liberation in the fractionation section0 ()2 and ()! end up in the refrigeration loop where they can react with water to form acids0 <roper operation and sizing of the depropanizer feed treaters can minimize corrosion0 Enits without depropanizer feed treaters are at the greatest ris for severe corrosion0 )ne al ylation unit does not operate its depropanizer due to this corrosion problem0 1orrosion problems in these fractionators can be effectively controlled through the use of chemical neutralizers0 =eutralizers can be applied to the feed or the reflu. of these columns0 3he neutralizer used in the deisobutanizer must be nonvolatile at the overhead conditions of this column so that it does not enter the reaction section with the isobutane recycle0 =onvolatile neutralizers will also protect the reboilers in the fractionation section0 =eutralizers used in the depropanizer should partition to the water phase in the overhead accumulator to prevent them from recycling bac to the reaction section0 >eboiler fouling in the al ylation unit is typically the result of corrosion problems in the unit0 3he corrosion products can migrate down the column and concentrate in the reboilers0 1orrosion products can also come in with the fractionator feed from upstream e2uipment0 3he corrosion products become bound to the reboiler with polymers and ester decomposition products0 While most refiners have a routine of water washing the reboiler on,line$ this tends to be a short term solution "the bundles get less clean each time#0 >outine water washing must be continued until the reboiler can no longer perform as re2uired0 1hemical antifoulants can be applied that will help prevent polymer formation and eep the corrosion products dispersed0 +n most cases$ we have been able to economically e.tend reboiler run lengths to the desired turnaround schedule with a properly designed antifoulant program0 19+=C We have had fouling problems in our al ylation D+4 side and bottom reboilers0 We are currently using a =alco6A..on dispersant with good results0 Question ? 4hat are your e*.eriences 0ith7 and the causes of7 foa'ing in s.ent acid tanks or acid trucks>railcars3 19+=C 9t <ort 9rthur$ we do not have any problems with foaming in our spent acid tan s or truc s0 'oaming usually occurs due to the presence of hydrocarbons in the spent acid0 'E((A::C We have had occasions where we have had foaming problems in the spent acid railcars0 We have determined that

this is caused by al ylate in the spent acid$ so we have several steps that we go through to try to get all of the al ylate out0 -uestion 1@ %o0 do you trou/leshoot the acid 0ash electrostatic .reci.itator to ensure that it is 0orking efficiently3 (oes anyone test for acid in the effluent3 4hat .rocedure is used3 &A=BAC 3he operation of our acid wash electrostatic precipitator has been basically trouble free0 3he operators monitor performance by watching level$ temperature$ amps$ and volts0 9cid carryover is maintained below 18 ppm0 We have found that$ in our unit$ operating at a lower level improves overall performance of the electrostatic precipitator0 We do not test for acid in the hydrocarbon effluent on a routine basis0 We have obtained semi,2uantitative data on the acid in the effluent by direct sampling of the hydrocarbon$ followed by titration in the lab0 4+=')>DC 3roubleshooting the acid wash is typically done on an indirect basis0 3he inlet and outlet acid strengths should be monitored on a wee ly basis to see how much non,acidic material is absorbed0 3here is a test method for measuring free acid in the effluent from the electrostatic precipitator0 3he method involves centrifuging a weathered sample and volumetrically determining the amount of acid that separates from the hydrocarbon0 &A>4A>3 W0 W+K+G "@erichem 1ompany#C @erichem offers Astere. technology$ which uses fresh sulfuric acid along with a 'iber 'ilmL contactor to remove both the acid and neutral esters which cause fouling in the downstream D+40 (ince the 'iber 'ilmL contactor has no moving parts or electrodes that short out with emulsions and corrode in the acid environment$ virtually 188? on stream time between turnarounds is achieved$ along with minimal acid carryover0 -uestion 11 (iscuss e*.erience 0ith running a/o,e @.9 olefin s.ace ,elocity in sulfuric acid alkylation units. S.ecifically co''ent on reaction +one te'.erature li'itations7 corrosion .ro/le's7 alkylate yields and acid consu'.tion effects. &9&=C Des$ we operate both of our al ylation units above 80- space velocity0 We suffer a little because of that0 )ur corrosion rates are somewhat high0 )ur temperatures are a ma.imum of -* '$ and we routinely run at -* ' for a large part of the year0 )ur worst corrosion occurs in our lowest strength acid system0 3hat final contactor operates at 55,57? sulfuric acid0 We have e.perienced contactor tube lea s as fre2uently as every % months to 12 months0 9 lot of this is due to a very localized corrosion$ sort of li e an impingement effect0 We are designing a splash plate to protect that nozzle entry point0 )ur octane numbers are somewhat lower than what may be desirable0 4ut overall$ our al ylate production is much higher$ and we accept these less than perfect conditions in order to ma.imize our al ylate production0 ')(3A>C We have had some similar e.periences0 We have two of our contactors that operate at this space velocity0 1urrently$ we have not seen any corrosion problems0 )ur 1 18O molecules are about two times what they normally would be$ and we see a slight increase in the 78? point and in the endpoint0 9cid consumption does not seem to have been affected0 &A=BAC )peration at or above 80- olefin space velocity is profitable in our case$ provided that we maintain contactor temperatures below -* '0 We have e.tensive D+4 feed pre,treating that includes a fresh acid wash system0 3his tends to minimize the corrosive impact of the esters formed at the high space velocities0 )ur acid consumption is higher and our al ylate yield is slightly lower0 + also refer you to page 128 of the 177! =<>9 QP9 3ranscript$ where there is a substantial amount of information on this topic0

'E((A::C + would just li e to say that about * or - years ago$ we did operate our al ylation unit at ma.imum charge rate0 3hat was our whole goal in life , to put as much charge through the unit as we possibly could0 We were running very warm on our contactor temperatures0 We were using over 1 lb of sulfuric acid per gallon of al ylate0 3hat was$ in our opinion$ the right way to run the unit0 We brought B41 in to do one of their famous yield and energy surveys0 3hey told us that we probably did not want to run the unit that way0 We did a series of test runs and a lot of economics and determined that yes$ they were right0 3hat was one thing we were not doing properly0 We totally changed our philosophy on running the unit0 We cut the rate bac $ got the contactor temperatures down$ and we cut our acid consumption in half0 We definitely got phone calls from )lin at that point0 3he octane on our product went up 2uite a bit0 )ur al ylate yield per barrel of feed went up0 We were actually ma ing almost as much al ylate at the lower charge rates as we were at the higher charge rates0 (o overall$ that was definitely the right move for us to ma e0 -uestion 12 Is there 'uch industry e*.erience 0ith using /au*ite for effluent treating3 4hat /enefits and costs can /e e*.ected fro' s0itching to /au*ite3 Since our refinery is short on iso/utane7 can anything else /e used for dry-out during /au*ite regeneration3 <A3A>()=C We have a bau.ite treater downstream of a reactor in one of our refineries0 +t removes any residual acid and neutral esters from the stream prior to the fractionation in the deisobutanizer0 3here is very little tray corrosion and very little fouling in the deisobutanizer0 =o chemicals are needed in the overhead system$ since all the bad material is ta en out upstream0 3he two bundles and reactors have a service life of over 2* years0 9 further benefit is that the isobutane recycle stream is dry$ which decreases the acid consumption0 9l ylate 2uality is improved by removing the side reaction products0 4+=')>DC (3>931) notes that it is generally not cost,effective to switch an e.isting unit to bau.ite treating$ unless the e.isting treating system is wholly inade2uate and has to be replaced away0 +n bau.ite treating$ the bau.ite is regenerated "dried# by recirculating an isobutane stream0 3his typically does not affect the isobutane consumption appreciably0 &owever$ there is some capital investment re2uired for the e2uipment to condense$ vaporize and pump the isobutane through the circuit0 9n alternative is a once through sweep of natural gas$ if the natural gas is dry enough0 -uestion 1 (iscuss 0hat corrosion has /een e*.erienced in sulfuric acid or %F alkylation alkylate s.litter to0er o,erhead syste's. &A=BAC We have no significant corrosion in our al ylate splitters or aviation gasoline towers0 <A3A>()=C We have a yes and no answer0 +n one of the refineries$ we have not seen any problems in the &' al ylate splitter overhead0 3his system has a fired reboiler0 +n another system$ we have had some problems with the fluorides apparently brea ing down "it is an &' unit#0 3he chrome parts of valves in the overhead system have had some problems0 3his tower is reboiled with an 9G) pumparound0 ')(3A>C We use a corrosion inhibitor and a neutralizing amine in the overhead system to maintain a p& of about / and in the overhead water boot$ and our iron levels are down below 18 ppm0 3hat normally eeps us down to a corrosion rate of about 2 mils0 Ender normal operating conditions$ the corrosion rate is very low0 We have e.perienced some upset conditions where we have eaten up overhead condensers pretty 2uic ly0 D9F+D (0 @c19''>AD "A..on >esearch P Angineering 1o0#C

+n sulfuric acid al ylation splitter towers$ corrosion is due to the brea down of neutral esters releasing () 20 3he ()2 in the overhead system will combine with free water and give you a corrosive environment0 +n a modern A>PA auto,refrigerated sulfuric acid process$ neutral esters are not formed to any significant e.tent by proper setting of operating conditions$ and thus the problem is precluded0 (3AFA @93&A> "1hevron#C +n &' al ylation plants$ if you have corrosion in the overhead$ there is a li elihood of the reboiler steam lea ing through0 +f the water is reaching the overhead with the fluorides$ it will cause low p&0 +t could be a very small lea that may not be really evident$ but we have seen it0 -uestion 1" %as anyone e*.erienced .lugging .ro/le's on the flash dru' side of the suction tra.>flash dru'3 If so7 0hat 0as the cause and>or solution3 %as anyone docu'ented a case of hydrate for'ation3 @9:ABC +f you are getting plugging in the flash drum side of the suction trap6flash drum$ it can be caused by ice or hydrates0 3his happens when water gets into the bottom of the depropanizer0 1hec the depropanizer operation and ma e sure that you are not getting any carryover from the depropanizer feed treating section$ and that you are running the depropanizer effectively0 4+=')>DC When a small amount of water is returned to the flash drum in the depropanizer bottoms$ the water will freeze at the temperatures and pressures in the flash drum$ resulting in plugging of the suction screens for the pumps0 3he solution is to increase the overhead temperature of the depropanizer , which increases water removal potential , or to increase the pressure in the flash drum such that freezing does not occur0 19+=C We have had the same problem with water lea ing into the system from an e.changer0 -uestion 18 %as anyone e*.erienced fouling or .lugging in the alkaline 0ater 0ash heater or de.ro.ani+er feed heater3 If so7 0hat 0as the cause and>or solution3 4as any of the 'aterial that fouled the e*changer collected and analy+ed3 If so7 0hat 0as the co'.osition3 'E((A::C We have recently commissioned a caustic wash system upstream of the depropanizer on our al ylation unit0 +t is actually upstream of the feed heat e.changer prior to the depropanizer0 We have had a lot of plugging problems in the heat e.changer as well as in the depropanizer0 We are slowly but surely troubleshooting our way out of these problems0 We have determined that the plugging has been caused by the caustic salts0 4+=')>DC (ome analysis provided by (3>931)$ based on their e.perience$ is that the foulant is typically *8? organics$ based on the loss in ignition analysis$ with the remainder being inorganics comprised of calcium and magnesium carbonate0 <lugging in the al aline water wash heater is usually due to hardness in the ma eup water$ and thus the deposits0 ')(3A>C We have found that fouling in the al aline water wash heater is almost always preceded by an upset in the reactor section0 +f the iso6olefin ratio falls below / or if the spent acid strength falls below 55?$ we tend to see polymerization in the reaction section$ and polymer collection in the al aline water wash heater0 )ur analysis of the material in the fouled e.changer shows it to be about -8? inorganic "mostly iron# and %8? organic "mostly 1 %,1organic acids$ 1!,17 aldehydes$ and 1-,115 substituted al anes#0 &A>4A>3 W0 W+K+G "@erichem 1ompany#C @erichem recently replaced a conventional caustic wash for a major Auropean refiner with a 'iber 'ilmL caustic wash ahead of the sulfuric acid al ylation unit depropanizer0 3he unit has been on stream less than 1 year$ but the benefits have been significantly reduced caustic carryover resulting in improved life of the trays and the reboiler0

. !echanical -uestion 19 4hat is the e*.erience on erosion>corrosion of no++le ti.s and candles in olefin feed distri/utors of alkylation units3 4hat 'aterials and>or coatings ha,e refiners used to .re,ent this da'age3 Our unit is e;ui..ed 0ith an Alloy 2@ s.ray no++le on each candle 0ith a tungsten car/ide insert. <he candle is a car/on steel .i.e ni..le 0ith a 1greycoat1 a..lied. Our unit is fitted 0ith 1Lightning1 tur/ine ty.e 'i*ers. 19+=C +n our <ort 9rthur plant during our last inspection$ we noticed some slight crac s on the feed nozzles and the spider vanes0 3he impellers were chec ed$ but they showed no signs of erosion or corrosion0 ". #eneral -uestion 1: 4hat are the .anelistsA thoughts on .reneutrali+ing the s.ray 'itigation 0ater3 %as anyone used sodiu' silicate in this ser,ice3 >)@9=C We thin the best approach is to allow the runoff flow to a nearby impoundment area where it can be subse2uently neutralized with lime0 +f there is no local impoundment area adjacent to the unit$ we would recommend installing a pump pit and pumping the overflow into a nearby di ed area$ again$ for subse2uent neutralization0 <re,neutralization would be our last choice due to its high cost and problems associated with spray nozzle plugging0 >)4A>3 A0 D9F+( ">0A0 Davis 1hemical 1orporation#C Dears ago$ + wor ed for a company that manufactured &'0 )ne of the products used for any spills was sodium silicate0 +t forms a sodium silica fluoride$ which is totally insoluble and can be swept up and disposed of0 -uestion 1= 4hat is the current 1/est1 .ractice for 0ashing the residual % 2SO" fro' an alkylation unit after draining for turnaround3 Is a neutrali+ing circulation used7 or is deluging 0ith 0ater to the se0er a co''on .ractice3 If a circulating /asic 0ater 0ash is used7 0hat is the ty.ical flo0 diagra' for it7 and ho0 is the .% of the 0ater 'onitored and controlled3 19+=C We inject *8 baumQ caustic into the wash$ carefully time the wash$ chec p& to determine whether to add more caustic or stop$ and then chec to ma e sure that the p& is in a safe and legal range to drain0 We dump from one settler to another to conserve the caustic0 'E((A::C We also circulate caustic through our three contactor systems0 We have a 2* wt? caustic solution0 We ta e the waste caustic to our waste treatment facility0 $. Alkylation-%ydrofluoric Acid 1. Feed -uestion 1? 4hat .ro/le's are caused /y alkylating a'ylenes3 4hat conta'inants cause the different .ro/le's7 and ho0 can the .ro/le's /e 'itigated3 <A3A>()=C 3here are several concerns with the al ylation amylenes0 +t depends on your balance of >F< reduction needs and your operating costs associated with the amylene processing0 3he inclusion of heavier hydrocarbons with the amylenes sometimes can occur$ particularly where you are really running your '11 debutanizer very hard$ as we run ours0 +f our G1 shows a component called "1 -O$" we now we have gone too far0 We thin it is probably something li e cyclopentenes and other heavier items0

&igher molecular weight sulfur compounds can also come through if your @ero. system has some problems0 +sobutane consumption increases not only from the al ylation of the olefin$ but also because of the significant hydrogen transfer that occurs with amylene0 9gain$ this is all a balance between what you really want to do with >F< reduction and these other operating costs0 3he isopentane and normal pentane are going to end up in the gasoline pool anyway0 4ut maybe you would rather have them go there with the '11 gasoline as opposed to the al ylate$ depending on how you are using your al ylate for octane optimization0 (9@EA:(C + li e some of the things @r0 <eterson said here0 With amylenes$ of course$ you usually have a large amount of dienes which$ if not removed$ will form light 9() in the al ylating unit0 9lso$ the 1 * mercaptans are harder to treat in a standard @ero. unit0 (elective hydrogenation$ operated to remove sulfur$ can have the added benefits of saturating diolefins and converting 1,butene to 2,butene to improve al ylate 2uality0 (o there are some advantages there0 +t should also be noted that to get the amylenes$ a lot of saturated pentane must typically be ta en0 =ormal pentane lowers al ylate octane while isopentane increases the vapor pressure0 9lso$ for refiners who have ether units$ if you have not prefractionated$ you are going to ma e 39@A and dilute your ether with unconverted 1 *s0 (3AFA @93&E> "1hevron#C 9 long time ago we did a test al ylating large amounts of amylenes in an &' unit$ and were astonished to find that the hydrogen transfer of the 1* olefins could be as high as -*?0 +n other words$ -*? of the 1 * olefins was going to ma e isopentane instead of al ylate0 (o the point of al ylating was almost disappearing due to the high vapor pressure of isopentane0 2. Process -uestion 2@ 4hat has /een your e*.erience 0ith %F and %C sensors for ,a.or detection3 Please gi,e your o,erall .hiloso.hy of selecting different technologies and e*tent of success>relia/ility 0ith each ty.e and 'ake of sensor. >)@9=C 9shland has had good success with our current sensors0 3here are 2! phototype sensors scattered throughout the &' unit in our largest plant$ and there are % 2uasi,mass spectrometers that sample ambient air around the pumps0 3he phototype sensors made by @olecular 9nalytic bounce a light beam off a mirror0 When the mirror becomes distorted with acid$ the light pattern changes and alarms0 3he 2uasi,mass spectrometer pulls ambient air into a cleaning and drying system$ and actually analyzes the air0 3his instrument can detect 8 ppm to 18 ppm of hydrofluoric acid0 3he philosophy in selecting the sensors was to get ine.pensive$ proven sensors for general monitoring$ and get a more sophisticated instrument for monitoring areas which are more li ely to e.perience a lea 0 -uestion 21 Bo0 that so'e of the ne0 ,a.or su..ression additi,e syste's ha,e started u.7 0hat has /een the e*.erience 0ith their .erfor'ance3 &9&=C +n Ruly$177/$ 3e.aco and E)< completed the latest field test on a new$ more cost,effective additive called 9l aid$ at 3e.aco;s Al Dorado refinery0 3his test was very encouraging0 3he main objective was to determine the increased operating costs$ if any0 3here were no substantial increases in operating costs as far as they could determine0 3he flash chamber testing of the unit circulating acid sample ta en during the additive operation shows substantial reductions in aerosol formation$ in comparison to the circulating acid without the additive operation0 We are very encouraged by these test results$ and intend to conduct a more e.tensive field test this fall0 9fter a successful field testing period$ we intend to go commercial with this product ne.t year0 :9>>D W0 (&)A@9BA> "<hillips <etroleum 1ompany#C <hillips started up their reduced volatility al ylation process ">eF9<# at the Woods 1ross >efinery near (alt :a e 1ity$ Etah$ in early 9ugust0 (ince that time$ the process has wor ed e.tremely well0 3he al ylate product 2uality and yields have been observed to be e2ual to or maybe slightly better than that seen with traditional &' catalysts0 3he operability and the reliability of the unit have been good$ with only one minor piece of mechanical e2uipment having to be modified from the original design0 +n addition$ the early data indicate a possible reduction in &'

consumption$ and we e.pect to have additional data over the coming wee s to further prove the viability of this new process0 -uestion 22 For %F alkylation syste's7 0hat instru'ents are refiners using to indicate acid regenerator colu'n /otto's le,els3 4e currently use a te'.erature indicator 0ith so'e success. <A3A>()=C We are still using the temperature indication method in the 9rdmore >efinery to control level in our &' regenerator0 )ur 9lma >efinery$ however$ is a little more advanced than we are on this0 3hey have a radiation system aimed diagonally across the level control region of their regenerator$ and they have seen some very encouraging results from this0 3hey do not overdraw too low$ so they are able to save some acid0 3hey can also stabilize the operation$ because they now where the level is$ instead of waiting for a temperature to indicate , almost li e a batch system0 (9@EA:(C +n >obinson;s &' al ylation unit$ we successfully operate a 3e.as =uclear fi.ed source detector level indicator at the bottom of the acid regenerator0 3emperature indicators above and below this instrument act as a bac up system0 &9&=C 9t Al Dorado;s &' al ylation unit$ they also found that temperatures and D< cells were not very reliable0 3hey also have installed nuclear detection devices$ and have found them to be much more reliable0 -uestion 2 For %F alkylation syste's7 0hat instru'ents are refiners using to indicate acid settler le,els other than sight glasses and (P cells3 (9@EA:(C 9t @arathon;s Garyville <hillips &' unit$ we use an )&@9>3 nuclear level indicator to monitor the acid level in the settler0 3he instrument continuously measures the density in the settler and physically travels from the top to the bottom of the vessel about every 10* hours0 3he instrument plots the density versus level in the vessel0 3he difference in density between the acid and the hydrocarbons is very distinct ma ing this a very useful level indicator0 3o date$ the instrument itself has been very reliable$ but has been somewhat subject to mechanical problems$ due to the physical nature of the instrument$ e0g0$ the detector moving up and down0 9t >obinson;s E)< &' al ylation unit$ we also use an )&@9>3 nuclear detector profiler for the mi.er settler and for the acid storage drum0 )n the &' acid boot levels$ we have used a combination of capacitance probes$ as @r0 'oster has described$ and a displacer unit0 We have actually removed the sight glasses from these boots for safety reasons0 3he dual technology combination has proven effective0 3he capacitance probe does not suffer from hangups associated with the displacer0 4ut the capacitance probe has had problems reading emulsions during start,ups , problems that the displacer has not had0 We have also completed a trial installation of a nuclear guage designed to be mounted in a level bridle$ to supplement a displacer$ with success0 3he capacitance probes are preferred$ however$ due to substantially lower initial cost0 <A3A>()=C We currently have nuclear level detection in our acid settlers0 We are loo ing at some other technologies0 We do not now the results$ yet0 >)@9=C We currently use )&@9>3 gauges$ which were purchased directly from )&@9>3$ and which use a cesium nuclear source0 3his is a two,tube system0 )ne tube is a source on a pulley$ and the other contains a Geiger detector0 3hese systems are now considered obsolete$ and we are evaluating replacing them with newer bac ,scatter technology$ which uses a single tube and a much smaller source0 We have also installed several <ro,@ag units$ which are magnetically coupled to e.ternal systems that use a monel tube and an internal float0 We have had problems with some of the monel tubes due to the low and variable 1urie point of monel0 +t can become magnetic if the 1urie point happens to be above the settler temperature$ rendering it useless0

B,>ay also ma es a bac ,scatter system$ but we have no e.perience with it0 4>+9= R)&=()= "E)<#C E)< offers a density profile system that uses a low strength radioactive technology to indicate the settled acid$ the emulsion and the settled hydrocarbon levels0 3he instrument has been widely used in the industry in the current density profile system version and other density profile versions for many years0 -uestion 2" %o0 successful ha,e 'agnetic dri,e .u'.s /een in %F ser,ice3 %o0 do they co'.are 0ith other sealless .u'.s3 (9@EA:(C 'resh &' acid pump seal failure is a classic problem in &' units0 Aven with much effort over the years$ @arathon has not been able to solve this problem0 We are currently evaluating two upgrades for this service0 'irst$ sealless magnetically coupled &' acid pumps were installed in Garyville0 9t this point our success with these pumps has been marginal$ and + probably could not recommend this design based on Garyville;s e.perience0 3he initial capital cost is high compared to traditional designs$ the failure rate has been higher than e.pected$ and the repair costs are high$ in the S18$888 to S1!$888 per event range0 9n alternative$ new technology has been developed and installed in >obinson0 3his technology is the application of an eductor system to educt fresh acid from the storage drum into the mi.er settler0 9 flash acid eductor trial was successfully completed on =ovember 1*$ 177/0 )bviously$ balancing the system flows and pressures is ey to operating the eductor successfully0 We plan to design and install a 1*8 gpm eductor for unit start,ups0 Rust to add a little bit about the eductor design$ it educts &' using a slipstream of 22* gpm of cooled$ high pressure "!2* psig# iso recycle from upstream of the &' reactor as the motive fluid into the eductor$ and it draws 2* gpm from the acid storage drum$ which operates at *8 psig0 3he fresh acid and isobutane mi.ture "2*8 gpm# is then discharged into the mi.er settler at 218 psig0 3he eductor is inherently sealless0 3here are no moving parts$ so it is more reliable than a conventional pump0 3he installed capital cost of the eductor is about half the cost of a sealless magnetically coupled pump0 'inally$ + just want to mention that in our emulsion pump$ or circulating acid pump$ in the E)< unit$ we do use a tandem seal$ and have had very good success with that$ and have no plans to change that design0 C. &efor'ing 1. Process -uestion 28 4hat is the o.erating e*.erience of refor'ing units /eing controlled /y ad,anced controls and o.ti'i+ers3 4hat o.erating .ara'eters are utili+ed for control to o.ti'i+e .erfor'ance3 19+=C +n our :ouisiana plant$ our reformer has advanced controls$ including D@10 +t has been in place for almost a year now$ with good results0 3he controls maintain inferential and analyzer variables on reformate octane$ >F<$ and light end cuts by manipulating reactor temperatures$ the tower operating pressures and temperatures$ etc0 We also have purchased and are in the process of installing an 9pplied 9utomation '3=+> analyzer0 We hope to have that installed by year end0 +t will model >)=$ benzene$ aromatics$ and >F<0 9lso$ in our <ort 9rthur plant$ they have been using advanced control since 175*$ and are in the process of starting up an on,line optimizer0 <A3A>()=C )ne of our refineries introduced advanced controls in the semiregenerative reformer about 18 years ago$ and they have wor ed 2uite well0 3hey do inferential octane controls by loo ing at the W943$ the feed rate$ and other variables0 3hey minimize the hydrogen recycle ratio in both the reformer side and at the hydrotreater side0 3hey minimize pressure in the reactor section$ all$ of course$ relative to the constraints of the catalyst system0 +n the stabilizer system$ pressure is minimized to match a predetermined allowable off,gas rate0 >eflu. ratios and pass balancing controls on the towers are used0 3he big ey to ma ing this successful is to ma e sure the operators understand what the systems are doing0 )perators tend to really get concerned when they see an automatic system start changing the pressure on a tower0

>)@9=C 9shland has had good e.perience with reformer advanced controls0 General advanced control design calls for control of the reformate octane by resetting reactor weight average inlet temperatures against both charge and interheater constraints0 9 bed profile controller maintains an operator,entered specification and temperature profiles across the bed0 >eactor li2uid hourly space velocity is used as a feed forward parameter in reformate octane predictive controllers0 @ost success has been found in those systems using 9shland;s =+> on,line technology to measure reformate octane0 (ome reformers rely upon a calculated octane value$ which is updated with laboratory values0 )ptimization parameters include temperature profile across the beds$ final reformate octane$ and the amount of naphtha$ which bypasses the reformer to achieve an overall octane demand$ as dictated by gasoline blending0 3he 2uality of the feed being introduced into the reformers is also an optimization parameter$ which is$ of course$ controlled by the split at the dehe.anizers or naphtha splitters upstream of the units0 9ll of our 11> units have on,line e2uations which are used to calculate co e on catalyst$ which is based upon an o.ygen balance around the regenerator0 &0 10 B:+A(1& "3reiber 1ontrols +nc0#C We have implemented advanced control and on,line$ closed,loop unit optimization on a catalytic reforming unit0 We used our multivariable predictive control software$ )<1 ")ptimal <redictive 1ontrol#$ to control reactor weighted, average reactor temperature and inlet temperature profile by manipulating furnace outlet temperatures0 'urnace tube temperatures are constraint variablesC the controller will attempt to meet the desired temperature profile through the reactors while respecting ma.imum limits on tubes in temperatures0 'or optimization$ li e the al ylation model + discussed yesterday$ we used our 1>) "1losed,loop >econciliation and )ptimization# software to perform an economic optimization using a first,principles$ non,linear chemical engineering model of the entire plant0 3he model is in simultaneous e2uation form$ so the same model is used for a full reconciliation and parameter update$ followed by an economic optimization0 What is uni2ue about this reformer application is that the model starts at the crude unit atmospheric tower and includes the hydrotreater and the naphtha splitter0 3he current crude slate is nown$ so the optimizer rigorously calculates the naphthenic and paraffinic content of the reformer feed and calculates the change in weighted average temperature re2uired to maintain a target octane0 3he crude slate changes every ! days and the octane target changes twice wee ly0 3he optimizer also computes and implements the optimal feed 7*? point on the atmospheric column$ and the optimal feed *? point on the naphtha splitter0 =ew values are calculated for up to 2* setpoints and sent to the controllers every %* to -8 minutes0 3he application has shown high uptimes and had a payout in the range of - to 7 months0 :AA A0 3E><+= "&oneywell &i,(pec (olutions#C 9dvanced process controls on catalytic reformer units have been very effective in stabilizing unit operations and pushing constraints such as feed rate$ e2uipment limits and carbon ma e0 We have installed on,line closed,loop optimization on several units$ including multiple reformer simultaneous operations0 + would li e to point out that the flat profile of profit versus operating conditions may result in an optimizer eventually downgrading to just a constraint pusher$ something that needs to be watched very closely0 + would li e to note another problemC we see some optimization problems have been put on reformers where the unit is varying octane as an independent variable$ which is a local optimization$ but it does not fit into the refinery;s general operating plan and results in a non,optimization of the plant0 3he summer edition of &ydrocarbon 3echnology Quarterly contains an article + wrote that reviews the different operating parameters for optimization of reformers$ and includes some economic data on the impact of moving independent variables0 <9>+@9: B9=3+ 4+(W9( "+ndian )il 1orporation :imited#C 'or a semiregenerative type of reformer$ with the oil plate heat e.changer$ how are feed and effluent lea s detected? &A=BAC +n our refineries$ we commonly use radioactive tracer technology to detect lea s0 + suggest that you can contact the people at 3ru,3ec in :a<orte$ 3e.as0 3hey provide innovative lea detection solutions0 'E((A::C +f you are tal ing about the feed effluent e.changer$ we loo for isohe.ane in the product0 +f it ma es it that far$ we probably have a lea 0

>)@9=C We generally use sulphur he.afluoride and inject it into the feed$ and then loo for the pea s$ using gas chromatography to find that lea 0 +f you see just one pea $ or if you see two pea s$ you now you have a lea 0 (9@+> &9:9W9=+ "(audi 9ramco#C + would li e to forward this 2uestion to <eterson0 We have a semiregenerative E)< reformer$ which runs on a pneumatic control0 @y 2uestion is$ what is re2uired to have an optimization on the reactors$ or on the octane$ as you mentioned? <A3A>()=C 3he refinery that has the advanced controls is on a D1(I it is a 4ailey system0 3he 9rdmore refinery has not done advanced controls on a 4ailey system$ and we have not attempted anything on pneumatics0 We are in the process of converting the rest of our refinery over to distributive control$ and we are also in the process of going bac in some of these units and loo ing at advanced controls0 4ut at this point$ we have done nothing with pneumatics0 3A>>D D0 3E1BA> "@9<1) <A3>):AE@$ +nc0#C &elium can be used to detect tube lea s in feed6effluent e.changers while they are in service0 &elium is injected on the tube "feed# side of the e.changer0 9 gas chromatograph is connected to a bleeder on the shell side$ outlet$ of the effluent e.changer0 9fter the helium has been injected into the feed side of the e.changer$ the gas chromatograph will indicate multiple spi es of helium if any of the e.changer;s tubes are lea ing0 9=GA:) 'E>'9>) "E)<#C 3he summation of the panelMs responses is a good place to start0 E)< has been involved with many 9<1 projects in recent years0 3he implementation of 9<1 in reforming projects incorporates the use of E)<Ms proprietary reforming models to provide setpoints and constraints for the advanced control layer$ typically a multivariable predictive controller "@<1#0 @ore than !8 projects for both fi.ed,bed and 11> platforming process units have been completed0 3ypical unit operation re2uires conversion of the octane or aromatics target specified by the refinerMs Aconomics and (cheduling Group into a weighted average inlet temperature "W9+3#0 Esing a nonlinear model of the reaction system$ E)< as developed a model that provides that target over a wide range of operating conditions0 (ince the platforming process unit is often critical to the refinerMs ability to produce gasoline and6or aromatics$ ma.imum throughput can be achieved by pushing unit constraints typically to ma.imize unit charge rate0 3he constraints may include furnace tubewall temperatures$ feed and recycle gas reactor hydraulic limits in 11> units and co e production "either to match burn capacity of the 11> or hit a run,length target on a semiregenerative unit#0 1o e production is strongly influenced by the hydrogen to hydrocarbon ratio$ but is difficult to control because of the time horizons involved compared to other process variables and the fact that only the co e production rate can be controlled0 )nce co e is produced$ it can only be removed by combustion0 <rocess units typically fall into two classes regarding optimization potential0 constrained optimum or global optimum0 'or a standalone reformer$ operation to constraints is typically the only optimization potential0 (ince the constraints can be identified by either unit parameters "valve positions$ temperatures$ etc0# or calculated variables "the tubewall temperature$ pinning or co ing#$ the use of an @<1 that can push constraints is typically sufficient to realize ma.imum potential from the unit0 &owever$ when the reformer is part of a "naphtha comple.$" which might include a naphtha splitter and an isomerization unit "such as E)<Ms <ene. process unit#$ there are opportunities for trade,offs in feed rates and compositions that can only be evaluated by more comple. optimization calculations0 3o ma e these calculations$ rigorous$ inetic models of the units and detailed simulation of separations and other unit operations are necessary0 3his form of optimization is significantly more comple. in development and e.ecution$ but offers sizable benefits to the refiner0 + agree with @r0 >oman with regard to the use of =+> technology$ e.cept that we would use E)< Guided Wave analyzers for this aspect of the information feedbac system0 =+> is still considered a "secondary method$" as opposed to octane number determination via an engine which is a "primary method0" 3hat being said$ =+> is being used for routine on,line control and analysis functions today in refineries around the world as it can rapidly and accurately mimic ""statistically e2uivalent"# many of the analyses now re2uired and performed by primary methods on gasoline blends0 3wo 9(3@ practices6methods have been developed covering the use of =+> analyzers and their calibration0 3he first is 9(3@ A1-** which covers the chemometric calibration of an =+> analyzer0 3he second is 9(3@ D-122

which has just passed ballot and will be published soon0 3his standard covers the validation of an =+> "system"$ in other words "assuring that the analyzer system;s results are statistically e2uivalent to the primary method0" -uestion 29 4hat has /een the industry e*.erience using density grading to reco,er CC& catalyst that 0as conta'inated 0ith 1heel1 catalyst3 %as anyone atte'.ted to e* situ regenerate 1heel1 catalyst for reuse3 'E((A::C +n 177*$ we used this process with 1>+ here in :ouisiana0 + would refer you to the 177* =<>9 QP9 3ranscript where @r0 Dale Ammanuel provided a very comprehensive answer0 &A=BAC We have no direct e.perience with density grading0 &owever$ we have been told that this process is well proven and has been used successfully by several refiners0 We have completed an e.,situ regeneration of our heel catalyst0 3he carbon content on the heel catalyst was between %8 wt? and *8 wt?0 9fter inspection of the catalyst$ we determined that it was not suitable for reuse0 We 2uestion the viability of regenerating and reusing heel catalyst with this much carbon0 19+=C When dumping the reactor$ we separate out the last *8 drums or so0 We send them to 1>+ for density grading$ and the heel catalyst will be sent out for metal recovery$ while the good catalyst is returned to the unit and reloaded0 <9E: '+(&A> "3>+193$ +nc0#C 3>+193 has performed three off,site regenerations of 11> catalyst containing "heel" catalyst that was returned to the 11> unit for reuse0 +n each case$ carbon levels were reduced to below 80% wt? with e.cellent surface area retention0 We do not believe that density grading is necessary0 Aach catalyst lot contained "heel" catalyst with over %8 wt? carbon that would have been separated through density separation0 9n e. situ regeneration of all of the catalyst from the reactor saved the e.pense of density grading$ and all the catalyst was returned to service in the 11>0 3he regeneration in 3>+193;s uni2ue ebullating bed reactors returned a greater amount of 11> catalyst from the reactor section$ including heel catalyst$ than would have been available after density grading$ and saved the cost of purchasing fresh catalyst for ma eup0 -uestion 2: 4hat .rocess ,aria/les can i'.ro,e the hydrogen .urity fro' a CC& refor'er contactor3 4hat .rocess add-ons ha,e /een used to further increase .urity for high .urity uses7 such as hydrocrackers and resid hydrotreaters3 <A3A>()=C We use an absorption of the net offgas from the reformer with refrigerated low pressure separator li2uid0 3he primary purpose of installing the system was to recover the :<Gs that used to go to fuel gas or to the hydrotreaters0 4ecause the purposes is :<G recovery$ we ta e the debutanizer or stabilizer overhead gas and recycle it bac in front of this absorber to recover what would have been lost in that stream0 +f you get too cold or too high in pressure$ you can set up an ethane recycle$ where you absorb it in the front end and reject it out the bac end0 +t just comes around and around and the debutanizer$ in our case$ would have been undersized to handle this0 9nother cautionC if this hydrogen is going to a unit downstream that has a centrifugal recycle compressor$ it may need a few heavy ends just to build enough pressure from the density of the gas0 With gas too pure$ we have had some problems toward end of run in a hydrotreater with high reactor delta <s holding bac recycle ratio0 3he hydrogen purity upgrade is on the order of !? to -?0 @9:ABC 3he 11> unit ma es a higher yield of hydrogen compared to a semiregeneration unit0 3he hydrogen tends to be of a higher purity$ because there are a lot less crac ed gases associated with the hydrogen0 3hese gases can be further upgraded downstream$ to whatever purity level is re2uired in your hydrocrac ers$ using <(9 systems 0 49>:)AWA=C @y answer is with regard to which process variable can improve & 2 purity from a 11> reformer0 3he only

significant handle you have is pressure0 >educing pressure improves purity$ and that has been the whole thrust of 11> technology0 &owever$ in a modern 11>$ you do not have very much room to move down in pressure0 3hat answer may apply more to an old$ fi.ed,bed$ semiregenerative reforming unit0 -uestion 2= 4hat are ty.ical targets for 'oisture and chloride in the recycle gas for se'iregenerati,e7 cyclic7 and CC& units3 Are these targets de.endent on catalyst ty.e or age3 %o0 are chloride>0ater le,els controlled7 and 0hat is the ty.ical ,aria/ility3 39(BA>C We generally recommend the same water and chloride on the catalyst for both the semiregenerative and 11> processes0 We try to maintain the water level to about 1* ppmw to 2* ppmw$ and the &1: levels between 1 ppmw to 2 ppmw0 3he ratio of water to chlorine is therefore usually in the range of 18C1 to 2*C10 3he real target is to maintain a chloride level on the catalyst between 807 wt? and 101 wt? of chlorine0 )n the 2uestion of type and age$ we do not generally differentiate between catalysts0 4ut there is a difference on age$ since the chlorine retention ability reduces with age0 3herefore$ we should maintain a higher chloride level with a lower ratio of about 28 to 2* for fresh catalyst and a 18 to 1* ratio on the other aged catalysts0 3he targets in the recycle gas stream are dependent upon the type and the age of a catalyst being used0 1hloride retention is determined by two main factorsC the type of impurities that are in the alumina used to ma e the catalyst$ and$ of course$ the surface area of the catalyst0 'or control$ it is important to be able to sample correctly0 3his calls for a sampling device$ or a sample thief$ which can be used to e.tract samples0 3hen$ the chloride levels on the catalyst can be measured$ and the operations adjusted0 +f there is no sampling device$ then the control becomes more of a blac art0 9s an alternative to sampling the catalyst$ normally the water and chloride levels are controlled by measuring the water and the &1: in the recycle gas and adding the appropriate amount of alcohol and6or chloriding agent0 3o achieve a constant water to chloride balance$ it is important to eep a constant moisture level in the feed0 +f the moisture level in the feed varies$ then you will always be chasing that water to chloride balance0 3here continues to be difficulty in measuring or in getting instrumentation for proper analysis of the water content0 &owever$ we have to be very careful with the instruments re2uiring re,calibration0 With the 11> process$ it is not re2uired that a sample has to be ta en from the reactor$ since a sample can be ta en at the regenerator0 3his sample device can be mounted on the % in0 dump line0 <A3A>()=C + would agree with the comments and the general ranges of control and the means of control0 + would stress that ta ing a sample of the catalyst be used to calibrate your licenser;s recommendations as to correlating moisture and chloride content in recycle gas0 +t is far better to now what you really have than to be thin ing that you are doing o ay0 We had also another case where we had poor stripping of the carbon o.ides from the 11> catalyst coming bac into the system0 3he carbon o.ides were apparently undergoing the shift reaction and ma ing some water in the reformer$ which was ma ing moisture control more difficult there0 3his carbon mono.ide was also getting over to our isomerization unit where it was shifting there and ma ing water and deactivating the isomerization catalyst0 3his is not easy for us to find0 Dou can try to Drager tube for 1)$ but hydrogen in the system interferes in the test0 (o we have actually had to send samples off to places that can find the 1) in the recycle gas0 9=GA:) 'E>'9>) "E)<#C 'or semiregenerative operation$ E)< generally recommends effective feed stripping "to less than 1 ppmw & 2)# and injection of % ppmw &2) into the feed0 3his practice normally results in 1* mol ppm to 28 mol ppm & 2) in the recycle gas0 (ome moisture is recommended to facilitate chloride distribution$ but more than !8 mol ppm in the recycle gas has adverse selectivity and stability effects0 3he chloride "&1l# content of the recycle gas depends on catalyst type and age$ but generally varies from a trace to 1 mol ppm to 2 mol ppm0 3he chloride injection rate is varied according to catalyst type$ reactor temperatures$ performance indications$ e.perience$ and analytical results if made possible by catalyst sampling devices0 1yclic units tend to have high and variable moisture as a result of freshly regenerated catalyst being returned to service at intervals0 3here is rarely if ever a need to inject & 2) into a cyclic unit0 3he variability of recycle gas moisture content and varying amounts of chloride being released from freshly regenerated reactors ma es chloride

control very difficult and the recycle gas &1l concentration highly variable0 3he catalyst age and type also affect the recycle gas &1l concentration0 E)< does not design cyclic units0 'or 11> platforming units$ there is no need to inject & 2) or chloride into the reactor section$ e.cept for periods of e.tended regenerator downtime0 3he regenerated catalyst chloride content is controlled by injection into the regeneration tower to a target value which depends on catalyst type0 3he spent catalyst chloride content is slightly lower due to loss of chloride in the reactors0 3he amount of chloride lost is a function of catalyst residence time in the reactors$ the recycle gas moisture content$ and the reactor temperatures$ but is normally relatively small0 =ormally$ there is sufficient moisture from the regeneration so that no water injection is necessary0 >ecycle gas &1l concentration depends on catalyst type$ catalyst age and recycle gas moisture content$ and can vary from less than 1 mol ppm to as high as 5 mol ppm or 7 mol ppm if the catalyst surface area is very low and6or the recycle gas moisture is abnormally high0 E)<Ms surface areas stable catalysts help to limit chloride loss0 D0B0 BE1&&9: "+ndian +nstitute of <etroleum#C 3he water content of recycle gas for (,> bimetallic catalyst is targeted in the range of 1* ppmv to 28 ppmv0 'or this value of moisture$ chloride dosing may be done intermittently to maintain chlorine content in the catalyst at around 108 wt?0 'or recycle gas moisture of 28 ppmv to !8 ppmv the chloride in the feed is ept at 1 ppmw0 +t is further increased to 2 ppmw for recycle gas moisture of !8 ppmv to %* ppmv0 'or higher moisture content in recycle gas$ the reactor inlet temperatures are reduced as per the advice of the catalyst supplier0 When the moisture content increases$ it becomes necessary to loo into stripper operation0 +n order to meet a minimum target of 1* ppmv moisture in recycle gas$ it may be desirable to inject water with feedstoc "! ppmw to * ppmw#0 Water injection is done after thoroughly confirming the moisture content of the recycle gas0 (9@+> &9:9W9=+ "(audi 9ramco#C What is the latest technology in moisture analyzers on a recycle gas for a semiregenerative reformer? 19+=C Dupont *-8 (ensitivityC 80* ppm by vol0 9ccuracyC T18? of reading or 2 ppm$ whichever is greater$ on all ranges0 >epeatabilityC T!? of reading or 80* ppm$ whichever is greater0 1alibrationC &as a built in moisture generator for calibration0 =oteC Fery accurate$ and dependable0 >angeC =ormal running 8 ppm to *8 ppm moisture0 Esed for normal running on the 1>E because of the low concentration of moisture in the gas0 >anare. @oisture 9nalyzer @odel J@9,/214 =o specifications in the manual on accuracy or repeatability0 1alibrationC using a separate moisture generator source0 >angeC 8 ppm to 1888 ppm moisture0 3he larger range allows us to utilize this meter during startup0 9lso$ the reading on this meter is usually * ppm to - ppm lower than the Dupont meter when the concentration falls down to normal operations0 <lan to replace this one with a @ee o moisture analyzer0 -uestion 2? (o o.erators 0ait until /reakthrough on their sulfur and chloride guard /eds to decide 0hen to change out the /eds3 Is there a /etter 'ethod3 &A=BAC )ur strategy with chloride guard beds is to wait for brea through0 We recently began to monitor both organic and inorganic chlorides using (ensidyne tubes "these are model U1%: for hydrogen chloride$ 802 ppm to %8 ppm#0 We found that Draeger tubes only detect the inorganic chlorides0 3his is an important distinction since the organic chlorides also contribute to fouling in hydrotreater e.changers0 + am unaware of a safer or better method at this time0

<A3A>()=C We normally wait for a brea through in our sulfur guard bed0 We detect this either with laboratory analysis of the splitter bottoms$ the heavy naphtha$ which is not always real precise at these low sulphur levels that you see out of a sulphur guard bed0 9 more reliable test$ but with a little time lag$ is to loo for the & 2( in our debutanizer offgas0 3his gets magnified in the 9rdmore >efinery$ because we recycle this gas bac to the reactor effluent system for :<G recovery0 9s far as catalyst sampling down the bed in the sulfur guard bed goes$ we had installed catalyst samplers designed after the method used for the vapor phase reformer catalyst samplers0 3his did not wor very well on the li2uid system$ so we have abandoned use of those0 9s for chloride traps$ we have one on the :<G from the reformer going down to the saturated gas fractionation0 3hat was put in to help control corrosion in the line to the saturated gas and in the saturated gas unit itself0 We probably have grossly oversized this vessel$ because it has run about ! years$ and it was designed for 7 months0 4ut the reason for that is probably the difficulty of actually pinning down how much &1l is in an :<G stream0 +t is not real easy to do that with Drager tubes0 39(BA>C Well$ as you heard$ and based on our e.perience$ most operators do wait for brea through to replace their sulfur and chloride guard beds0 3here are other techni2ues which are involved$ including monitoring the pic up and so on$ but those methods tend to be somewhat inaccurate0 9creon 1atalysts has helped to resolve this problem by allowing companies to have a spare charge of material on,site at no charge until it is placed into service0 49>:)AWA=C + agree with the comment that most people$ in fact all people that + now$ go to brea through0 + would echo @r0 <eterson;s comment that the debutanizer offgas is a real sensitive indicator when you are starting to see sulfur brea through0 +t is magnified$ and you will see a detectable change there faster than anywhere else0 19+=C +n <ort 9rthur$ we have two guard reactors in series0 )nce we spot a brea through in the lead reactor$ we switch to the lag reactor$ then change the catalyst out in the lead0 We monitor the delta 3 across the second guard bed as the first line of defense against brea through0 +f the Delta 3 becomes too large$ it is time to change out the lead guard bed0 'urthermore$ if the nitrogen in the second guard bed effluent becomes high$ we now we need to do an emergency changeout of both beds0 ':A31&A>C )ne of our customers has a strategy which is slightly different than what has been described so far0 With respect to the sulphur guard$ the cost of guard catalyst is minimal compared to its benefit0 9n estimate of bed loading is therefore made based upon the inlet sulfur loading and feed rates0 1hange out is done prior to the calculated end of run0 With respect to the chloride guard$ it is less critical$ which allows for testing of the brea through before changing the catalyst0 'E((A::C +n <ort 9rthur$ we do not have a sulfur guard bed0 We do have chloride beds on our gas and our li2uid streams on our reformer$ and we do run them until we see brea through0 -uestion @ In the refor'er recycle hydrogen gas there is a fairly high ;uantity of hea,y hydrocar/ons 50e ha,e 'easured o,er 2C6. %o0 does this affect the refor'er catalyst in ter's of coking and con,ersion3 >)@9=C +t is important to now the composition of the heavy hydrocarbons0 +f the material is aromatic$ there should be very little effect0 3he hydrogen to hydrocarbon ratio will decrease slightly$ and this will tend to lower conversion to aromatics and also increase co e laydown0 &owever$ if the heavy material contains appreciable amounts of olefins$ as can occur in low pressure units$ they can undergo 'reidel,1rafts al ylation with the aromatics and form a heavy green oil0 3his normally occurs when the aluminum bed used to remove the chlorides ages and becomes saturated with aluminum chloride0 +t then acts as a 'reidel,1rafts catalyst$ and the result is severe valve fouling in downstream compressors0

<A3A>()=C We have an old reformer$ which we have been constantly trying to push more and more through0 We have a fairly high velocity and a fairly small low pressure separator0 We do see a little bit of full range material coming bac around0 3his concerns us$ because we have reciprocating recycle compressors$ and they do not li e to pump very much li2uid0 We have had to loo at the design of the piping system into these compressors$ and put a little trap pot on the one that has the worst piping to help catch the li2uids to eep us from having compressor problems0 19+=C We operate in a 80/ to 10/ range without any bad effects0 K+D9D 9KK)EK "(audi 9ramco#C @r0 1ain$ regarding nitrogen in the feed$ because this is a difficult product$ how do you now if your test is effective? 19+=C 3he =2 test is 9(3@ D%-270 We test the =aptha hydrotreater product before it is charged to the platformer0 )ur specification is greater than 80* ppm0 We then adjust the reactor temperature accordingly to remove =2 and sulfur0 3&+A>>D D9>DA "<all 1orporation#C Fery recently$ one of our customers in Aurope as ed us to do a survey because he was e.periencing recycle gas compressor brea down due to li2uid carryover0 We installed a test system made up of a high efficiency li2uid gas coalescer0 We installed this downstream of the noc out pot and upstream of the compressor0 We measured indeed between 1? and$ on pea condition$ up to -? of li2uid hydrocarbon carryover with the recycle gas0 3he good news was that our li2uid gas coalescer was able to remove all that li2uid carryover down to a level of below 801 ppm of li2uid in a gas0 >0 >9R9@9=+ "@angalore >efinery and <etrochemicals :td0#C We have a slightly different problem$ that is the condensation of reformate downstream of the chloride treater in the hydrogen at inlet to the <(90 (o$ we would li e to now how$ in cold countries$ you avoid the condensation there which ultimately plugs the catalyst and reduces efficiency? &+GG+=(C =o reponse0 &A>)( DA>G>AG)>+9= "Falero >efining P @ar eting 1ompany#C @y 2uestion concerns the problem of an accurate analyzer to detect the moisture level in the recycle gas in order to control the chloride and water balance0 +t is 2uite common$ and + want to as the panel and the audience what other method is available to chec the appro.imate water level in the recycle gas in order to adjust either the chloride or water level to reach the balance? 9s you now$ you might see a high chloride level in the recycle gas0 Does this mean that your chloride level has increased or is it because a high water level has leeched out chloride from catalyst? Enless you now the appro.imate 2uantity of water in the recycle gas$ the action ta en could be either adding additional chloride or reducing water0 &9&=C )n water detection in the recycle gas$ we have tried moisture on,line analyzers but they have not been very effective for us0 (o$ we have resorted bac to an old techni2ue$ called the dew point analyzer$ which is just a stainless steel cup0 Dou put dry ice in it$ and then you pass the gas over it and watch for the dewpoint change with a thermometer0 3hat wor s fairly well$ once you become proficient in the techni2ue0 We use that to monitor our moisture level0 39(BA>C Des$ + would support that wholeheartedly0 3he old techni2ue often wor s best$ and it is actually 2uite accurate0 Dou should poll licensees to find out what success they have had with the moisture analyzers0 +f you do have a problem with them$ go bac to the old techni2ue0 +t is a really good one0

R)(A1BC We do have moisture analyzers0 We use them more for detection of spi es in the feed or upset conditions0 We usually add alcohol as water and control it based on feed$ and find that much more reliable than the analyzer itself0 &A>)( DA>G>AG)>+9= "Falero >efining P @ar eting 1ompany#C +s anybody using analysis of recycle gas$ methane to heavier ratio$ to estimate the water level? <A3A>()=C We have used that as a trending tool0 We have loo ed at the methane to methane plus ethane and propane ratio$ and if we see that ratio going up$ then we are probably drier than we want to be0 +f we see that ratio going down$ we could be wetter than we want to be0 We generally use this in areas where we do not do a lot of moisture injection and control$ li e some semiregeneration units where we do not have a lot of upsets and do not change octanes all that much0 4ut it has been helpful in the past to find some problems0 (9@EA:(C +n regard to the gentleman who as ed the 2uestion about low nitrogen level detection in the reformer feed$ we recently got into this topic because of a <ene. unit where any ind of nitrogen level is undesirable0 Dou definitely want to target below a 80* ppm range$ because of the destruction of the catalyst0 +n a reformer$ of course$ you want to stay below 80* ppm$ because it is the limiting reactant in salt formation0 We found that detection below about 2 ppm was not accurate0 9s a matter of fact$ we involved our research center0 We continue to do the nitrogen test$ but it is more for loo ing for blatant nitrogen problems than actually controlling nitrogen in a 80* ppm or below range0 We just do not thin it is accurate in that range0 9fter chec ing$ we use the 9(3@ D%-27 test method but have not been able to achieve the results described by @r0 Rohnson of E)<0 ')(3A>C We found a G1 specifically for very low levels of nitrogen0 +t is manufactured by R0D0 "Robin Dvon Amission# 1orporation$ and it is a spectrophotometer method utilizing +1< "+nductive 1oupled <lasma# with a nitrogen channel0 We hope to be able to measure it down to the 188 ppb range and lower with that0 4>+9= R)&=()= "E)<#C We have typically used a chemluminescence method for determination of total nitrogen in light naphthas for isomerization units0 3he method is 9(3@ D%-270 +n that procedure$ the limit of detectability is listed as 80! ppmw0 )ur lab has been able to push that level down to 801 ppm by adjustment of sample size0 + suggest that those of you who have not used this method will find it to be a fairly easy method to analyze for nitrogen in the feed0 -uestion 1 4here in the refor'ing .rocess is the .reci.itation of a''oniu' chloride a .ro/le'3 4hat effect does the reactor section o.erating .ressure ha,e on the chloride de.osition .ro/le'3 ')(3A>C We have had a lot of problems with ammonium chloride deposition since going to 188? Fenezuelan crude operations0 9mmonium chloride precipitation temperature is directly proportional to the product of the partial pressures of hydrogen chloride and ammonia0 Depending on your reformer feed nitrogen content$ these salts can plate out anywhere between the feed6effluent e.changers and the recycle compressor$ and includes your reform stabilizer$ as well0 3his can occur at 288 ' for low concentrations of ammonia and &1l to as high as 2-8 ' for higher concentrations0 +n order to determine where in your system the deposition can occur$ you need the sublimation curve for ammonium chloride0 3his is based on the product$ of course$ as + mentioned a minute ago$ of the ammonia and &1l partial pressures0 E)< has a good graph of this0 3hese partial pressures can be reasonably estimated from nowing the nitrogen content in the reformer feed and the &1l concentration in the hydrogen recycle0 Dou chec where this sublimation condition coincides with the temperature conditions in the reformer$ then you can determine where the precipitation will ta e place0 +f you are increasing the nitrogen content of your feed$ or if you suffer a nitrogen upset or a chloride upset$ this precipitation will tend to occur in the cooler regions of your reformer0 9s far as pressure is concerned$ lower pressure can move the deposition to the cooler part of the system$ and higher pressure can move the deposition to a hotter part of the system0 +t all depends on where the least painful place to

deposit your salts is0 @ost of us do not have that much room to move on pressure$ and yield considerations usually dictate where we run our pressures0 'E((A::C We have e.perienced some ammonium chloride salt plugging in our refinery on the reformer0 3he first place we have seen this is in our depentanizer on our reformer0 We periodically have to do an on,line water wash to clear this up0 +t is pretty obvious when we need to do thisI the tower starts acting up0 (o we wash it and everything lines out fairly well0 We have also had problems in our downstream hydroprocessing units0 (pecifically$ we have a toluene disproportionation unit$ and the compressor on that unit has a suction screen0 3he compressor 2uit operating , basically 2uit wor ing0 We pulled the screen and discovered a good layer of salt on that screen0 We went bac to our reformer and discovered that we had some bloc ed valves around our chloride bed that were partially open$ and that we were actually bypassing material around it0 )nce we got those bloc ed in$ we no longer had that problem0 We also periodically feed reformer hydrogen as fuel gas to our gas turbine0 We have also seen some salt deposits on the filter on the fuel gas upstream of that gas turbine0 + believe that the cause for the salt is$ as @r0 'oster mentioned$ in large part due to the nitrogen in the feed to the reformer0 We do not analyze for this nitrogen$ so + would be very interested in hearing about how his analyzer wor s out0 + now that we run more nitrogen in our feed than E)< would recommend$ and that is something that + am going to continue to wor on$ as far as getting that nitrogen down0 9s far as the chloride side of it$ + believe that the causes of the chloride carrying through on a 11> are more related to the design of the unit0 )ur particular unit was designed in the mid,to,late /8s$ and it does have a problem of chlorides being carried out of the reduction zone into the reactor and on through the system0 + believe E)< did modify their design to correct that problem0 49>:)AWA=C + just wanted to put in a pitch to eep the chloride in the reformer via traps$ and do not e.port it to the hydrotreater where it is going to cause plugging and corrosion$ as well0 19+=C 9t our :ouisiana plant$ our problems show up in our absorber de,ethanizer tower$ so we ta e an opportunity to wash our tower whenever we can0 9t <ort 9rthur$ the depropanizer is occasionally affected by deposition of ammonium chloride$ and we have a caustic wash tower to remove the chlorides in this propane stream0 R)(A1BC We have noticed problems downstream of the semiregenerative reformer with precipitation of ammonium chloride in the stabilizer shortly after start,up and mid,cycle0 3he salts were attributed to high nitrogen in the feed0 3he ammonium chloride was removed by injecting water into the stabilizer feed , a very simple procedure0 We have ammonium chlorides in the recycle during regeneration which are washed out after the regeneration process0 We have not encountered ammonium chloride deposits in the reformer during the high nitrogen in the feed associated with salts in the stabilizer0 We have ammonium chloride in one of two hydrogen booster compressors0 3he ammonium chlorides are predominantly in the booster compressor operating at a lower cylinder jac et temperature0 9mmonium chloride problems in the reformer are a nitrogen problem0 3here are usually enough chlorides available in the system to react with all the nitrogen in the feed0 3he temperature at which ammonium chloride sublimes is a function of the concentration of &1l and ammonia0 +t is also a function of the water in the vapor phase0 +f the salt is present on the pipe upstream of the compressor$ and if the mole fraction of water increases in the recycle$ the salt can and does move0 +t can vaporize and then form again downstream0 9s operating pressure increases$ the temperature at which sublimation occurs also increases$ thus ma ing the salt problem worse0 +n our case$ the sublimation is occurring in a booster compressor operating at a low temperature0 <A3A>()=C )ur biggest problem is in the debutanizer stabilizer$ and we occasionally have to do a water wash0 )n the water wash$ we reduce the temperature so that the brine can leave the bottom of the tower0 )therwise$ we just may rearrange where the salt is if we do not let the salts go out the bottom0 When you are done with this$ you want to ma e sure that you get all of the water out of your overhead receiver$ so that you do not have new &1l coming up and forming a very low p& and highly corrosive situation in the receiver0

We would agree that good denitrification is important0 We do not have a real good naphtha hydrotreater0 We have a !88 psi separator$ so we have to be 2uite careful in what crudes we buy and how much nitrogen is in the naphtha portion0 >)@9=C We occasionally get problems on our recycle compressors due to deposition of ammonium chloride salts0 We will inject a small amount of naphtha on the run to try to wash them out or redistribute them0 )n occasion$ we have even used a couple of gallons of water for a wash0 )bviously$ that has to be done through a 2uil so that it is properly dispersed0 &A>4A>3 W0 W+K+G "@erichem 1ompany#C @erichem offers 1hlore. technology with a 'iber 'ilmL contactor to remove hydrochloric acid and ammonium chloride upstream of the stabilizer by means of an al aline water wash0 We have four units operating on 11>s in Rapan0 3he results have been a significant decreased fouling of the stabilizer trays and the reboiler0 3&+A>>D D9>DA "<all 1orporation#C We have installed several of our very high efficiency li2uid gas coalescers on the recycle gas line on reformers$ both in the E0(0 and in 1anada0 +nstalling these high efficiency li2uid gas coalescers results in dramatically improved reliability of the compressor by removing the ammonium chloride0 D0B0 BE1&&9: "+ndian +nstitute of <etroleum#C 9mmonium chloride in the recycle gas can deposit in coolers$ separators$ stabilizers cold trays and recycle compressor creating fouling$ under deposit corrosion or mechanical problem0 +t is worth remembering that 80* ppmw of organic nitrogen in the feed leads to appro.imately 2 tons per year of =&%11 for a million ton plan0 -uestion 2 %a,e the high yield catalysts li,ed u. to their e*.ectations3 4hat yield i'.ro,e'ents ha,e /een reali+ed3 (oes the yield i'.ro,e'ent decrease at lo0er .ressures3 39(BA>C 3here is a publication on the >G,*52 promoted bimetallic catalyst0 3his catalyst has been very successful0 3he publication is by <ro1atalyse and 9creon0 3his particular publication summarizes the overall yields obtained0 3he high yield *52 catalyst has met performance e.pectations in all of the units to date0 3he 1*O yield benefits have been on average 2 vol? to % vol? points over the incumbent catalyst0 3he hydrogen yield benefits have$ on average$ been about 1*8 scf6bbl to !88 scf6bbl above the performance of the incumbent catalyst0 'or lower pressure operation with this catalyst$ the more the difference is enhanced0 +n other words$ there is a greater yield benefit0 &owever$ this could be mas ed by more catalyst deactivation by co e which occurs more rapidly$ of course$ at the lower pressure0 3he least that could be said about the unit operating pressure is that it has not affected the >G,*52 catalyst yield benefits0 ':A31&A>C )ne customer reports recently loading E)< >,/2 and having seen a 10*? increase in li2uid volume yield0 3hey feel the catalyst has lived up to its promise0 9=GA:) 'E>'9>) "E)<#C E)< offers high yield catalyst systems for both 11> platforming and semiregenerative platforming units0 +n 11> platforming$ one unit is operating with E)<Ms >,1/8 series high yield catalyst0 3his catalyst met performance guarantees and matches predicted performance0 3here are now 2/ platforming units operating with E)<Ms >,/2 staged loading catalyst system which provides a yield advantage without sacrificing stability0 3he e.pected yield advantage has been observed commercially0 'or either catalyst system$ there is no significant effect of pressure on the yield advantage within typical operating ranges0 @+1&A: >)D "<etro 1anada <roducts#C

We have been using >G*52 for 2 years now0 +t has lived up to e.pectations0 We have seen the higher hydrogen yield0 9lso$ + would li e to comment on the robustness of the catalyst0 We operated it severely and it still survived0 +t has gone through major sulfur and humidity upsets and its activity recovered 2uic ly0 1atalyst loading was done using a proprietary catalyst dispenser supplied by the manufacturer0 Dield predictions were conditional to this type of loading0 We are presently in our second cycle with >G*520 3he regeneration procedure for this catalyst has been simplified compared to our past e.periences0 3he catalyst was regenerated successfully and is again performing within the yield projections0 3hese results were obtained despite periods of higher than normal = 2 in our feed and a 1*? increase in unit charge0 1ompared to selectivity projections$ we have seen an increase for certain aromatics which has benefitted our operation0 -uestion 4hat are the .ro/le's associated 0ith reducing the .ressure in either a CC& or cyclic refor'er7 and do the yield /enefits 2ustify the lo0er .ressure o.eration for a gasoline or an aro'atics unit3 @9:ABC 3his 2uestion deals with the problems in reducing pressures in catalytic reformers$ specifically a 11> or cyclic reformer0 3he overwhelming success of E)<;s 11> process dramatically illustrates the benefit of operating at low pressures in reforming0 Aconomic and other reasons have resulted in E)< settling in$ it appears$ at a separator pressure in the range of %* psi to -8 psi on the latest generation of 11>s0 +f you are trying to operate at lower pressures than that$ you are going to probably encounter some problems that are associated with dehydrogenation reactions0 Dou will see olefins showing up in your products while operating at very low pressures0 9s you lower the pressure$ if you have the ability to do that with your compressor$ you are going to lower hydrogen to oil recycle ratio0 3his will accelerate co ing and dehydrogenation reactions0 )ne refiner reported to me that he did a little e.perimentation on his own0 &e had e.cess capacity in his reformer 11> recycle compressor$ and he began lowering the pressure0 &e saw a continued increase in li2uid yields and hydrogen production0 When he got down to about !8 psi pressure$ however$ he got into a situation where olefin and diolefin formation was so rapid that he was fouling the compressor and e.periencing vibration0 &e brought the pressure bac up0 <A3A>()=C )ne barrier we have reached trying to lower pressure in our unit$ which we have generally been trying to do$ is some harmonics in our vertical feed6effluent e.changer0 9pparently$ we get into a flow regime where$ at the lower pressures$ the velocities are just right and we get some tube vibration0 We can ind of play the e.changer0 We can get the vibration from different places in the e.changer as we raise and lower the pressure0 )bviously$ wearing a hole in the tube in the e.changer is not a good idea$ so we run the pressure as low as we can$ but just above where we can hear the noise0 +t is a noise that ind of snea s up on you0 +t is not li e a bang or an alarm0 Dour operators may have to be warned to listen for obscure noises0 >)@9=C 9t our 1attletsburg refinery$ we have two 11> units$ one that runs at 118 psig$ and a second unit that runs at *8 psig0 We normally run the lower pressure 11> at higher severity to ta e advantage of the better yields0 We see a rapid decline in clay treater life in our sulfolane unit when we switch the feed from the 118 psig unit to the *8 psig unit due to olefins0 3his is a particular problem$ since this clay treater on our sulfolane unit is undersized$ and operates at a 105 li2uid hourly space velocity0 We would normally design these clay treaters for a 80* li2uid hourly space velocity0 3his forces us to actually lower the percentage of aromatics in the feed to the sulfolane unit when we would prefer to feed the higher aromatic material from the *8 psig 11>0 39(BA>C + reflect some of @r0 @ale ;s comments$ e.cept + am promoting the +'< technology0 With the lower 11> pressure$ there is no real operating problem$ but the rate of co e ma e$ of course$ will rise0 9s long as the regenerator is large enough$ the increased co e ma e is no problem0 3here is an increase in hydrogen production$ and of course$ more reformate$ typically about a 1? gain in production of the reformate0 &owever$ from an economic standpoint$ lower pressure will result in an investment cost increase$ due to the size of the recycle and net gas compressors$ the size of the lines$ size of the furnaces$ etc0

'rom operating cost viewpoint$ there will be an increase in power consumption of the recycle and net gas compressors0 3here will be limitations$ as have been pointed out$ for ultra,low pressure operation and$ typically$ that is the recycle gas compressor0 9t ultra,low pressure units$ that are presently designed for catalyst turnovers in ! to % days$ "188 regenerations per year#$ reducing the pressure will re2uire a high regeneration fre2uency with an eventual detrimental effect on the catalyst;s ultimate life0 9t low operating pressures and high severity$ when you are running about 188 >)=$ the olefin and diolefin contents in the reformate do significantly increase0 >educing the average reactor pressure from 18 bars to !0* bars$ or let us say$ 1*8 psi down to about *8 psi$ virtually doubles the amount of olefin and diolefin contents of the product0 3he problems that you get are typically the following0 'or gasoline production$ there will be greater instability of the gasoline and increase in additive that will be re2uired0 'or aromatics production$ there will be an increase$ as already mentioned$ and the need of clay treatment$ which gives rise to clay life and clay disposal problems0 'or this last point$ we do have the 9rofining process licensed by +'< and &>+$ which is the selective hydrogenation of olefins and diolefins in the reformate0 We feel that that is a good solution0 'or the other points on the yield benefits resulting from further pressure reduction$ we do not consider those to be attractive enough compared to the associated problems which have already been highlighted0 'E((A::C )n our E)< 11>$ we have plenty of room left in our regenerator0 (everal years ago$ we too a hard loo at running lower pressure0 )ur unit currently runs at appro.imately 118 psi on the product separator0 We have two 188? booster compressors that have not been nown for their reliability over the years0 +n order to run a lower pressure$ we were going to have to run these two machines in parallel0 9fter doing a very thorough economic evaluation$ we decided that the reduced reliability associated with running both machines 188? of the time would pretty much overcome all the positive benefits of the increased yields and increased hydrogen production0 9=GA:) 'E>'9>) "E)<#C 3he panelists have provided some e.cellent information with which E)< generally agrees0 >egarding @s0 'ussellMs comments on the net gas compressors$ E)< has reviewed this situation with customers$ and many with the same concern have decided to add a third reciprocating compressor in parallel to handle the additional net hydrogen production that results with the higher reformate yields and6or higher severity operation following the revamp0 4ased on more modern compressor designs$ the reliability of reciprocating machines is now in the 78O? range$ reducing maintenance concerns0 >evamps must be designed to accommodate the constraints put forth by the customer0 +n general$ you try to save as much heater as possible$ as well as the recycle compressor0 E)< has performed dozens of process unit revamps$ either to upgrade e.isting older 11> platforming process units$ or to convert semi,regenerative reformers to the 11> platforming process0 E)< has found that most concerns can be overcome$ and performance and financial objectives met$ through detailed studies that include good communications with the customer0 9s noted by the panel$ lower pressure operation improves catalyst selectivity$ increasing yields$ but compressor limitations coupled with lower operating pressure will decrease the available hydrogen recycle "& 26&1 ratio#$ thus increasing co e ma e0 3he effect of the improved selectivity on the heat of reaction needs to be accommodated0 3he increased co e production due to lower pressure and &26&1 needs to be accommodated0 3he effect on gas6li2uid separation also needs to be considered0 E)< has a lot of e.perience in revamping platforming and 11> platforming units to lower pressure and in revamping regeneration sections to higher capacity0 (3E9>3 G>9D "1riterion 1atalyst 1ompany#C 1riterion has recently commercialized a new 11> catalyst$ <(,%8$ which is generally targeted for first generation units with co e burning capacity limits0 &owever$ it can also show benefits in more recent generation units due to its increased stability0 +n pilot plant tests$ the catalyst has shown a !8? to *8? reduction in co e on catalyst0 >efiners will be able to use this to either reduce pressure and increase yield$ bringing the co e bac up to the precatalyst changeout level$ increase feed rates or process different low grade feedstoc s0 3he catalyst is a modified platinum6tin version of <(,280 2. !echanical -uestion " 4hat 'ethods ha,e /een used to control salt /uild-u. in the recycle co'.ressor7 other than 0ashing it3 %o0 effecti,e ha,e they /een3

')(3A>C 'or control of salt build up in the recycle compressor$ we have tried several methods with some successC li2uid hydrocarbon injection at the compressor suctionI dispersant injection at the compressor suctionI and installing demister mesh at the compressor suction0 3hese have all wor ed to some degree$ but none with raving success0 + can recommend any of those$ but before you do any of them$ be sure to wash your compressor$ because you do not want to start dispersion injection into a running compressor that is not clean0 Dou may fla e off pieces of salt with significant problems afterward0 3hese are all treating symptoms of a problem0 3he problem is that if nitrogen gets into your system$ and if you maintain a &1l concentration in the reformer$ you are going to form ammonium chloride salts somewhere$ and they will deposit somewhere0 3he best method is to minimize nitrogen entering the reformer section0 (ince we went to a higher nitrogen feed content$ we have had to revisit our &D( reactor and operate it more as an &D= reactor0 )ne e.ample of a discovery that we found was that over the years$ we had neglected to run it at as a high a pressure as we were capable of running it$ because as an &D( reactor$ it was not that big a deal0 9s an &D= reactor$ it was0 (o we found that we had some room to move upward in our hydrotreating pressure$ and we were able to raise the pressure *8 psi$ with a few very minor modifications0 )ur goal$ ultimately$ is to control total nitrogen content to the reformer down below 2*8 ppb0 + tal ed a minute ago about the method for analysis and E)< did$ too0 3he overall thing + would advise you to do is to start loo ing at your hydrotreating as a denitrification operation0 3hat means loo ing at your catalyst$ as well0 3here are catalysts on the mar et now that do a much better job of denitrofication than what you may have used in a reformer hydrotreater in the past0 49>:)AWA=C + would reinforce the statement about catalysts0 3he 1alifornia refineries have been dealing with high nitrogen feedstoc s in the reformer hydrotreaters for many years0 @uch of the rest of the country has tended to use naphtha hydrotreaters as a place to reuse spent catalyst in a second or third service0 9s you shift your feed slate$ it is important to put in a high activity$ fresh$ =ic el @olybdenum catalyst0 Dou will be surprised at how much better you can do0 4+=')>DC + agree with the previous comments about trying to treat the cause and not the symptom$ and instead getting at the root cause0 'or those refiners who are still having problems with fouling$ dispersant,based antifoulant programs can be very effective0 +t is very important that you start those up on a reasonably clean system0 )nce the system gets too fouled$ you just stand a real ris $ especially on a centrifugal machine$ of creating imbalances that can tear a compressor apart0 + did want to note a couple of things that are very important to designing a program that is going to be successful0 @ost of the programs that are unsuccessful$ + thin $ are because of poor thought going into them0 'or any dispersant program going into a compressor$ good atomization of the product is a ey to success0 Esing a pneumatic atomizing nozzle$ with recycling a small amount of the gas from the discharge of the machine$ is one way to go0 3his would be applicable to reciprocating compressors$ especially where you can not tolerate any li2uid0 )bviously$ the entire system needs to be well designed and built to withstand constant vibration and potential metal fatigue0 3he last thing you want is some small piping around that compressor that is going to brea loose0 +f you can tolerate some li2uid "a centrifugal machine#$ using a light naphtha as a carrier through an atomizing nozzle can be very effective as a means to disperse the product0 +n this case$ you have some naphtha carrier going through the machine$ which will also help carry the dispersed salts out of the compressor0 3he choice of the product itself is very important0 +t must be compatible not only with the carrier$ but also must have good light hydrocarbon compatibility and good salt dispersing capability0 3hese are a few of the things that you really need to loo at closely if you are going to consider a chemical treatment alternative0 19+=C 9t (tar$ salt build,up on the recycle compressor has not been a big problem for us0 We normally water wash with hot condensate whenever we are down0 3&+A>>D D9>DA "<all 1orporation#C

+ guess at this point + should just reiterate the statement + made earlier0 )ur high efficiency li2uid gas coalescer can really protect compressors$ and remove any trace of ammonium chloride and then suppress any e.tensive maintenance0 BAF+= 'A>>9: "1+3G) >efining P 1hemicals#C 3here is one thing to be aware of$ too$ when you use dispersants in washing systems to move the salts0 When you do your @)1 review$ chec the metallurgy of your e2uipment downstream$ because we did e.perience metallurgical problems and severe corrosion problems with injecting various inhibitors to try to prevent salt deposition0 -uestion 8 For continuous catalyst regeneration syste's using stainless steel instead of Inconel7 ha,e there /een .ro/le's 0ith stress corrosion cracking3 4hat .recautions need to /e taken3 >)@9=C We did not use 15,5 austenitic stainless steel materials in any of our regenerators since they are susceptible to stress corrosion crac ing in hot chloride environments0 3he presence of chlorides can be particularly harmful when the unit is down and free water might be present0 +ncreasing the nic el content above !2? increases the resistance to chloride stress corrosion crac ing and is recommended0 @onel$ +nconel and +ncoloy are all acceptable0 We use +nconel -88 material and have not had any problems0 -uestion 9 4hat is the ty.ical life of the ,ertical co'/ined feed e*changer 5not Packino*6 in refor'ing ser,ice3 4hat ty.e and fre;uency of ins.ections and 'aintenance are reco''ended3 19+=C 9t <ort 9rthur$ we inspected ours after a 18 year run$ and it did not show any problems0 9t our Delaware 1ity plant$ we also did not have any problems0 3ypically$ the bottom baffle and distributor are inspected during every turnaround$ which is appro.imately every % years0 'E((A::C 9t our <ort 9rthur refinery$ we have two parallel vertical feed6effluent e.changers on our 11>0 3hey have been in service for 12 years0 +n 177*$ we had a major turnaround on the unit$ and we strongly considered pulling these e.changers0 We actually put together a pretty detailed plan on how to pull them0 4ut as we got closer and closer to the day of the turnaround$ we decided against pulling them for several reasons0 =umber one$ they would ta e up space$ and the e2uipment re2uired to pull them would also ta e up space re2uired for other activities during the turnaround0 We made phone calls to E)< and to other refiners and determined that very few people have actually pulled these e.changers0 (o$ instead of doing that$ we did a pretty e.tensive inspection0 We did acoustic emissionsI we also did ultrasonics0 We removed the insulation and did ultrasonic testing in order to determine that the e.changers were fit for service0 We have not seen any heat transfer loss on these e.changers$ so we have never really had any re2uirement to pull them for cleaning reasons0 &9&=C We also have two vertical feed e.changers in service0 )ne is 5 years old in our service$ and it was a second,hand to us$ so it has several prior years service in addition to our service0 9nother unit has an e.changer that is over 18 years old now0 3he only problem we e.perienced was one lea ing baffle$ about 2 years ago0 =ow we inspect the bellows about every * years during turnaround0 3here are manufacturers recommendations for how to pull these bundles0 We studied these but we decided that we could not justify it$ either0 We have not seen any heat loss either0 @9:ABC )ur e.perience with these e.changers with our clients has been very good$ also0 9s a matter of fact$ one maintenance supervisor recently told me that his e.changer had already outlasted four refinery managers0 <A3A>()=C We have 1/ years of operation on our feed6effluent e.changer0 We have had three lea s of the e.pansion bellows at the bottom end0 3he first time one was found$ we were successful at weld repair for a while$ but that weld repair later failed again0 3he last time that we had the e.changer open$ we replaced the bellows0 We have never pulled the

e.changer to loo at the inside of the shell or to loo at the outside of the tubes0 We did do acoustical emissions testing to help us determine that the shell did not have any active indications "to use an inspector term#0 We had some heat transfer loss this last time$ and we were overjoyed when we too the dollar plate off the top to see that we had a bunch of tubes plugged0 We were able to wash that out and get all of our heat transfer bac 0 9s far as loo ing for lea s on,line$ @r0 >oman previously mentioned using the sulfur he.afluoride method0 We do not have the G1 detection method0 We use a beta particle generator and a little ammeter that measures the electron absorption by the sulfur he.afluoride tracer in the system0 3his system had also been used in one of our refineries to find reactor bypass in a reformer0 We were able to determine that$ yes$ we had to get in these reactors and seal the tops of the beds0 )ur turnaround cycles on the e.changers themselves are in the ! year to / year range0 >)@9=C )ur e.perience is the same0 3hese are the e.changers that never get pulled0 We have not had any lea s0 3hey do not foul0 )ne further item on the lea detection$ we have used all three methodsC radioactive tracers$ helium$ and sulfur he.afluoride0 We stopped using radioactive detection due to the handling problems0 +f you have the capabilities$ the sulfur he.afluoride is much more sensitive than helium0 (9@EA:(C +n our >obinson refinery$ we have not pulled the e.changers in their 1- years of service0 &owever$ due to loss of heat transfer prior to a spring turnaround this year$ we did try to chemically clean the shell side of these e.changers without pulling them0 We used a potassium permagenate solution and an acidizing wash0 1oming bac on,line$ we actually lost heat transfer0 We believe the problem was due to lac of velocity of the circulating solution$ and we thin we moved some of the deposits around0 (o we do$ in fact$ plan to pull those bundles in the near future0 3he way we intend to do this is to actually build a superstructure at the unit site and suspend the bundles for cleaning$ rather than laying them down0 (ince the QP9 session$ we have pulled and cleaned these bundles0 3he primary cause of fouling was tube,side pluggage of heavy hydrocarbons0 3he tubes had been hydroblasted without dropping the tubs and tube,side internals0 3his is a must for hydroblasting the tubes0 &ydrocarbon on both tube and shell sides was poly nuclear aromatics$ with a higher molecular weight on the shell side than on the tube side0 >0 >9R9@9=+ "@angalore >efinery and <etrochemicals :td0#C Did this 2uestion address only the non,<ac ino. e.changers? 9=GA:) 'E>'9>) "E<)#C 3he 11> platforming process unit at @angalore has a <ac ino. welded plate e.changer0 3hose e.changers have$ in 11> platforming service$ shown e.cellent non,fouling operation0 &owever$ in regard to this specific 2uestion$ the life of F1'AMs is similar to that of other process e2uipment0 3ypical life can e.tend well past 1* years$ but that can be shortened by internal vibration "especially in early vendor designs#$ improper maintenance$ corrosion$ and so on0 +nspection generally consists of pulling the shell cover$ dropping the floating head and dye chec ing the bellows0 A.changer component metal thic ness readings are also ta en0 +n fi.ed bed reforming service$ corrosion can occur at the bottom inside surface of the shell cover "a dead area# if this area is not regularly drained during regeneration and unit restart0 9lso$ there is another potential area for corrosion on the outside diameter of the tubes at the very bottom$ just above the floating head tubesheet0 Dou can see this without pulling the bundle0 E)< does not re2uire the pulling of this bundle unless necessitated by process reasons "fouling#$ or dictated by the regulatory agencies$ company policy or a real need to do so0 +f the bundle is pulled$ proper support of this piece is mandatory to avoid damage when handling or placing the bundle in the horizontal position0 (. Aro'atic )*traction -uestion : 4hat 'ethods are a,aila/le for re'o,ing chloride fro' a sol,ent syste'3

19+=C +n our Delaware 1ity plant$ we operate a solvent vacuum regenerator on a continuous basis to remove chlorides from the solvent0 We target appro.imately 188 ppm chloride level in the solvent0 39(BA>C +n &>+;s sulfolane aromatic e.traction process$ we do have a continuous slipstream to solvent regeneration0 3he amount that you put through is a function of just how well you are controlling your p& and o.ygen ingress into the recovery tower0 +n one of our licensed processes in Rapan$ we have run 15 months with water white sulfolane$ which is most unusual0 +t is an e.tremely tight unit0 3he two things that affect solvent degradation most are the build,up of acidic compounds due to high temperature operation and the o.ygen ingress0 Dou get acidic compounds forming 2uite readily when you have o.ygen lea ing in0 +t is often very difficult to detect the o.ygen ingress e.cept by loo ing at the degraded solvent that you pull from your continuous on,line regenerator0 We generally advocate removal of a small 2uantity every few wee s$ li e up to * gallons$ but this is directly a function of how well you are operating the unit0 We are not specifically loo ing at the chloride content as such0 We are just maintaining good p& control in a carbon steel system$ and we see no corrosion0 (o one thing$ based on the 2uestion$ that + am going to do is e.plore doing some testing on the spent (ulfolane to chec the chloride content$ and then + can compare notes with @r0 1ain0 R9()= =)A "E)<#C 3raditionally$ E)< has removed chloride from the solvent systems by passing a slipstream of solvent through single stage vacuum distillation or single stage steam strippping0 @ore accurately$ we allow mostly chloride salts to accumulate in the bottoms material of this type of e2uipment which is manually removed intermittently0 E)< recommends the injection of monoethylamine "@A9# to neutralize the acid contaminants that can form in e.traction units as a result of the brea down of the solvents0 (ome operators have used ion e.change to remove ionic species in general from the process units0 3his appears to be a very efficient method for those who have difficulty maintaining a clean solvent stream$ but this practice is not the norm for the majority of process units0 9 slipstream processing of solvent through activated carbon has also been pursued by some operators$ but this method$ also$ does not appear to be widely,practiced$ and would tend to produce more solid waste than the previous two strategies0 ). Poly'eri+ation -uestion = 4here is (i'ersol catalyst in2ected7 and 0hat ratio of alu'ina to nickel do you 'aintain3 39(BA>C 3he Dimersol process uses two different types of catalysts0 )ne catalyst is injected into the feed line and the other is routed to the recycle stream before entering the reactor0 3he ratio of these catalysts is somewhat proprietary information$ but the range is typically in the order of 12 to 1- on a molar basis0 3he injection points have been changed0 +njection is after the pumparound system at the coldest point of the loop0 3he nic el "soap" is injected to either the suction or the pumparound pump or into the feed0 3he nic el "soap" is usually where the highest concentration of propylene in the feed occurs0 We have found that 2uill injection is the best method for mi.ing0 <revious use of static mi.ers has been dropped from our designs0 <A3A>()=C )ur A9D1 is injected in the air cooled reaction recycle or pumparound cooler with the outlet returned bac to the reactor0 )ur aluminum to nic el ratio is currently being run within the range that @r0 3as er mentioned0 -uestion ? %as anyone had .ro/le's 0ith for'ing sludge in (i'ersol .u'.around coolers3 If so7 ho0 ha,e you controlled it3 39(BA>C (ome of our licensees have problems with sludge in the Dimersol pumparound cooler0 +'< and &>+ recommends

purging some of the reactor bottom stream to the downstream neutralization section$ occasionally$ to minimize the sludge deposits0 +n efforts to improve the overall situation$ we are now proposing a slightly different and new philosophy0 We now loo at having the process fluids in the tubes for high velocity0 &owever$ this may not meet the client;s re2uirements and therefore$ we may have water on the tube side in the E0(090 3his is a client choice0 +n addition$ the design and type of the pumparound cooler is important0 +t is important to avoid the dead areas which occur in the bo. headers in air coolers$ since this is where sludge can accumulate0 )ur e.perience is that sludge comes from impurities in the 1 ! feed0 3he main contributors are water and dienes and$ therefore$ driers can be justified0 :evels of contaminates which can cause problems are about * ppmw with diene and the saturation level of water$ which is about 1888 ppm in the 1 ! feed0 (o$ the solvent needs to be dry0 3herefore$ in start,up procedures$ a lot of emphasis is placed on ensuring that the unit is as dry as possible before operation0 1orrosion has been a problem in the units$ as well as erosion0 <A3A>()=C We are one of the units that has a problem with sludge formation0 We see it in our recycle cooler$ or pumparound cooler0 3his is an air cooler$ so we do have the material on the tube side of the e.changer0 9bout once a year$ we have to shut the unit down and clean the cooler$ the lines$ and the reactor0 We determine the need to shut down by a decrease in recycle flow and a decrease in the cooling capacity of the system0 9 bas et strainer has been installed in front of the cooler$ and + do not now how much of a change this has made to the situation0 3he cleaning is done by hydroblasting$ and because the system is intolerant of water$ we do a hot nitrogen purge or strip of the system to get all residual moisture out of the system before we reintroduce the feed and catalyst0 19+=C We monitor our feed 2uality for diolefins$ sulfur$ and moisture0 We regenerate our molecular sieve driers every 2% hours$ and we have lowered our reactor temperature from 12* ' to 118 '$ which seems to have helped0 We also blow down our reactors$ about *8 bbl6hr$ for * minutes every shift through the pumpout line to the caustic treating section0 (3AFA @93&E> "1hevron#C What we have found is that sludge is a way of life with a Dimersol circulation loop0 + suggest that if you are seeing a lot of sludge$ and your catalyst consumption is high$ especially the A9D1$ then you probably have a problem with the molecular sieve driers0 1hec the regeneration cycle$ the state of molecular sieves$ the regeneration temperature$ etc0 3hat is where we found our problem$ and were able to reduce the catalyst consumption by half0 -uestion "@ %o0 fre;uently do you check for conta'inants 5a''onia7 0ater7 diolefins6 in (i'ersol feed3 4hat test 'ethods are used3 &A=BAC We have an on,line water analyzer that chec s moisture in the discharge of our feed dryers0 3his analyzer can be switched to sample the dryer inlet as well0 We only chec for ammonia occasionally with Draeger tubes$ and have only had one or two minor upsets with ammonia in the last several years0 Generally$ if the water is ept out$ the ammonia will not be a problem0 We have not detected diolefins in our Dimersol feed0 While diolefins are difficult to detect and measure$ we have found gas chromatography to be a reliable method0 When testing for contaminants in the laboratory$ we use ion chromatography for ammonia$ and Barl,'ischer titration for water0 <A3A>()=C We probably do not analyze as often as we should for some of these contaminants0 We do try to control the amount of diolefins that get into the system by running our 1 !61% splitter in such a way that 2uite a bit of the propylene goes down the tower$ so that we do not have a very good chance of getting any of the diolefins going up the tower into the Dimersol0 We do have driers on the system$ and we try to eep the operation of the depropanizer or the splitter$ the drier$ the @ero. system$ and the :<G aiming system running very steady$ and just try to mind our business there to eep the dirt out of the system0

19+=C We have on,line analyzers for water and diolefins0 We use a <anametrics analyzer for water and a G1 for the diolefins0 39(BA>C + agree with everything that has been said0 Dou can use an 9(3@ method to chec for ammonia0 +'< and &>+ recommend testing the feed for contaminants on a daily basis0 'or the moisture$ the Du<ont and <anametric type have been 2uite good for measuring the moisture in the Dimersol feed0 'or diolefins$ we recommend the +'< D2,// method to test the diolefins0 F. Iso'eri+ation -uestion "1 %a,e the ne0 high acti,ity +eolite and chlorided iso'eri+ation catalysts .ro,en to /e a significant i'.ro,e'ent o,er their .redecessors3 ':A31&A>C 3wo new high activity chloride catalysts produced by 9 zo =obel$ named 93,2 and 93,2G$ have proven commercially to be more active than e.isting amorphous catalysts0 <resently$ a 1!$888 bbl6d 1 % isomerization unit in Dubai has been running very satisfactorily on 93,2 for more than 2V years with an estimated activity improvement of appro.imately %8?0 3his leads to higher isobutane formation due to the improved thermodynamics at the lower reactor temperature$ or to higher throughputs with the same yield0 'or 1* and 1- isomerization$ two refineries$ one in the E0(0 and one in Aurope$ have chosen to use 93,2G0 4oth are reaching their targets while using less catalyst than before0 )ther ways to e.ploit the catalyst improvement includeC 1# increasing isomerization capacity with the same product 2uality$ or 2# treating more severe feeds li e benzene0 +n the latter case$ the heat formation penalty$ which is caused by treating more benzene$ is compensated for by the lower operating temperature of the catalyst0 'E((A::C We are currently using the E1+ +sopar catalyst in our 3+< unit0 We loaded it about 1V years ago$ and we have been very happy with it0 +t is still holding close to start,of,run activity after *88 days on stream0 1onversion is also higher than with the catalyst we previously had in the reactor0 9nother plus is that the catalyst is more moisture tolerant , with e.cursions up to 588 ppm with only a temporary loss in catalyst activity0 4>+9= R)&=()= "E)<#C E)< has recently commercialized the :<+ 188 catalyst0 3his catalyst is based on a novel sulfated metal o.ide formulation0 3he catalyst is appro.imately 1*8 ' more active than the industry standard zeolites0 3his means that the operating temperature for this catalyst is in the !*8 ' to %88 ' range0 +t is also fully regenerable$ and tolerant to such contaminants as water0 3he new catalyst is used in the <ar,+som process$ and represents a very attractive revamp opportunity for improving the performance of e.isting once,through zeolitic units and 3+< units0 -uestion "2 %a,e any refiners e*.erienced e*cessi,e yield loss in iso'eri+ation units3 <o 0hat has this loss /een attri/uted3 <A3A>()=C 3he biggest impact that we have seen on yield loss in isomerization units has been when we go into a 1lean 9ir 9ct benzene destruction or benzene prevention mode$ where we try to include all of the benzene precursors "i0e0 1 compounds# into the isomerization unit instead of down into the reformer0 )ur naphtha splitter was not set up for a perfect splitting between 1- and 1/$ so we get a considerable amount of heptane type material into the feed0 9 considerable amount of this apparently crac s the propane$ and this propane is lost to the fuel system$ since we do not have an :<G recovery system on the stabilizer offgas0 We loo ed at putting in an :<G system$ just to collect this propane$ but with the caustic wash to control the &1l$ we have not been able to justify it0 )ccasionally$ when we feed some natural gasoline that has a little bit of normal butane in it through our naphtha hydrotreater$ and on

through the isomerization unit$ we get enough butanes that$ coupled with the propane$ may ma e recovery justifiable0 We are studying this at this time0 -uestion " %o0 are refiners addressing salt de.osition and corrosion in their iso'eri+ation units3 <A3A>()=C We thin we have seen ammonium chloride deposition in the reactors that has led to higher pressure drop in the system0 3he salt ties bac $ as discussed previously$ to the naphtha hydrotreating section$ and with the nitrogen in the feed0 We have a !88 psi separator naphtha hydrotreater with space velocity of about 12$ and are running some fairly high sulphur crude0 We cannot really go to the nic el,moly catalyst in this case$ as @r0 4arloewen had suggested0 (o we have had to limit the amount of high nitrogen crudes that we run0 We have been fairly successful at eeping the ammonia levels down in the reformer and in the isomerization unit since then0 9s for corrosion in the downstream part of the unit in the offgas scrubber from the stabilizer$ we used to have a lot of lea s in the caustic system0 What we now do is test the caustic for free caustic on a daily basis0 +n the past$ however$ at times we more than spent it0 We went to an operator p& test of the system on their rounds through the unit every % hours0 We are not trying to run to a / p& or anything li e that0 +f they see anything less than 12 p&$ they are going to be in trouble in a few hours$ so they change the caustic right then0 3hat has wor ed very successfully for / years0 We have not had an additional lea since we started loo ing at the p&0 (tartup procedures are very important to follow$ as far as ma ing sure we get rid of all the water in the system before we cut the reactors in is concerned0 We did have some corrosion in the stabilizer overhead receiver a few years ago resulting from trying to start up a little too soon0 3he time you save in starting up is not worth the problems of having to go bac and fill weld and change the operation of your unit0 (9@EA:(C 1oncerning corrosion$ + certainly agree with @r0 <eterson;s comments on the start,up$ particularly for the fractionation section0 Dou must get it dried out0 We have had problems in the <ene.ate rundown piping with actual pipe failures0 3o solve the problem$ we use a corrosion inhibitor in this rundown line to combat chloride,based corrosion0 3he corrosion appears to be caused by trace chlorides in the stabilizer bottoms where the wet regenerant stream from the feed driers combines with this rundown stream0 (ince we do not see corrosion at dew point in the piping from the driers to the rundown line$ we do not believe that the source of chlorides is coming from the regeneration of the hydrogen driers0 3he platformer wet gas wash tower does a reasonable job of removing <ene. feed gas chlorides0 We are replacing carbon steel with hastalloy in some of the piping$ particularly in the product stabilizer overhead around the water boot area0 4>+9= R)&=()= "E)<#C Rust a couple of comments on stabilizer corrosion0 3his tower operates perfectly dry and any water that gets into the tower$ either during a shutdown or during normal operation$ will cause corrosion0 3his is because there is a high concentration of &1l in the upper portion of the stabilizer0 +f the tower is ept dry$ you will eep the corrosion under control0 We strongly recommend against adding an amine or anything to the overhead receiver because of the high concentration of &1l in that system0 3he ey to the scrubber operation is to maintain the caustic strength at a level of about 2? before you change the caustic0 @ost of the scrubbers are a batch type operation$ and you do not want to drain all of your hydro.ide neutralization capability every time you change the caustic0 (o it is very important to maintain that caustic strength in the scrubber0 <A3A>()=C +n conjunction with what @r0 Rohnson just said$ + said before that we were chec ing the caustic strength about every other day0 We do it daily now$ and this p& is only a bac up system that we use in case something happens or the laboratory analysis is showing too high a number0 #. )therification -uestion "" 4hat are the e*.eriences 0ith ad,anced controls on ether units3 4hat are the key control .ara'eters3

19+=C We recently installed D@1 controllers in both the @34A and 39@A units$ and have had great success in controlling these units0 3he ey control parameters are methanol$ and optimization of the depentanizer on the 39@A$ as well as controlling the purity on both units0 4>+9= R)&=()= "E)<#C (everal producers of @34A have used advanced process control "9<1# to augment the control of the butane @34A column0 3he azeotropic mi.ture formed between methanol$ the various 1 %s$ and @34A$ enhances the difficulty in controlling the separation of the 1%s and methanol from the @34A0 9<1 has been used to adjust the column pressure$ the reflu. rate$ and the reboiler duty0 3his optimizes the @34A purity and minimizes @34A carryover into the overhead0 -uestion "8 4hat i'.act does feed sulfur content 5.articularly di'ethyl sulfide6 ha,e on !<$) catalyst life3 4hat solutions e*ist for reducing the i'.act of sulfur in the feed3 39(BA>C @34A is an acidic resin and is sensitive to basic compounds with the feed and to sulphur compounds also in the feed0 3he sulphur compounds which do impact mostly are mercaptans$ sulfur$ dimethylsulfide$ and D@(0 D@( have a very bad impact on the catalyst since it irreversibly deactivates the catalyst0 3here is really no good solution to the problem e.cept to accept the feed as is0 3he catalyst is relatively ine.pensive and there is less economic impact if you do deactivate it fully0 )bviously$ upstream improvements can be made by @ero. treatment of the feed$ or by using a selective hydrogeneration unit in front of the 39@A or @34A units0 4ut this$ of course$ will ta e planning and capital0 19+=C We found that /8? of the 39@A catalyst poisoning is a result of feed D@(0 D@( poisoning has reduced the catalyst life by 1 to 2 months based on analysis of the spent catalyst0 We are considering an 9:1)9 process that removes poisons from the feed$ using regenerative molecular sieves0 A>+1 (1&W9>3K "1D 3A1&#C D@( has been identified as a diffuse catalyst poison for @34A and 39@A catalyst0 (ulfur species$ such as mercaptan sulphurs$ do not present this problem with resonant catalyst0 3he e.act mechanism of the deactivation is unclear0 &owever$ the deactivation rate is nown to be sensitive to temperature$ D@( concentration$ and methanol concentration0 'or e.ample$ at the 1*8 ' range$ and -8 ppm D@($ the deactivation rate can be measured in terms of percent conversion loss per day0 (olutions include running at minimum reactor temperatures and ensuring ade2uate methanol flow to the system0 +n the case of @34A units$ minimize the amount of 1 *s in the feed$ as D@( distills with 1 *s0 'or 39@A units$ absorption systems are available which will remove D@(0 D9F+D :0 (@+3& "9lcoa +ndustrial 1hemicals#C 3o further elaborate on potential solutions$ either in a stand alone mode or as a trim to water wash systems$ there are activated alumina,based selective adsorbents that can remove mercaptans$ dimethyl sulfide$ dimethyl disulfide$ propionitrile$ and acetonitrile from either the isobutylene or isoamylene streams$ thereby protecting the etherification catalyst0 %. )n,iron'ental Control -uestion "9 4hat has the e*.erience /een 0ith scru//ing the CC& regeneration ,ent gas3 Are 'any refiners scru//ing this strea'3 &+GG+=(C 3he panel did not have an answer to this 2uestion0 Does anyone from the floor have a response? 9=GA:) 'E>'9>) "E)<#C

=early all E)< 11> platforming unit designs in the past 18 years have included vent gas scrubbing$ which we have offered since the early 1758Ms0 3he scrubbing is very effective0 @ore than 77? of the &11 and 78? of the chlorine in the vent gas is removed0 E)< now offers for sale a scrubbing system with an innovative contacting method0 @ore and more grass roots and revamped units$ regardless of location around the world$ are including vent gas scrubbing in the project scope to address environmental concerns and local environmental codes0 >0 >9R9@9=+ "@angalore >efinery and <etrochemicals :td0#C We have installed a fairly e.pensive caustic scrubbing system for the offgas$ as recommended by E)<0 3hey recommended that free caustic should be maintained at about 1? to 2?0 We found that caustic consumption was e.tremely high$ not because of chloride content$ which was in the ppm range$ but more because of 1) 20 (o what we did was that we dispensed with caustic and started scrubbing with demineralized water with a little caustic that will maintain the p& of /0*0 We have had no problem since then0