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Reformer feed, Reforming reactor design, Continuous and semiregenerative process.
FEED[12]
Reformer feed, Reforming reactor design, Continuous and semi regenerative process.Naphtha from thermal & catalytic crackers can also be used.
Tab:5.3
Characteristic of Typical Reformer FeedsPARAMETERS PARAFFINIC NAPHTHENIC
RONC 50 66
P/N/A(%vol) 66.8 /21.8/11.4 29.3/61.85/8.85
ASTM Distillation
IBP 92 88
30 115 115
50 123 123
70 133 132
90 147 145
95 152 150
155 161
Chemical Reactions
Two types of reaction involved in the octanizing process:Desirable Reaction which lead to higer octane number and to higher purity hydrogenproduction.They are the reaction to promote.Adverse Reaction which lead to decrease of octane no and a decrease in hydrogenpurity.They are the reaction to minimize.
RON:Research Octane NumberMON:Motor Octane Number
Tab:5.4 [12,1921]
RON MON
Cyclohexane 83 77.2
MethlyCyclohexane 74.8 71.1
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1.3 Dimethlycyclohexane 71.7 71
Benzene 114.8 100
Toluene 120 103.5
mXylene 117.5 115 Desirable reactions with H2 production[15,12,1721]
Naphthenes dehydrogenetionNaphthenic compound dehydrogeneted into aromatic with production of 3 moles of H2per mole of napthene.Promoted by the metallic function.Highly Endothermic.Thermodynamically favored by high temperature,low pressure and high number ofcarbons.Kinetically favored by high temperature ,high no. of carbons;not affected by hydrogenspartial pressure.At the selecting operating conditions,reaction is very fast and almost total.
Desirable reactions
Paraffin's DehydrocyclizationMultiple step reaction.Promoted by both acidic and metallic function.Kinetically favored by high temperature and low temperature.Dehydrogenation step become easier as paraffin molecular weight increases but iscompeted by Hydro cracking.At the selected operating condition much lower rate than that of Dehydrogenetionm.
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Linear Paraffin IsomerizationPromoted by acidic function.Slightly Exothermic.Fast.Thermodynamically dependant on temperature:pressure has no effect.Kinetically favored by high temperature:not effected by the hydrogen partial pressure.
Naphthenes IsomerizationDesirable reaction because the subsequent dehydrogenation of the alkylcyclohexane intoan aromatic.Difficulty of ring rearrangement and high risk of ring opening (paraffin formation).At the selected operating condition.theoretically low rate but subsequentdehydrogenation shift the reaction towards the desired direction.Slightly endothermic.Easier reaction for higher carbon number.
Naphthenes isomerisation
Tab:5.5
RON MON
Ethylcyclopetane 67.2 61.2
MethlyCyclohexane 74.8 71.1
Toluene 120 103.5
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Adverse reactions[12,1522]
HydrocrakingHydrocracking effect either paraffin and olefins.Promoted by both acidic and metallic functions.Favored by high temperature and high pressure.Exothermic risk of runaway reaction.At the selected operating condition,hydro cracking reaction could be complete but islimited by kinetics.
Adverse reaction
Consequences of CrackingDecreases of paraffins and increases of aromatics proportion(i.e increases in octane)inthe reformate and a loss of reformate yield.Decreases in hydrogen production(cracking reaction consuming hydrogen).Increase of light end production and low molecular weight paraffins.
HydrogenolysisPromoted by metallic function.Favored by high temperature and high pressure.Exothermic(risk of runaway reaction).
Hydrodealkylation
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Breakage of the branched radicial of an aromatic ring.Promoted by metallic function.Favored by high temperature and low temperature.Consumes hydrogen and produces methane.But at selected operating condition and with the selected catalyst,this reaction is notsignificant.
AlkylationAdditioh of an olifen molecule on an aromatic ring.Promoted by metallic function.Lead to heavier molecules which may increase the end point of the product.High tendency to form coke must be avoided.
TransAlkylation(alkyl disproportionation)Dismutation of 2 toulence ring to produce benzene and xylene.Promoted by metallic function.Favored by very serve condition of pressure and temperature.At the selected operated conditions,and with the selected catalyst this reaction isnegligible.
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CokingResult from complex group of reaction.Deatailed machanism not fully known yet.Linked to heavy unsaturated products(polynuclear aromatics) and heavy olifins traces ordiolefins present in the feed or in CCR reaction.Coke deposit reduces active contact area and reduces catalyst activity.Favoured by low pressure:In octanizing operating conditions necessity of a continousregeneration to maintain a low level of coke.
Chemical Reaction[12,2426] All these reaction occur in series and parallel to each other producing a complicated reactionscheme.In an effort to simplify the scheme according to the reaction rates the main reaction takeplace in the following order:
Tab:5.6
1 1st Reactor Dehydrogenetion/Isomerization
2 2nd and 3rd Reactor Dehydrogenetion/Isomerization/Crackingand Dehydrocyclization.
3 4th Reactor Cracking/Dehydrocyclization.
The catalyst distribution is:R1= 10%R2= 15%R3= 25%R4= 50%
Tab:5.7
Reactions Heat ofReaction(1)KCAL/MOLE
RelativeRate(2)Approx
Naphthenes dehydrogenetion 50 30
Paraffin dehydrocyclization 60 1 base
Isomerization:paraffins +23
Naphthenes +4
Cracking +10 0.5
Heat of reaction <0 = endothermic reactionFor pressure below 15kg/cm2
Conventional unit[12,1525]
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Fig 5.4 Conventional unit
Fig 5.5
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Continuous catalytic regenerative reforming
Fig 5.6 Continuous catalytic regenerative reforming
Continuous catalytic regenerative reforming
Fig 5.7 Continuous catalytic regenerative reforming
Objective of regenerative unit
Recover initial catalyst activity
Coke Removal 2 Burning ZonesMetal Redistribution & chloride adjustment OxychlorinationCatalyst drying calcination
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Fig 5.8 A typical FCC flow sheet to regenerate catalyst from spent catalyst
(Regeneration process)
Catalyst regenerator
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Fig 5.9 Catalyst regenerator
Process variables[12,2229]
PressureTemperatureSpace velocityHydrozen partial pressure(H2/HC)Quality of the feedOperating parameters summary.
Process variables
Each of them can be fixed by operator within the operating range of the equipmentindependently from the others.For one set of independent variable for same feed characterstics there is only oneperformance of the unit i.e one set of value for:
Product yieldsProduct quality(octane)Catalyst stability(coke make)
Pressure is the basic variable because of its inherent effect on reaction rates.Effect of pressure on reactions
Low pressure enhance hydrogen production by these reactions:dehydrogenationsdehydrocyclisation coking.Cracking rate reduces.The lower the pressure the higher the yields of reformate and hydrogen for a givenoctane number.But it developer high coking rate(compensated by continousregeneration).
Average catalyst pressure used is close to last reactor inlet pressure.During transient condition(startup,shutdown,upset)it is recommended to increase thepressure to lower coke formation.Limit of operation action.
Pressure rise limited by equipments design pressure.Pressure lowering limited by recycle compressor design for power and intake volume.
Effect of temperature
Most important and used operating parameter is space velocity.Catalyst activity is directly related to reactor temperature.By simply raising or loweringreactor inlet temperature operator can raise or lower product quality and yield.It is commonly accepted to consider the weight average inlet temperature(WAIT).
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where Ti 1,Ti 2 .......are inlet tempreature of reactor (wt catalyst of R1)....... are weight of catalyst in reactor
An increase of temperature (i.e WAIT) has the following effect.Increase octane.Decrease of yield (of C5+Fraction).Decrease of H2 purity.Increase of coke deposit.
A slight increase of temperature(WAIT) through the life of the catalyst make up for thisactivity loss.Larger and temporary changes in temperature required.
To change octaneat contant feed quality and quantity.To change feed quantity and still maintain octaneTo change feed quality and still maintain octane
Space velocity
Linked to resident time of feed in the reactor and effect the kinetics of the reforming reaction.
Operator must careful in mind that each time liquid feed rate is changed a temperaturecorrection must be applied if octane is to be maintained.Important Recommendation
Always decrease reactor inlet temperature first and decrease feed flow rate afterward.Always increase feed flow rate first and increase reactor inlet temperature afterward.
Effect of Hydrogen to Hydrocarbon Ratio
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where R is the recycle flow in Kg l h (or lb l h)M is the recycle gas molecular weightF is the feed rate in kg l h(or lb l h)m is the feed molecular weightY vol fraction of H2in the recycle gas
The recycle gas MW is obtained by chromatographic analysis as well as the H2 vol fraction(Y)The feed MW is obtained by chromatographic analysis or by correlation from its distillationrange and specific gravity.Operator can change H2/Hc ratio by lowering or increassing the recycle compressor flow.For a given unit the amount of recycle is limited by the recycle compressorcharacterstics(power suction flow).The H2/Hc ratio has no obvious impact on the product quality or yield.But a high H2/Hc ratio reduces the coke build up.It is stirctly recommended to operate with a H2/Hc ratio equal to (or higher than) designfigure.
Effect of feed quality chemical composition
Characterization of the Feedstocks:0.85 N + AWith a higher 0.85 N + A .
The same octane content will be obtained at a lower severity(temperature)and theproduct yield will be higher.Or the same severity temperature the octane content will be higher.The endothermic reaction heat increases and the feed flow rate will be limited by theheater design duty.
With a higher 0.85 N + A .Higher paraffin and napthanic content obtained.The hydrogen purity of the recycle gasdecrease and operation will be limited by the recycle compressor capacity.
ImpuritiesTemporary or permanent reduction of catalyst activity by poisons contained in the feed.
Feed quality
The feed distillation range is generally as follows:IBP (Initial Boling Point) 70100ocEP(End Boiling Point)150180oc
Light fraction:Cyclization of c6 more difficult than that of C7C8.The lighter the feed,the higher the requiredseverity for a given octane.Heavy Fraction:High naphthenic and aromatic content.Lower severity to obtain good yield.But polycycliccompounds which favor coke deposit.
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EP higher than 180oc are generally not recommended.
Operating parameters summary
Here after the theoretical effect on the unit performance of each independent processesvariable taken separately:
catalyst[2130]
Reforming of catalyst are bimetallic catalyst consisting of platinum plus promoters on aluminasupport, rhenium being essentially used.The main features of these catalyst are:
High purity alumina supportHigh mechanical resistance.Platinum associated with Rhenium high stability and selectivity.High regenerability.
The combination of these qualities give the following advantage:High Reformate Yield.High Hydrogen yield.High on stream Factor.Low Catalyst Inventory.
The main characterstics of catalyst other than it physical and mechanical properties are:[12,2532]
The Activity
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Catalyst increase the rate of desired reaction.Is measured in term of temperature
The SelectivityCatalyst ability to favor desirable reaction.Practicle measured by the C5 + Reformate and hydrogen yield.
The StabilityChange of catalyst performance(activity,selectivity) with time.Caused chiefly by coke deposit and traces of metal in feed.Measured by the amount of feed treated per unit weight of catalyst.C5 + Wt reformateyield is also an indirect measure of the stability.
Platinum (pt) plus other promoter(s) impreganted on to gamma alumina containing around1% wt chloride provide to acidity.Since 1967 bimetallic catalysts have been widely used.The second metal come from the group of metal like:
Rehinium(Re)Tin(sn)Iridium(Ir)Germanium(Ge)
Selection of metal
Depend on what you want from the catalyst:The ObjectivesStability and Cycle lifeSelectivity towards
Hydrogen H2Liquid Reformate(C5 + Reformate)Benzene yield in C5 + Reformate
Normal causes foa catalyst ageing/deactivationMental sintering
TemperatureMetallic PhasePresence of Chloride
Deposition of coke on metal and acid sites.Coking effect can be split.Degree of poisoning of deposited coke.Relative coking rate
The relative rate of coking is proportional to the hydrogenation function of the catalyst this isdependant on the metallic phase.
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Fig 5.10
selectivity[14,1222]
Desired yields are:HydrogenC5 + ReformateLow benzene
BenzeneYield can be minimised by prefactionnating the precursors (MCP,CH,nC6P)which arepresent in the fraction boiling between 70 to 85oC.Benzene is also produced by the hydro alkylation of alkyl benzenes.
Loss of desired yield is caused by crackingHydrocracking involving the metal plus acid sites.Hydrogenolysis involving the metal in the presence of hydrogen.
Catalytic Reforming
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Types of Catalytic Reformers[14,2534]
Steam reforming Catalyst regenerated insitu during shutdowns(624 months)CCR
Continuous Catalyst Regeneration.Insitu regeneration of part catalyst in a special regenerator.Continous addition of regenerated catalyst.
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Fig 5.11 A typical FCC flow sheet integrated with CDU, HDSD, VRDS, FCC to generate
different hydrocarbons from crude oil
Tab 5.8
RON & MON OF VARIOUS MOTOR FUELSTOCKS
Stock RON MON
Butane 95 92
Isopentane 92 89
Medium pressure reformate 94 85
Low pressure reformate 99 88
Heavy reformate 113 102
FCC gasoline 91 80
Alkylate 95 92
Isomerate 85 82
MTBE 115 99
Important Properties of FCC catalysts
Surface Area /Pore Size DistributionZeolite AreaMatrix Area
Pore VolumeCrystallinity
Unit Cell SizeSiliconAlumina ratio
Particle Size Distribution and Average particle SizeAttrition ResistanceThermal properties/ Hydrothermal propertiesMetal Content
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DensityCarbon and Sulphur ContentAcidity
Surface Area / Zeolite to Matrix ratio, Pore size distribution
ScopeMeasurement of SA, Z/M ratio and Pore size distribution of fresh/equilibrium FCCcatalysts/additives, zeolite, clay, alumina, etc.
PrincipleNitrogen at various pressures are adsorbed at liquid nitrogen temperature on thesamples and isotherms are generated.With the help of BET, BJH, TPlot etc., the abovementioned properties are measured.
InstrumentsFlowsorb2300, ASAP2010 of M/s Micromeritics,USA.
Typical range of SA for FCC catalysts 80300 m2/g.
Implications of SA
Surface Area (Fresh=175300, Ecat: 80150).Indirect measurement of activity and stability of the catalysts.Z/M ratio gives information about SA of zeolites (small pores of <20 Ao)and SA ofmatrix,(large pores>20 Ao).
Matrix area does not tell whether the matrix is active or nonactive.Loss of SA due toHydrothermal deactivation (zeolite destruction).Thermal deactivation (high regn. Temp.).Increased metal deposition on catalyst.Reduced Fresh catalyst addition rate.SA of 10 units can decrease the MAT activity by about 25 units.
Pore Volume by Water Titration
Scope: Measurement of Pore volume of Fresh and equilibrium catalysts.Principle: Catalyst is titrated by water until the fluidity of the sample is destroyed. Porevolume is calculated as volume of water titrated over weight of catalyst.Procedure: Sample calcined to remove carbon and moisture.Titrated with distilled water orDM water.Typical range: 0.150.45 cc/g Simple method, PV measurement can be done at Refinery
Pore Volume[1921]
Indications/Directions: Generally, higher pore volume in fresh catalyst means higherlevels of active matrix components.Decrease in pore volume in ecat means
Thermal deactivation.Hydrothermal deactivation of catalyst has little effect on pore volume.Changes in Unit operation .May indicate damage in the regenerator air grid/ catalyst distributor.
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XRAY Diffraction (XRD) Analysiss[1921,3336]
ScopeTo identify and quantify crystalline phase, to detect impurities, to measure crystallitesize, UCS and Silicaalumina ratio.
PrincipleXray patterns of test and standard samples are compared. Integrated intensities of thepeaks provide quantitative data.
InstrumentsRigaku, Japan XRD equipment.
Typical RangeZeolite in FCC catalyst from 540%; Fresh catalyst: 1540% E cat: 5 15 %.
UCS of Y Zeolite[1921,3336]
It is a measure of aluminium sites or the total potential acidity per cell.UCS is a indicator ofzeolite acidity. As the UCS decreases, acid sites become further apart since Al4+ion is biggerthan Si4+ion.SiO2/Al2O3 mol ratio =2, UCS=25 Ao;SiO2/Al2O3 mol ratio =15, UCS=24.4 Ao
Lower UCS means fewer active sites per unit cell.The fewer acid sites are further apart andtherefore inhibit hydrogen transfer reactions,which in turn increases gasoline octane as wellas production of C3 and lighter components.
PSD by Micromesh[1921,3336]
ScopeDetermination of Particle size and average particle size of FCC catalysts in the range of20150 microns.
PrincipleDry sieving procedure for determination of particle size in FCC catalysts by means ofcalibrated sieves of uniform and precise square opening.
ProcedureSample placed on top sieve, set shaken for specified time. Each sieve is weighed.
InstrumentRobot shifter RPS 75,Japan.
Typical Range
APS= 80 microns
Significance of PSD
PSD is an indicator of fluidisation properties of catalyst. 040 micron particles (520 wt%)improves the fluidisation.PSD is a function of cyclone performance, catalyst properties, catalyst makeup rate and unitoperating conditions.
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Case1: A decrease in the percentage of smaller particles (fines) possibly due to (a)deteriorating cyclone performance. (b)Reduced Catalyst attrition (c) Lower fines in the freshcatalyst.Case2: An increase in fines may indicate increased catalyst attrition possibly due to (a)changes in the fresh catalyst composition, (b) increased fines in the fresh catalyst (c)internal damage such as air distributor or slide valve.
Attrition Resistance[1921,3336]
ScopeTo measure ability of the catalyst to maintain integrity in the FCC system.
PrincipleCalcined catalyst microspheres are subjected to high velocity air jet.Catalyst fines areremoved from the attrition zones and weighed.Attrited catalyst is expressed as weightpercentage and termed as Attrition Index (AI).Higher the index lower is the attritionresistance.
InstrumentIn house fabricated.
Typical RangeAI of FCC catalyst 515%.
Increased attrition possibly due toProblem in the regenerator air grid.Large amounts steam to the regenerator/regenerated catalyst line.Excessive velocities (>300 FPS) in the feed nozzle can also cause attrition.Problem in the catalyst.
Apparent Bulk Density
ScopeApparent Bulk density (ABD) of fresh, equilibrium FCC catalyst having size less than 150microns.
PrincipleCalcined catalyst sieved and taken into cylinder kept under given vibration to increasethe packing efficiency, mass/unit volume is calculated to get ABD.
InstrumentsBulk density meter, Model 1H 2000, Seishin, Japan.
Typical Range0.7 0.9 g /CC.
Significance of ABD[1921,3336]
ABD is a also function of catalyst composition, manufacturing process and other physicalproperties such PV and PSD. Generally does not change unless the catalyst type changes.Normally ABD of Ecat is higher than the fresh catalyst due to thermal & hydrothermalchanges in the pore structure that occur in the unit and also due to catalyst loss.If we compare one catalyst with other, slightly higher ABD catalyst can increase the pressuredrop across the slide value and improve the catalyst circulation.High ABD (>1.0) can restrict fluidisation.Low ABD (<0.6) indicates A) Change in Catalyst B) Fines loss.
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Hydrothermal treatment of FCC Catalyst and additives[13,1921,3336]
ScopeFresh catalysts can be hydrothermally deactivated to simulate equilibrium catalysts.
PrincipleHydrothermal deactivation of fresh FCC catalysts is done at 788 oC for 3 hours at 100%steam whereas 750 oC for ZSM5 additive.
InstrumentsXytel and In house fabricated.
Significance of Metal Analysis
Alumina (Al2O3) content and Rare earth content is determined by catalystformulations.Changes in Alumina/ Rare earth content can be used to track catalyst changeout.Unexpected change indicate a change in catalyst formulations.The alumina content (2555%)indicate the inactive alumina and active alumina i.e. Aluminafrom clay, binder and zeolite.CO Promoter additive and SOx additives.The Sodium (Na) in the ECat is the sum of sodium added from the feed and sodium in thefresh catalyst. Severe problem if the Na >>0.5%; Lower in unit conversion &loss in OctaneNumber. A Increase in Na level of 0.1 unit can decrease MAT conversion by 3 units.Ni, V, Fe & Cu has the gas making tendencies of the catalyst, when deposited on FCCcatalysts.These metals originate from the FCC feed.
Carbon on FCC Catalyst[1421,3336]
ScopeTo measure percent Carbon content of regenerated or spend catalyst.
PrincipleCarbon is determined by combustion in a stream of dry oxygen and measuring carbondioxide by IR analyser.
InstrumentsLebold Heraus,Germany;Analysis time: >1 minute Carbon range from 0.0016 wt%.
Carbon level on the Ecat is the indicator of the regenerator effectiveness.Carbon on the catalyst:For complete combustion mode: 0.05% wt.For partial combustion mode: 0.1 or higher.
Contents
Refining Process and Catalysts.Fluid Cracking Catalyst (FCC).FCC additives.Reforming Catalyst.Catalyst Characterization.R & D & Commercialization Status in India.Conclusion.
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Catalyst Changeover
FCC Daily charge for replenishment, reactor regenerator cycle.Hydrocracking total charge, regeneration every 23 yrs.Reforming total charge, regeneration every 3 or more yrs.
Wide Range of Catalysts[1421,3336]
All units do not use same catalyst.Requirement of each unit are different in terms of catalyst requirement for different setupreaction scheme.Custom catalyst need of the day.
Catalyst & Additive Sourcing – Needs Consideration[1121,3336]
India is totally dependant of overseas supply.R & D have acquired many patents for catalys and additive formulations as well asmanufacturing process.Since Large amount of catalyst is required for a plant trial, decent size manufacturing facilityis to be created at first.Most of the refining catalysts are imported.Catalyst consumption is increasing.No major manufacturing facilities in the country.Research and development confined to isolated pockets.Urgent need to bridge gaps in scaleup and commercial activities.
Catalyst & Additive Sourcing – Needs Consideration
Excellent Knowledge base.Laboratory stage developments.Large gap between laboratory to plant.
Tab 5.9
Olefin yield comparison off Indmax with FCC &DCC
Process FCC DCC INDMAX
Yield,Wt%
Ethylene 5.1 3.1
Propylene 3.6 17.4 23.2
Isobutylene 1.2 4.8 10.0
Total butylene 11.0 18.9
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Gaps to be bridged for catalyst breakthrough
Rigorous evaluation under simulated conditions in association with user.Manufacturing Facilityto solve problems of
catalyst manufacture.scaleup.
Willingness to take risk by refineries.
References
1. Rao, B.K.B.(1990). Modern Petroleum Refining Processes (2nd Edition Ed.) Oxford & IBHPublishers. ISBN 8120404815.
2. James H. Gary and Glenn E. Handwerk (2001). Petroleum Refining: Technology andEconomics (4th ed.). CRC Press. ISBN 0824704827.
3. Mohanty, P., Pant, K.K., Parikh, J., Sharma, D.K. (2011) Fuel Process. Technol. 92, 600 608.
4. Mohanty, P., Pant, K.K., Naik, S. N., Das, L. M., and Vasudevan, P. (2011) ‘Fuel productionfrom biomass: Indian perspective for pyrolysis oil, Journal of Scientific & Industrial Research70,668674.
5. James. G. Speight (2006). The Chemistry and Technology of Petroleum (4th ed.). CRC Press.ISBN 0849390672.
6. Patel, M., Pant,K. K., Mohanty, P. (2011) Renewable hydrogen generation by steamreforming of acetic acid over CuZnNi supported calcium aluminate catalysts. Nanocatalysisfor Fuels and Chemicals 9, 111137.
7. Mohanty, P., Patel, M., Pant, K. K. (2012) Sustainable hydrogen from steam reforming ofacetic acid as a model oxygenate over CuZn supported calcium aluminate catalyst.Bioresources Technology 123, 558565.
8. Zaidi H.A and Pant K.K. (2004) Catalytic conversion of Methanol to Gasoline rangehydrocarbons, Catalysis Today, 96, 155160.
9. http://www.setlaboratories.com/cat1/tabid/80/Default.aspx10. http://www.petroleumrefining.com/index.php?option=com_content&view=article&
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