18

ReformingThermal andCatalytic
Reforming means rearrangement of moleculeswithout much affecting the average molecular weight
of feed which is generally naphtha of gasoline boiling range. Reforming is carried out to produce high
quality (octane number) gasoline by heating with or without catalyst the naphtha. Low octane number
thermally cracked gasoline (is also a feed for reforming) is also subjected to reforming to improve its
quality(octanenumber).
Reformingcanbethermalorcatalyticasinthecaseofcracking.Catalystapartfromacceleratingthe
process also enhances the yield and quality (octtme number) of gasoline. The gasoline produced by
reforming is called reformed gasoline or reformate. Thermal reforming has been almost completely
replacedbycatalyticreforming.
Feed forreforming.Thefeed isgenerallynaphthaproduced duringstraightrundistillation ofcrude
oil, catalytic cracking and coking process. The best result is obtained with naphtha (produced during
straightrundistillation)havinghighnaphthenecontent.
Reforming products. Besides the main product i.e. reformate or reformed gasoline, reforming also
produceslighterhydrocarbons(gases),hydrogenandtracesofveryhighboilingmaterials.Thehydrogen
rich gaseous product is recycled'?th the naphtha feed. The reformed gasoline has a wider boiling range
thanthefeedanditsvOlatilityisincreased.
Reactionsincatalyticreforming.Since,aromaticshavethehighestoctanenumberandisoparaffins
are next to them, most of the desirable reactions during reforming tend to produce high octane number
hydrocarbons from lower ones. Octane number mcreases in the order paraffin +olefin + naphthene +
isoparaffin +aromatic.
The main reaction in the reforming process is dehydrogenation of naphthene to produce aromatics.
Other reactions occurring during reforming are dehydrocyclisation of paraffins, isomerisation,
hydrocracking,dehydroisomerisation,dehydrogenationetc.
Thevariousreformingreactionsareillustratedbelow.
REACTIONS
Thougholetinshavehigheroctanenumberthancorrespondingnparaftins,stillthisreactionis
undesirablebecauseloweroletinspolymerisetoproducegummymaterialswhichisunwanted.
Thermalreforming.This is carried outinabsence of catalystand issimilarto hightemperature,low
pressurethermalcracking.Feedisusuallynaphthaandtheproductsaremainlygas(1314%)andgasoline
(7580%) of octane number 8186 rest being polymer (unwanted gum) and losses. A flowsheet for
thermalreformingisgiveninFig.18.1.
CatalyticReforming.Reforminginthepresenceofacatalystiscalledcatalyticreforming.Twotypes
ofcatalystareusedviz.nonpreciousmetaloxidetype(e.g.molybednaorchromiasupportedonalumina
base)andpreciousmetaloxidetype(e.g.platinumonasilicaaluminaoraluminabase.Platinumismore
active and selective catalyst, however, it is easily poisoned by compounds containing sulphur, nitrogen,
arsenicetc.andneedspretreatmentofthefeedfortheremovaloftheseimpurities.Catalystmaybeinthe
formofpowder,beadorpellet.
REACTIONS
Fig.18.1.ThermalReforming.
Fixed bed, moving bed and fluidised bed processes are in use. Various commercial catalytic
reforming processes in use in oil refineries are Platforming, Catforming, Hydroforming, Fluidised
HydroformingandThermoferCatalyticReforming(TCR).
Reformingisnormallyaoncethroughprocess.Thereactorconditionsarenormallyinthe
range ofT=450550CandP=1545kg/cm2.Fluidisedbedandmovingbedfrocessesarerun
in high temperature ranges at about 15 kglcm2. High pressure upto 45 kg/cm are for the fixed bed
process.
Effect of variables in catalytic reforming. Catalytic reforming is carried out over a wide range of
reaction conditions, the most important of which is pressure. Other variables are recycle gas rate,
temperature,spacevelocityandthecatalystparticlesize.
Effect of Temperature. Temperature in catalytic reforming is in the range of 450550C. If
temperature is less than 450C then catalyst is inactive whereas if temperature exceeds 550C then
hydrocracking predominates. Cyclisation reaction occurs at 470490C whereas isomerisation reaction
occurs at 4050C above that for cyclisation. Dehydrogenation reaction occurs upto 500550C. At 700
800C,olefinformationstarts.
Effect of Pressure. Dehydrogenation of naphthene which is desirable in reforming reaction and is
favoured by low pressure and high temperature however, this condition also favours the formation of
cokewhichdeactivatesthecatalyst.Depositionofcokecanbereducedbyoperatinginanatmosphereof
hydrogenthe higherthepressureof hydrogen,thesloweristhecoke deposition.Increasingthepressure
of hydrogen does not severely retards the dehydrogenation ofnaphthenes which produce high octane
numberaromatics.Hence,catalyticreformingiscarriedoutundersubstantialpressurewiththehydrogen
productrecycledtothereactionzone.Aspressureandhydrogenrecycleratioisincreased,gasolineyield
(at a given octane level) reduce~. Lower pressure are permissible with lower boiling feed which has a
lowertendencytoformcoke.
Effect of catalyst particlesize. With very active catalysts, theinterior portion is ineffective because
reactionoccursbeforethereactantscanpenetratetothecore.Inthissituation,theactivityofthecatalyst
increasesastheparticlesize,isreduced.Withplatinumcatalystthe
effectissubstantial.Indecidingtheparticlesize,catalystactivityistobebalancedagainst
pressuredropthroughthecatalystbed. .
Effect of trace materials in feed. High sulphur in feed inhibits dehydrogenation and promotes
hydrocracking over platinum catalyst thereby reducing the yield of liquid products. High sulphur
concentrationalsoacceleratesdeactivationofcatalystespeciallyatlowhydrogenpressure.
Presence of nitrogen in feed to platinum catalyst reforming unit inhibits dehydrocyclisation of
paraffinandhydrocracking.
Reformed 9osoline
High
pressurevesseI
Halides promote the activity of a platinum on alumina catalyst and its some concentration in the
catalyst is necessary for good operation. However, if halide concentration becomes too high, excessive
hydrocrackingresults.Halidesarenotnecessarywhensilicaaluminabaseis
usedforthecatalyst.
Metalssuchasleadandarsenicpoisonthecatalyst.Tetraethyllead isalsoacatalystpoison. Yieldin
catalyticreformingdependsuponthechargestock,catalystandoperatingcondi
tions.Iffeed has1525%naphthenesthenthereformate willhave1118%benzene,1820%tolueneand
2224%xylene.Withincreaseinseverityofoperation,yieldincreasesatthecost
ofquality (i.e.octanenumberreduces).
Inatypicalcatalyticreformingofnaphthaofboilingrange85180C,theyieldwasasfollow:
gasolinecomponent =84% unsaturates =4%
hydrogen =11% losses =1%
Commercialcatalyticreformingprocess
nonregenerativeprocesse.g. plat:'rming
Fixedbedprocess
regenerativeprocesse.g. bydroforming
ThermOfercatalyticreforming(TCR)processMovingbedprocess
Hyperformingprocess
FluidisedbedprocessFluidisedhydroformingprocess
Someoftheimportantcommercialprocessesaredescribedbelow.
NonRegenerativeFixedBedPlatformingProcess
One ofthe mostwidelyusedcatalyticreformingprocessisthenonregenerativeplatformingprocess
which employs normally a three to five reactor system. The catalyst is platinum and halogen (normally
platinicchloride) onaluminabase.Thecatalyst is not regenerated insitubut isreplaced when operating
temperaturecan notbe increased furtherto maintainthe octane number of gasolineproduced. Acatalyst
lifeof200barrels(i.e.7000imperialgallon)offeedperpoundofcatalysthasbeenreported.
Preheated naphtha withan endpointof190Cis mixed with hydrogenrichrecyclegasandpartially
preheated by indirect heat. Final preheat is obtained in a preheat furnace and the feed to reactor is at a
temperature between 455C to 530C. Pressures of 3347 kglcm2 is used. Reactor space velocity varies
from 1.5 to 3 volume of feed per hour per volume of catalyst. Hydrogen rich recycle gas is dehydrated
andfreedfromhydrogensulphidebyscrubbingwithmonoethanolamine.
Productafterpassingthroughthewatercooledcondensorsentersahighpressureseparatorwherethe
unstabilised reformate is recovered. The major portion of the gas is recycled while the tail gas is sent to
the absorber system for removal of C. and higher hydrocarbons. The two most important reactions are
aromatisation (endothermic) which takes place mainly in the first reactor, and the hydrocracking
(exothermic)whichtakesplaceinthelaterreactors.
Gasolineyieldanditsoctanenumbervarieswiththereformingseverity (i.e.temperature
andpressuremainly).Reformingofasampleofnaphthagavethefollowingresult.
Lowseverity gasolineyield =91.5%andoctanenumber=85(unleaded)
Highseverity gasolineyield=85.2%andoctanenumber=95(unleaded)
'Catforming' is a similar reforming
process which permits occasional
regeneration of catalyst in situ
intervals between regeneration varying
fromseveralmonthstooneyear.
A flowsheet of platforming process
isgiveninFig.18.2
Regenerative Fixed Bed Bydroforming
Process
This process uses a catalyst
containing 810% of molybedna on an
alumina support. Temperatures of 480
540C and pressures from 14 to 20
kg/cm2areused.Thecatalystbeadsare
regeneratedafter4to8hoursoperation.
Both upflow and downflow
regeneration is done to hold the
temperature between 565 to 595C. A
high partial pressure of hydrogen is
maintained during hydroforming
processbyrecyclingthe
hydrogen produced by the dehydrogenation of naphthene and cyclisation of paraffins. Desulphurisation
alsotakesplace,mostofthesulphurpresentbeingremovedashydrogensulphide.Gasolineyieldismore
than75%withanoctanenumberof8085(unleaded).
ThermoferCatalyticReforming(TCR)MovingBedProcess
.
tohopper I
Regenerators
Depressurisingleg
Catalystconv~yersystem
Fig.18.3.FlowsbeetofTeRmovingBedProcess.
Reoctor
TCRprocessusesasinglereactoroperatingat12kg/cm2and510540C.A
regeneratingkilnoperatingatatmosphericpressureand540570CisusedtoreIn............... ~ wIre
fromthedeactivatedcatalyst.Catalystisusedintheformofbeadsandcontainsabout32%
chromia on alumina base. Since, it is fairly resistant to poisons in feedstock, no pretreating of feed is
necessary.
After being heated separately, thefeedstock and recycle stream are combined and enter the reartor.
Reactor space velocity is maintained at 0.7 volume oil per hour per volume catalyst. The catalyst to oil
ratio(volume)is0.3.Theproductsarecooledandthensenttofractionatorwhererecyclegasstreamand
liquid reformate are separated. Catalyst is injected from top hopper and after moving down the reactor
goestoadepressurisinglegandthentothe
regenerator.About25tonslhr.ofcatalystcirculatesinareformerdesignedfor15000 barrelsof
naphtha/day.Normalcatalystattritionrateisabout0.2lb/barreloffeed.
AflowsheetofTCRmovingbedprocessisgiveninFig.18.3
FluidisedBedHydroformingProcess
Inthisprocess,apowderedcatalystcontaining10%ofmolybednaand90%aluminaiscirculated
betweenareactorandaregeneratorbythefluidisedtechnique.Fluidhydroformersoperateat480Cand
1420kg/cm2(sameas
fixed bed hydroforming unit). To maintain this reaction
temperature while supplying the endothermic heat of
reaction, the recycle gas is heated to 650C. The feed
temperature is kept below 540C to minimise thermal
cracking.Fluidisationeqablesthetemperaturetobecon
trolled in the reactor very closely preventing the
excessive reforming with production of gases that take
place in fixed bed units. Similarly, regeneration
temperature is more closely controlled by the use of
cooling coils in the regeneration unit. Catalyst
circulation rate is about 1 kg catalyst per kg naphtha
charge. A gasoline yield of about 80% with octane
number of 95 (unleaded) can be obtained by this
process.
A flowsheet of fluidised bed hydroforming unit is
giveninFig.18.4.
Cotalysthopper.