DiscoveredbyFranzFischerandHansTropschatthe

KaiserWilhelmInstituteforCoalResearchinBerlin,Germany
in1923.Thetwocreatedtheprocessin1925.

TheFischerTropschProcessisasetofchemicalreaction

thatconvertamixtureofcarbonmonoxideandhydrogenintoa
liquidhydrocarbons.
Theprocess,akeycomponentofgastoliquidtechnology,

producesapetroleumsubstitute,typicallyfromcoal,natural,or
biomassforuseassyntheticlubricantoilandassyntheticfuel

Twomaincatalystused
Iron (Fe) - Used for both Low Temperature and High Temperature process
Low Temperature (200-240oC)
High Temperature (300-350oC)
Cobalt (Co) - Much higher activity than Fe and much more expensive than
iron based catalyst.
Used for Low Temperature (200-240oC)

Two rarely used catalyst

Nickel (Ni) - is a very active metal, however, tends to promote the synthesis of
methane, which is the least desired product of FTS.
Ruthenium (Ru) - is an extremely active catalyst metal, very rare metal and is
extremely expensive.

Gasification is a process that

converts organic or fossil based
carbonaceous materials into carbon
monoxide, hydrogen and carbon
dioxide. This is achieved by
reacting the material at high
temperatures
(>700C),
without
combustion, with a controlled
amount of oxygen and/or steam.
The development of catalytic partial
oxidation technology for the
conversion of natural gas to
synthesis gas (CO + H2) from steam
reforming to autothermal reforming
to direct oxidation. (required
temperature to around 800C
900C)

Steam Reforming is a process in

which methane from natural gas
is heated, with steam, usually with
a catalyst, to produce a mixture of
carbon monoxide and hydrogen
used in organic synthesis and as
a fuel. (The outlet temperature
of the syngas is between 9501100 C and outlet pressure can
be as high as 100 bar)
Purification of Synthesis Gas Removal of Dust, Carbon Dioxide
and Sulfur Compounds.

The 4 main reactor type design in F-T

 There are multiple FT plants throughout the world

Plant in Malaysia produces low-sulfur diesels
South Africa uses both coal and natural gas
There have been proposed facilities in the US to turn

coal and waste-coal into FT fuels

 TheBergiusProcessisaverysimpleprocessforconvertingbrowncoal

completelyintocrudeoilinventedbyDr.FriedrichBergius.
Themostimportantresultofhisresearchwasthehydrogenatingeffect

ofhydrogenoncoalandheavyoilsunderhighpressure,in1912and
1913.

Dr.BergiusreceivedtheNobelPrizein1931forthiscontributionto

industrialscience.
Thebrowncoal,alsoknownaslignite,isgroundintoafinepowderand

placedintoahighpressurereactorwhereitisreactedwithhydrogen
gasathightemperatureandpressure.

First the coal is pulverized and

mixed with water and a solvent to
create slurry.
This slurry is then hydrogenated
in a reactor at a pressure of 200
bars (2800 psi) and a temperature
of 450 0C.
Hydrogen is injected in the
reactor (Hydrogen accounts for 5
to 14% of the total mass in the
reactor).
The reaction occurs to a catalyst
made of Nickel and Molybdenum
(Ni-Mo) doped with Silicium.
During this reaction, the carbon
reacts with hydrogen to create
alkanes

Crackingistheprocesswherebycomplexorganicmoleculessuchas
kerogensorheavyhydrocarbonsarebrokendownintosimplermolecules
suchaslighthydrocarbons,bythebreakingofcarbon-carbonbondsin
theprecursors.
Cracking
PRIMARYPROCESSINGUNIT
indemand
ProductiSECONDARYPROCESSINGUNIT

Secondaryunitsareinstalledto:
Upgradelowergradeproducts
Increasevalueaddedproducts
Maximiseproductionofproductsonofspecialtyproducts
Minimiseproductionofundesiredproducts

Types of Cracking Process

1. Thermal Cracking - breakingdownlargemoleculesbyheatingathigh
temperatureandpressureistermedasthermalcracking.Thermal
crackingisfurtherclassifiedintothefollowingclasses.
Liquidphasethermalcrackingprocess:Thehigherboilingfractionse.g.,

fueloil,lubricatingoilareconvertedintolowboilingfractionsbyheating
theliquidsatatemperatureof750K,underapressureofabout10
atmosphere.
Vaporphasethermalcrackingprocess:Lowboilingfractione.g.,
keroseneiscrackedinthevaporphaseatatemperatureofabout875K
andunderapressureof3atmosphere.

TYPES OF CRACKING PROCESS

2. Catalytic Cracking - higherhydrocarbonscanalsobecrackedatlower
temperature(600-650K)andlowerpressure(2atm)inthepresenceofa
suitablecatalyst.
Atypicalcatalystusedforthispurposeisamixtureofsilica(SiO 2),4parts;
alumina(Al2O3),1part,andmanganese-dioxide(MnO2),1part. Catalytic
Crackingproducesgasolineofhigheroctanenumberandthereforethis
methodisusedforobtainingbetterqualitygasoline.
3. Steam Cracking - higher hydrocarbons are mixed with steam in their
vaporphaseandheatedforashortdurationtoabout900C,andcooled
rapidly. This process is suitable for obtaining lower unsaturated
hydrocarbons.

HYDROCRACKING

Hydro cracking is a two-stage process combining catalytic

crackingandhydrogenation,whereinheavierfeedstocksare
cracked in the presence of hydrogen to produce more
desirableproducts.
The process employs high pressure, high temperature, a
catalyst,andhydrogen.
Hydro cracking is used for feedstock that are difficult to
processbyeithercatalyticcrackingorreforming,sincethese
feed stocks are characterized usually by a high polycyclic
aromatic content and/or high concentrations of the two
principalcatalystpoisons,sulfurandnitrogencompounds.

TWO-STAGE HYDROCRACKING
In the first stage, preheated feedstock
is mixed with recycled hydrogen and
sent to the first-stage reactor, where
catalysts convert sulfur and nitrogen
compounds to hydrogen sulfide and
ammonia. Limited hydrocracking also
occurs.
After the hydrocarbon leaves the first
stage, it is cooled and liquefied and
run through a hydrocarbon separator.
The hydrogen is recycled to the
feedstock. The liquid is charged to a
fractionator. Depending on the
products
desired
(gasoline
components, jet fuel, and gas oil), the
fractionator is run to cut out some
portion of the first stage reactor outturn. Kerosene-range material can be
takenasaseparateside-drawproduct
or included in the fractionator bottoms
withthegasoil.

TWO-STAGE HYDROCRACKING
The fractionator bottoms are again
mixed with a hydrogen stream and
charged to the second stage. Since
this material has already been
subjected to some hydrogenation,
cracking, and reforming in the first
stage, the operations of the second
stage are more severe (higher
temperaturesandpressures).Likethe
outturn of the first stage, the second
stage product is separated from the
hydrogen
fractionator.

and

charged

to

the

CATALYTIC REFORMING
Catalytic reforming is an important process used to convert low-octane
naphthas into high-octane gasoline blending components called
reformates.
Reforming represents the total effect of numerous reactions such as
cracking,polymerization,dehydrogenation,andisomerizationtakingplace
simultaneously.
Depending on the properties of the naphtha feedstock (as measured by
the paraffin, olefin,naphthene, and aromaticcontent)andcatalystsused,
reformates can be produced with very high concentrations of toluene,
benzene, xylene, and other aromatics useful in gasoline blending and
petrochemicalprocessing.
Hydrogen, a significant by-product, is separated from the reformate for
recycling
and
use
in
other
processes.

Catalytic Reforming Process

THERMAL CRACKING PROCESS

Coking is a severe method of thermal cracking used to upgrade heavy
residuals into lighter products or distillates. Coking produces straight-run
gasoline (coker naphtha) and various middle-distillate fractions used as
catalyticcrackingfeedstock.

Thermal Cracking

Catalytic Cracking
Lowtemp

RequiresHightemp

Highconversion

Lowconversion

Lowcoke

Highcoke

LongRun-length

ShortRun-length

Controlonproductpattern

Nocontrolonproductpattern

Benefits of FCCU:
Convertsheavyendsintodesiredlighterproducts
Reactioninvolvesregroupingofmoleculestoprovidethequalityproduct
Flexibilityinproductpattern
ProductionoflowermolecularweightspecialproductslikePropylene,Butylenes
ReducestheSulphurcontentinliquidstreamsbyconvertingintoH2S
Minimiseproductionofundesiredproducts

REACTORS

ALL OF THE CRACKING REACTIONS TAKE PLACE IN THE CATALYST RISER.

The hydrocarbon vapors "fluidize" the powdered catalyst and the mixture of hydrocarbon vapors
and catalyst flows upward to enter the reactor at a temperature of about 535 C and a pressure of
about 1.72 bar.The reactor is in fact merely a vessel in which the cracked product vapors are:
Separated from the so-called spent catalyst by flowing through a set of two-stage cyclones within
the reactor and the spent catalyst flows downward through a steam stripping section to remove
any hydrocarbon vapors before the spent catalyst returns to the catalyst regenerator. The flow of
spent catalyst to the regenerator is regulated by a slide valve in the spent catalyst line.

ISOMERIZATION
Isomerization converts n-butane, n-pentane and n-hexane into their
respectiveisoparaffinsofsubstantiallyhigheroctanenumber.
The straight-chain paraffins are converted to their branched-chain
counterpartswhosecomponentatomsarethesamebutarearrangedina
differentgeometricstructure.
Isomerization isimportantfortheconversionofn-butaneintoisobutane,
toprovideadditionalfeedstockforalkylationunits,andtheconversionof
normalpentanesandhexanesintohigherbranchedisomersforgasoline
blending.
Isomerization is similar to catalytic reforming in that the hydrocarbon
molecules are rearranged, but unlike catalytic reforming, isomerization
justconvertsnormalparaffinstoisoparaffins.

ISOMERIZATION CATALYSTS

Aluminum chloride catalyst plus hydrogen chloride

are universally used for the low-temperature
processes.
Platinum or another metal catalyst is used for the
higher-temperatureprocesses.
Inatypicallow-temperatureprocess,thefeedtothe
isomerization plant is n-butane or mixed butanes
mixedwithhydrogen(toinhibitolefinformation)and
passed to the reactor at 230-340 F and 200-300
psi.

C4-ISOMERIZATION

C5 AND C6 ISOMERIZATION

C5 AND C6 ISOMERIZATION

Alkylation combines low-molecular-weight olefins

(primarily a mixture of propylene and butylene) with
isobutene in the presence of a catalyst, either
sulfuricacidorhydrofluoricacid.
Theproductiscalled alkylateandiscomposedofa
mixture of high-octane, branched-chain paraffinic
hydrocarbons.
Alkylateisapremiumblendingstockbecauseithas
exceptional antiknock properties and is clean
burning.Theoctanenumberofthealkylatedepends
mainly upon the kind of olefins used and upon
operatingconditions.

Sulfuric Acid Alkylation Process

Type sulfuric acid (H2SO4) alkylation units, the
feedstock (propylene, butylene, amylene, and fresh
isobutane) enters the reactor and contacts the
concentratedsulfuricacidcatalyst(inconcentrations
of 85% to 95% for good operation and to minimize
corrosion).
The reactor is divided into zones, with olefins fed
through distributors to each zone, and the sulfuric
acid and isobutanes flowing over baffles from zone
tozone.

The alkylation unit is fed isobutane and olefinic C4S,

which react in a sulfuric acid catalyst.

Hydrofluoric Acid Alylation Process

Olefin and isobutane feedstock are dried and fed to a
combinationreactor/settlersystem.
Uponleavingthereactionzone,thereactoreffluentflowstoa
settler(separatingvessel)wheretheacidseparatesfromthe
hydrocarbons.
The acid layer at the bottom of the separating vessel is
recycled.Thetoplayerofhydrocarbons(hydrocarbonphase),
consisting of propane, normal butane, alkylate, and excess
(recycle) isobutane, is charged to the main fractionator, the
bottomproductofwhichismotoralkylate.

The alkylation unit is fed isobutane and

olefinic C4S, which react in a Hydrofluoric acid
catalyst.