7
T he refining industry is investing heavily in new processing units to produce ultra-low-sulphur (ULS) fuels. As a result, hydrogen utilisation is increasing, on-stream factor and hydrogen reliability are becoming more important, and resources for other investments are scarce. Catalytic reforming is the preferred technology for producing high-octane gasoline and is usually the refinery’s main source of hydrogen. Although existing reformers in North America are generally not fully utilised, many are older semi- regenerative (SR) or cyclic units with cycle times that are incompatible with continuous ULS fuels production. They produce less gasoline and hydrogen than newer ultra-low-pressure continuous catalytic regeneration (CCR) units. CCR reforming More than 35 Octanizing and Aromizing CCR reforming processes for gasoline- and aromatics-orientated catalytic reforming have been licensed world- wide. Ten new units were licensed in 2005. The Axens CCR reforming process is schematically represented in Figure 1, including key features for producing high-octane gasoline or aromatics-rich petrochemical streams from naphtha. The catalyst circulation systems of these reformers are designed for long and active catalyst service as well as ease of operation and maintenance. To ensure low catalyst attrition, the lift system must be designed for continuous, smooth, non-pulsating and gentle lifting. Catalyst is continuously transferred to the regenerator, where the coked catalyst undergoes a sequence of steps involving controlled coke combustion, oxychlorination and calcination to restore the catalyst activity and metals redispersion. The proprietary RegenC-2 dry burn loop regeneration system is able to perform complete catalyst activity restoration under mild conditions to maintain catalyst activity and mechanical strength. The catalyst circulation and regeneration operations are highly automated and require minimal operator attention. The reformer’s side-by-side reactor arrangement, as shown in Figure 1, has several advantages over the stacked design. Access for construction, inspection and future modifications to the reactors, as well as to the internals, is greatly increased. In addition, thermal expansion problems are minimised and the reactor structure is lighter and lower to the ground. This enables an optimal radial reactor design (L/D) without height constraints and a simplified internals structure that is less prone to mechanical problems due to thermal expansion. The reactor placement also provides for shorter catalyst transfer lines, shorter hot transfer lines between reactors and heaters, plus minimal non- flowing heel catalyst volume due to the use of spherical heads (less than 0.5% of the catalyst inventory compared to many times this in other designs). These advantages translate into significant immediate and longer-term savings in investment, construction and mainte- nance costs. The key to unit performance and long catalyst life in CCR reforming is the RegenC-2 catalyst regenerator technol- ogy. Combined with recently developed and commercialised catalysts, regener- ators incorporating this technology can provide sustained catalyst performance over hundreds of regeneration cycles. Significant technology and monitoring improvements in the coke burn and catalyst oxychlorination zones result in increased catalyst life and improved operating flexibility. RegenC-2 consists of four independent zones, depicted in the block flow diagram in Figure 2. These zones include: A primary burn zone equipped with a dry burn loop to minimise moisture during combustion — A finishing zone with oxygen and temperature control (no sharp exotherms or carbon breakthrough) Octanizing reformer options Staged investment and reformer technology improvement strategies are available for increasing hydrogen production, cycle time and reliability. Options include revamps to SR reformers and hybrid SR/CCR Dualformers, as well as new CCR unit investments Bruno Domergue and Pierre-Yves le Goff Axens Jay Ross Axens NA REFINING PTQ Q1 2006 www. e ptq.com 67 Recovery system Recycle compressor Sep r o t a r a Hydrogen rich gas Reformate to stabilisation Feed Booster compressor 1 - R 2 - R 3 - R RegenC-2 Regenerator Reactorsand heaters Figure 1 Axens CCR reforming process

Ptq q1 06 Oct Ani Zing Reformer Options

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The refining industry is investingheavily in new processing units toproduce ultra-low-sulphur (ULS)

fuels. As a result, hydrogen utilisation isincreasing, on-stream factor andhydrogen reliability are becoming moreimportant, and resources for otherinvestments are scarce. Catalyticreforming is the preferred technology forproducing high-octane gasoline and isusually the refinery’s main source ofhydrogen. Although existing reformersin North America are generally not fullyutilised, many are older semi-regenerative (SR) or cyclic units withcycle times that are incompatible withcontinuous ULS fuels production. Theyproduce less gasoline and hydrogen thannewer ultra-low-pressure continuouscatalytic regeneration (CCR) units.

CCR reformingMore than 35 Octanizing and AromizingCCR reforming processes for gasoline-and aromatics-orientated catalyticreforming have been licensed world-wide. Ten new units were licensed in2005. The Axens CCR reforming processis schematically represented in Figure 1,including key features for producinghigh-octane gasoline or aromatics-richpetrochemical streams from naphtha.

The catalyst circulation systems ofthese reformers are designed for longand active catalyst service as well as easeof operation and maintenance. Toensure low catalyst attrition, the liftsystem must be designed for continuous,smooth, non-pulsating and gentlelifting. Catalyst is continuouslytransferred to the regenerator, where thecoked catalyst undergoes a sequence ofsteps involving controlled cokecombustion, oxychlorination andcalcination to restore the catalystactivity and metals redispersion. Theproprietary RegenC-2 dry burn loopregeneration system is able to performcomplete catalyst activity restorationunder mild conditions to maintaincatalyst activity and mechanicalstrength. The catalyst circulation and

regeneration operations are highlyautomated and require minimaloperator attention.

The reformer’s side-by-side reactorarrangement, as shown in Figure 1, hasseveral advantages over the stackeddesign. Access for construction,inspection and future modifications tothe reactors, as well as to the internals, isgreatly increased. In addition, thermalexpansion problems are minimised andthe reactor structure is lighter and lowerto the ground. This enables an optimalradial reactor design (L/D) withoutheight constraints and a simplifiedinternals structure that is less prone tomechanical problems due to thermalexpansion. The reactor placement alsoprovides for shorter catalyst transferlines, shorter hot transfer lines betweenreactors and heaters, plus minimal non-flowing heel catalyst volume due to theuse of spherical heads (less than 0.5% ofthe catalyst inventory compared tomany times this in other designs). Theseadvantages translate into significant

immediate and longer-term savings ininvestment, construction and mainte-nance costs.

The key to unit performance and longcatalyst life in CCR reforming is theRegenC-2 catalyst regenerator technol-ogy. Combined with recently developedand commercialised catalysts, regener-ators incorporating this technology canprovide sustained catalyst performanceover hundreds of regeneration cycles.Significant technology and monitoringimprovements in the coke burn andcatalyst oxychlorination zones result inincreased catalyst life and improvedoperating flexibility.

RegenC-2 consists of fourindependent zones, depicted in theblock flow diagram in Figure 2. Thesezones include:— A primary burn zone equipped witha dry burn loop to minimise moistureduring combustion— A finishing zone with oxygen andtemperature control (no sharpexotherms or carbon breakthrough)

Octanizing reformeroptions

Staged investment and reformer technology improvement strategies are available forincreasing hydrogen production, cycle time and reliability. Options include revamps

to SR reformers and hybrid SR/CCR Dualformers, as well as new CCR unit investments

Bruno Domergue and Pierre-Yves le Goff AxensJay Ross Axens NA

REFINING

PPTTQQ Q1 2006w w w. e p t q . c o m

67

Recoverysystem

Recyclecompressor

Sep

rotara

Hydrogenrich gas

Reformate tostabilisation

Feed

Boostercompressor

1-R

2-R

3-R

RegenC-2Regenerator

Reactors and heaters

Figure 1 Axens CCR reforming process

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— An oxychlorination zone for metalsredispersion— A calcination zone to dry thecatalyst.

Coke burning is the principal functionof a catalyst regeneration system. It isessential that this step be carried out tocompletion. However, the coke burningstep is the primary contributor to threenegative factors concerning catalystperformance and life:— Metallic phase sintering, whichlessens catalyst performance; inparticular, stability— Partial dechlorination of the carrier,which reduces catalytic activity— Hydrothermal sintering of thecarrier, which decreases mechanicalstrength and ultimate catalyst life.

The hydrothermal sintering of thealumina carrier, which occurs duringregeneration and, in particular, duringcoke burning, results in a decrease of thespecific surface area of the catalyst. Theleading factors involved in carrier ageing

are the moisture level, temperature andcombustion time. It is therefore criticalthat the water content is kept as low aspossible in the combustion gases. Thisobservation has led to the incorporationof a dry burn loop in the RegenC-2regenerator to dry the recirculatingcombustion gas.

The benefits of a dry burn loop areshown in Figure 3, where catalystsurface area decay (carrier degradation)is plotted against a number of regenera-tion cycles for the same catalyst in threeregeneration systems:— Hot burn loop: recirculating burninggas is hot and wet — Cold burn loop: recirculating gas iswashed but not dried — Dry burn loop: recirculating gas iswashed and dried.

In normal operation, the metaldispersion is reconditioned in theoxychlorination zone. The dechlorina-tion that occurs in the coke burningsection is predominantly the result of

the moisture level in the burn zone.Accordingly, a reduction in the moisturecontent during combustion lowers thecatalyst dechlorination, which has threeadvantages: — Equipment required for chloridetreatment in the combustion effluents isreduced— Corrosion potential downstream ofthe combustion effluent treatment isreduced— Chloriding agent addition duringoxychlorination to compensate for thedechlorination during coke burning isreduced.

Overall, the dry burn loop RegenC-2regenerator affords several advantages:— Extends catalyst life: a significantincrease in catalyst life compared to thehot burn loop (>900 cycles has beendemonstrated)— Reduces catalyst attrition viacontrolled temperature and less severethermal cycling— Increases catalyst stability throughoptimisation of the oxychlorinationoperating parameters throughout thecatalyst life— Improves regenerator operationflexibility due to the separation of theburn and oxychlorination gas loops— Reduces downstream corrosion dueto better chloride retention andmanagement— Discharges of a clean vent gas; ie, nochloride-removal equipment is required.

CCR catalystsThe CR 400/700 and AR 500 catalystseries are formulated to meet the specificneeds of gasoline and aromaticsproduction respectively. They aresupplied in either a calcinated orreduced state.

The development of CR 401/AR 501follows and anticipates the trend forhigh-performance ultra-low-pressureoperation for new or existing units. CR401/AR 501 have been specificallydeveloped for reactor pressures of 3.5–7barg (50–90psig), while for higherpressures CR 405/AR 505 are preferred.The high-performance low-densitycatalysts CR 701 and 702 are favouredwhen reduced catalyst loading isrequired.

The combination of catalystproperties, regenerator design andcatalyst-transfer systems results in verylow catalyst attrition (<2% of theinventory per year, or <0.0015% ofcirculation). The consequence ofattrition is greater than the inconve-nience and expense of catalyst addition.As fines are produced and build up inthe unit, the pressure drop can increaseand catalyst circulation problems canarise. In some designs, this causes a“dump and screening” of the catalyst on

PPTTQQ Q1 2006

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Primaryburn

Spent catalyst

Finishingburn

Dry burnloop

Drycombustion gas

Air

Air

Chloridingagent plus water

Oxychlorination

Oxychlorinationcalcination gas

Regenerated catalyst

Calcination

Figure 2 RegenC-2 regeneration block flow

–60

–80

–40

–20

Base

eR

lavite

usfr

ecam

2g/

Number of regenerations

Unit BUnit A Unit CUnit D Unit E

Dry burn loop

Cold burn loop

Hot burn loop

Figure 3 Surface area decline vs regeneration cycles in commercial units

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a yearly or biannual basis, resulting inadded downtime to remove the finesand clean the reactor screens. With theside-by-side design, fines production isminimised and on-stream timemaximised.

The superior strength and stability ofthese catalysts has recently beendemonstrated in a third-party CCR unit.After change-out to CR 702, catalystattrition dropped by 50% (Figure 4),resulting in improved catalystcirculation and a reduction in catalystmake-up costs.

When the CR 702 catalyst wasintroduced into the unit, catalyststability was also improved and thechloride addition rate was reduced by afactor of four, thereby loweringoperating costs and fouling/corrosion ofthe downstream equipment.

Semi-regenerative reforming In conventional semi-regenerative (SR)reforming units, many reactor designsand operating conditions vary widelyfrom 10–30 barg (150–450psig). Theolder higher-pressure units exhibitrelatively low reformate and hydrogenyields, while modern units, operatingaround 14 barg (200psig) with improvedinternals and catalyst systems, canprovide reliable and excellentperformance. Modifications to SR units,hardware and catalyst can providesubstantial performance improvements.Some of the most significant changesinvolve the feed effluent exchangers andradial reactor performance improve-ments combined with a new generationof platinum-rhenium (PtRe) catalyst.These and other related modificationsincrease the reformer cycle length whileproviding incremental increases in theamount of hydrogen needed for ULSfuels production.

It is not unusual to find four, eight oreven 12 feed effluent exchangers in theSR reaction section (Figure 5). Thisdesign results in a high pressure dropand poor heat transfer, limitingoperation in two ways: the recyclecompressor pressure drop (P) is higherand the heat duty of the first heater ishigher. Replacement with a modern lowpressure drop, high-efficiency weldedplate exchanger can significantlyincrease unit throughput and decreasetotal pressure to improve yields.

Reactor internalsFixed-bed radial flow reactors are usedwhenever a low pressure drop is criticalto good performance, such as in fixed-bed reformers. It has been standardpractice in radial reactor design toeffectively waste the top 15% or so ofthe catalyst bed with a bafflearrangement to avoid reactants short-

circuiting the bed as it settles.Catalyst settling during the course of

the run generates a gap between the topof the bed and the cover plate. Were itnot for the shroud extending down intothe bed, the reactants would passpreferentially through the gap (Figure6). In addition, because of the highresidence time due to poor flowdynamics in the shroud volume, thecatalyst loaded at the shroud levelattains higher than average coke levels.The coke found in the shroud region isdifficult to burn during regeneration, socentre pipe grid damage is frequentlyobserved in the top of the bed.Expensive reforming catalyst andreactor volume are also wasted (unusedplatinum inventory).

In the early 1990s, a cost-effectiveway to recover the unused bed volumewas developed. The conventional metal

shroud was replaced with Axens’Texicap, a flexible “textile cap” flowguide that moulds to the shape of thetop of the bed. This was first used in1992 at a European refinery. The flowguide settles along with the bed, so thereis no need to design dead space, and theformerly dormant catalyst section isnow active. The reactor pressure drop isalso reduced, as the reactants now flowthrough a greater catalyst bed cross-section; ie, the reactor can accept10–15% additional feed.

Texicap is an engineered composite ofrefractory fibres and fillers containing noasbestos. It is impermeable andwithstands the normal hydrogen/hydrocarbon atmosphere as well as thesevere operating conditions of multipleregenerations encountered in reformers.Installation and removal are easy,requiring about one-tenth of the

PPTTQQ Q1 2006

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REFINING

0.05

0.000 TTime in operation, T

0.10

0.15

0.20

0.25

An

oitirtt,

RC

C fo

%

0.2

0.0

0.40

0.6

0.8

1.0

Cni e

dirolh

j%t

w ,noitce

Fines production

CR 702 catalystLower attritionBetter chloride retention

••

Chloride injection

Figure 4 Reduced fines production (attrition) with CR 702

Aircooler

Heater1

Heater2

Heater3

Unstabilisedreformate

Hydrogenrich gas

FeedBooster

compressor

Feed/effluentexchanger

Chargepump

R1- R

2-

3-R

eS

pr

otara

Reactors

Figure 5 Semi-regenerative reformer

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manpower and time typically needed toremove and replace a shroud and coverassembly. For a four-reactor reformerturnaround, this time can be reduced byat least 50 hours, thereby improving theon-stream time of the unit. To date,Texicap has been installed in over 70radial reactors. Improvements have beenseen in unit performance and economicsdue to better utilisation of the reactorvolume and shorter downtime forremoval and installation:— Cycle lengths are improved at thesame severity— Severity can be increased at constantcycle length— Platinum inventory can be reducedat same effective throughput— Coke burning is complete and safe— Centre pipe maintenance is reduced— Downtime for catalyst change-out issignificantly reduced.

Second-generation catalystRG 582 was the first commercial PtRepromoted catalyst. Providing maximumC5+ and hydrogen yields together withexcellent stability, it is used in over 70SR and cyclic reformers. RG 682 is thelatest high-performance PtRe promotedcatalyst. This catalyst is designed for SRreformer applications, but can also beapplied to cyclic reforming.

This optimised trimetallic catalystfeatures an “unbalanced” or “skewed”Re/Pt ratio (greater than one) as well asa third promoter metal. Adding

rhenium to a Pt/alumina catalystdramatically improves stability (cyclelength) by decreasing the rate of cokeformation and its toxic effect on catalystactivity.

The new formulation enablesexcellent results to be achieved withimprovements in yields, activity, stabilityand ease of regeneration, even at highercoke levels. The greater resistance andtolerance to coke have extended cyclelife by more than 35% over that of a“conventional” balanced bimetallicPt/Re catalyst. More than 20 loads of RG682 are currently in operation.Commercial feedback has confirmed RG682’s outstanding selectivity, activity,stability, regenerability and ability torecover after sulphur upsets.

The implementation of previouslydescribed unit and catalyst changes canresult in extended cycle length andincreased yields of reformate andhydrogen. In many cases, thesemodifications are able to meet theincreased hydrogen requirements ofnew clean fuels hydrotreating units.However, cycle length may still bean issue, as ULS demands leave noroom for off-spec material or losthydrogen production during catalystregeneration.

Semi-regenerative or CCR?When contemplating a new project orreplacing a SR reactor, considerationshould be given to a staged investment

PTQ Q1 2006

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AfterBefore

Gainedwith

texicap

Catalystdeadspace

Figure 6 Texicap radial reactor installation

Case 1 Case 2 Case 3 Transform.Phase 1 Phase 2

Process SR Octanizing SR OctanizingRON 96 100 96 100Reactor pressure, barg (psig) 14 (200) 3.5 (50) 14 (200) 7 (90)Yields, wt%

H2 2.4 3.4 2.4 3.2C5+ 84.3 89.1 84.3 87.9

Investment, million $ 22.2 31.8 23.5 Phase 1 + 6Op. cost, million $/yr 2.1 2.9 2.1 2.7Prod. revenue, million $/yr 11 25 11 22

Investment options (10 000bpsd)

Table 1

Page 5: Ptq q1 06 Oct Ani Zing Reformer Options

strategy. Modern SR units can providethe desired performance by using radialreactors that are designed to transforminto a CCR unit at a future date whenfunds are available or capacity andseverity requirements dictate. Providingfor a future transformation requiressome forethought and minimal pre-investment.

As an example, consider a referencecase: 10 000bpsd feed of Middle Easternnaphtha in a reformer designed toproduce 96 RON of reformate with aminimum cycle length of one year and ahydrogen delivery pressure of 21 barg(300psig). This can be accomplished in aSR unit operating at about 14 barg(200psig) or in an ultra-low-pressureCCR operating at about 3.5 barg(50psig). The CCR design also givesconsiderable flexibility on severity, suchthat a reference severity of 100 RON canbe considered.

The CCR has a substantial yieldadvantage, but a somewhat higher cost.An alternative approach would be toconsider a transformable design,whereby a SR unit is built with the abilityto be converted to a CCR at a later date.These three cases are summarised inTable 1.

In the transformable case, the SRradial reactors are elevated andconfigured with catalyst inlet and outletconnections for the future addition ofthe catalyst-transfer equipment andregenerator. To optimise performance,the pressure is reduced when the unit istransformed to a CCR. The hydrogenrecycle rate is also significantly loweredso that the recycle compressor can beretained, but to be able to deliver theproduct hydrogen at the same pressureanother stage of booster compression isrequired. The resulting unit is almost asefficient as the ultra-low-pressure CCR(Case 2). These changes are shown inFigures 7 and 8.

Commercial exampleSome years ago, a refiner in southernEurope was considering a new reformingunit to help with the production ofgasoline. The refinery was planning onexpanding and wanted the flexibility ofa future CCR unit. The unit was built asa three-reactor SR unit and operated at98 RON and 300psig.

Several years later, the unit capacitywas expanded by 50% with the additionof a fourth reactor and a slight reductionin pressure to improve yield selectivity.More recently, the need for more octanedue to mandatory FCC gasoline desul-phurisation presented an opportunity toimplement the transformation to CCR,which was originally anticipated with afurther reduction in pressure and anincrease in severity to 103 RON. The

Phase 2 transformation to CCR wasconducted during a scheduled refineryshutdown and required four weeks;retubing the furnaces was the limitingfactor.

The sequence of unit transformationis summarised in Table 2. With a little

forethought, a unit was designed thatcould be expanded by over 50% with anincrease in severity from 98–103 RONand minimal pre-investment. A similarstrategy can be considered if existingold SR reactors require mechanicalreplacement.

PPTTQQ Q1 2006

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Recyclecompressor

Sep

rotara

oceR

tnca

nite

dru

m

Hydrogenrich gas

Unstabilisedreformate

Feed

Boostercompressor

R-1 R-2

3-R

Reactors

o ceR

tnca

nite

dru

m

Hydrogenrich gas

Ustabilisedreformate

Recyclecompressor

H2

Sep

rotara

Feed

Equipment to be implemented or revamped

Boostercompressor

R-1

2-R

R-3

Regenerato

Catalyst circulation loop

Figure 7 Phase 1 SR

Figure 8 Phase 2 SR to CCR conversion

Phase 1 Phase 2 Phase 31979 1991 2000

Capacity, bpsd Base 1.5 x Base 1.6 x BaseRON 98 98 103Mode of operation SR SR CCRNumber of reactors 3 4 4Reactor pressure, barg (psig) 20 (300) 16 (240) 8 (120)Reformate yield, wt% 79.0 80.1 78.0

Phased construction industrial example

Table 2

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Hybrid designWhen considering an existing SR unitthat is not equipped to be transformedto CCR, it is still possible to capturesome of the benefits of a CCR design. Inthe mid-1980s, the Dualforming process

was developed and commercialised. Thisenables the revamping of a conven-tional reformer with the addition of anew moving-bed reactor and regenera-tion system to produce higher-octanereformate, plus increased hydrogen

production and yield selectivity at aminimum capital cost. Five Dualformersare currently in operation and others arebeing designed (Figure 9).

With Dualforming, the objective isto make maximum use of existingequipment, while improving reformateyield, hydrogen production and/or cyclelength compared to a SR unit. For anexisting three-reactor SR unit, thepotential benefits of adding a fourthreactor to increase throughput and/orcycle length are first evaluated. Then, aDualforming case is appraised to allowfor more severe operation. In manycases, significant improvement incatalytic reforming flexibility may berealised at less than 50% of the capitalinvestment costs of a new CCR.

It is well known that reducingoperating pressure in a catalyticreforming unit substantially improvesthe yield of reformate and hydrogen(especially hydrogen). It is also knownthat lower-pressure operations in fixed-bed units increase the formation of cokeon reforming catalyst and significantlyreduce cycle life. The Dualformingprocess addresses both the positive andnegative factors of lower operatingpressure.

A significant advantage of the processis the maximum use of existing reactorsection equipment in the SR catalyticreformer. The revamp includes theaddition of a new reactor that operateswith continuous catalyst circulation. Asshown in Figure 9, the new reactor andregenerator are integrated into theexisting reactor train of the conventionalreformer and operate at a pressure lowerthan the original unit and consistentwith Pt-Sn CCR catalysts — less thanabout 17 barg (250psig).

The reduction in unit pressure allowsfor the use of the more selective Pt-Sncatalyst system in the last reactor, butrequires careful evaluation of the recyclecompressor so that the unit severityprofile, pressure and hydrogen recycleare compatible with the cycle lengthand yield objectives. In many cases, thiswill lead to the installation of a low ΔP,high-efficiency feed/effluent heatexchanger to minimise the pressuredrop. Other major pieces of equipmentinvolved in the revamp include anadditional inter-heater for the newreactor, a booster compressor to exporthydrogen at the original design pressureand, of course, the regeneration system.

The configuration shown in Figure 9allows for the operating pressure to bereduced in the SR section of the unit.The amount of pressure reduction islimited primarily by the pressure dropthrough the unit and by the existingrecycle compressor. The SR section isthen operated at a lower severity and

Aircooler

HeaterH-1

HeaterH-2

HeaterH-3

Unstabilisedreformate

Hydrogenrich gas

FeedRecycle

compressor

New feed/effluentexchanger

Chargepump

R-1 R

-2

3-R

Newheater

H-4

Newreactor

R-4Reactors

Regenerator

eS

pr

otaraFigure 9 Dualforming flow diagram

8280

8486889092949698

100

Days on stream40 80 120 160 200 240 280

Typical RON of 6

320 3600

%tw ,

dleiy &

NO

R etamr

ofeR

7374757677787980

7071

72

h/t ,yticapa

C

RON Feed rateRef yieldRON-SR

Figure 10 Dualformer commercial data

Scheme:20 000bpd, 100 RON Existing SR unit Dualforming Octanizing CCRCycle length, month 6 12/cont. ContinuousYields, wt%

H2 1.7 2.4 3.1C5+ 76.3 81.9 87.4

Revamp investment, million $ Base unit +18 +40Cat & utilities, million $/yr 3.1 5.3 7.8Prod. revenue, million $/yr – 14.1 28.4

SR reformer revamp to Dualforming or full CCR

Table 3

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reaction temperature to satisfy cyclelength requirements, with the new CCRreactor operating at a higher severity tocomplete the reaction. In one example,the average reactor pressure of thereformer was reduced from 26 barg(375–220psig).

The overall result of the Dualformingprocess sees an improvement in bothreformate and hydrogen yields andoctane performance at a lower capitalcost than the CCR process. Acomparison of the operating conditionsand yields from an SR unit, a revamp toDualforming and a major revamp toCCR are presented in Table 3.

Data from the five commercialDualforming units operating since 1987have demonstrated reliable operationover the cycle length of the fixed-bedportion of the unit. Data from one unitis shown in Figure 10. The reformateoctane leaving the fixed-bed reactor (SR)and the final product octane are steadythroughout the one-year cycle, with aconstant octane boost of 6 RON pointsacross the reactor. Optimising the fixed-bed cycle length with the severity in theCCR Dualformer reactor is a keyparameter based upon commercialexperience.

The added reactor and regenerationsystem allow the new, final reactor tooperate continuously and at a higherseverity than the fixed-bed portion ofthe unit. But ultimately, a Dualformingunit will be limited by the fixed-bed SRsection of the unit, as these reactors stillrequire shutdown for regeneration.

In a variation on the Dualformingdesign, the new reactor-regeneratorsystem is located downstream from thefixed-bed reactors, separator and recycle

hydrogen loop. As a result, the newreactor can be operated at a very lowpressure, thereby bypassing theconstraint of the existing recyclecompressor. This configuration is calledDualforming Plus, which also is capableof processing the combined effluentfrom several fixed-bed units formaximum unit flexibility.

AdvancesAdvances in CCR reforming (Octanizing/Aromizing) using the latest catalysts (CR401, CR 702, AR 501) and incorporatingthe new RegenC-2 regeneratorsignificantly reduce CCR reformingoperating costs by lowering catalystdeactivation and attrition, as well aschloride consumption. The processprovides high on-stream unitavailability with maximum liquid yieldsand high co-production of hydrogen tosatisfy the reliability and hydrogenrequirements of new ultra-low-sulphurfuels hydrotreating units. Theseadvances are demonstrated by 14 newCCR unit references since 2004 and tenreferences in 2005 alone.

Some refiners have opted to invest intransformable units that operate as SRunits at a lower capital cost, but with theability to be converted to CCR operationlater to stage their capital investment.This option is particularly attractive iflarge unit expansion is planned in thefuture or much higher severity foraromatics production is envisaged.

Not all refiners have the option ofinvestment in new units and requireways to maximise the use of existingassets or staging investments. ExistingSR reforming units can benefit from thenew RG 682 catalyst and hardwaremodifications such as Texicap to betteruse the reactor volume and increasecycle length as well as reformate andhydrogen yields. For large increases inseverity and/or capacity, a provenhybrid Dualforming design using anadditional reactor with a CCR loop cancombine some of the attributes of a CCRsystem while maximising the reuse ofexisting SR equipment.

This article is based on a presentation fromthe 2005 Axens European Refining Seminar inVienna. Octanizing, Aromizing, Texicap,Dualforming and DualformingPlus are marksof Axens.

Bruno Domergue is product line manager,catalytic reforming and paraffinsisomerisation with Axens in Paris, France.Email: [email protected] Ross is technical manager with AxensNorth America in Princeton, New Jersey,USA. Email: [email protected] le Goff is technical managerwith Axens in Paris, France. Email: [email protected]

“Existing SR reforming unitscan benefit from the new RG 682 catalyst andhardware modifications such as Texicap to better use the reactor volume andincrease cycle length, as well as reformate andhydrogen yields”