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OVERVIEW OF CATALYTIC PROCESSES IN REFINING AND PETROCHEMISTRY

2009 - IFP Training

CONTENT
CATALYST MARKET IN the REFINING INDUSTRY

THE TARGETS OF A REFINERY

PETROLEUM PRODUCTS CHARACTERISTICS

DIFFERENT TYPES OF CATALYSTS , FORMULATION AND REACTORS' TECHNOLOGY

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MAIN CATALYTIC TRANSFORMATION UNITS, THEIR PLACE IN THE REFINERY


Gasoline producing processes Gas producing processes

CATALYSTS IN THE REFINING INDUSTRYCATALYSTS IN THE REFINING INDUSTRY

Catalysis

Catalysis is involved in most refining products and processes

CATALYST = STRATEGIC MATERIAL

Catalysts help
- increase the desired reaction rates - obtain selectively the desired products
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Two types of catalysts can be distinguished : Homogeneous catalysts : the catalyst. Is mixed in the liquid phase with the reactants and the products. Merox catalysts can be placed in this category, as well as HF or H2SO4 acids for alkylation Heterogeneous catalysts : the catalyst is a porous solid, showing different shapes : powder, extrudates or or bead s The reaction medium can be gaseous , liquid or gas-liquid . This type of catalysts play a very important role in the industry, being unavoidable in refining and heavy petrochemistry processes

Market for catalysts and adsorbents


Refining :
Production of fuels

Petrochemistry : 800 M M

2300 M M

Pollution removal: removal:


Fixed sources : 400 M M Engines: 1700 M Engines: M Industrial: 500 M Industrial: M

Worldwide market : 7000 M M

Synthesis gas : 750 M M

Polymerisation : 2400 M M

Chemistry : 800 M M
Source IFP SME presentation 231003

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Catalyst market in the refining industry


12 000
Hydrocracking

30 000
Claus

in Tons/year
1000
Isomerisation

8000
Reforming

130 000
Hydrotreatment

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FCC

655 000
Source : IFP School C. TRAVERS 2007

Industrial catalytic reactions (1)


MANUFACTURE OF SYNTHESIS GAS and HYDROGEN Steam reforming of hydrocarbons over nickel catalysts CO + H2 Water-gas shift reaction (CO + H2O CO2 + H2) over catalysts of iron oxide or

mixed oxides of Zn, Cu and Cr


REFINING and MANUFACTURING of BASE CHEMICALS : Catalytic cracking diesel, gasoline, aromatics, olefins,... catalytic reforming gasoline, aromatics. Catalytic isomerization light gasoline and isoparaffins Catalytic hydrocraking gasoline, fuel oils, diesel. Hydrodesulfuration and hydrotreatments. selective hydrogenation of pygas Oxidation Claus process and tail gas treatment Polymerization various oligomers (gasoline, olefins for detergents and plastics).

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OTHER REACTIONS Alkylation cumene, ethylbenzene, gasoline. benzene, naphtalene. Catalytic Hydrodealkylation of alkyl aromatics TO BE MENTIONED in inorganic chemistry NH3 synthesis on iron catalyst. SO3 synthesis by SO2 oxidation, on Pt or V2O5 based catalyst NO Synthesis by NH3 oxidation de , on Pt Rh based catalyst

Industrial catalytic reactions(2)


Hydrogenation : Aromatics to naphtens, nitriles and nitro compounds to amines,
Dehydrogenation : Paraffins olefins Hydration : Ethylene diolefins ; Alcohols ketones

ethyl alcohol.

Selective oxidation : alcools aldehyde (methanol to formadehyde); ethylene to ethylene oxide Oxychlorination and chlorination : Ethylene + HCI + 02 Dichlorethane ( Methanol synthesis from gas on ZnO, Cr2O3
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VCM vinyl chloride monomer).

Polymerizations Polyethylene on Cr2O3 or supported Ni.

Hydrogenations : Benzene cyclohexane. Nitriles (ou dinitriles) amines (ou diamines) (nylon for ex.). Phenol cyclohexanol (adipic acid et nylon). Nitrobenzene aniline. Hydrogenations of fatty acids Selective hydrogenations . Dsydrogenations : Paraffins Alcohols Hydratations : Ethylne Controlled oxidations : Ethylene ethylene oxyde on silver based catalyst. Methanol formol on silver based catalyst or Fe2O3 , MoO3 Ethanol acetaldhyde Benzene malc anhydrid on V2O5 or MoO3 Naphtalne or o-xylene phtalic anhydrid on V2O5 Propylene acroline, acrylonitrile, on Bismuth molybdates or phosphomolybtates alcool thylique. olefines diolfines ( butane butene ktones (isopropyl alcohol to acetone) butadiene)

Refining targets

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The targets of a refinery: To produce, from different and changing crudes, petroleum products To adjust the quantities : transform the less valuable cuts into needed cuts To adjust the quality: lead the various cuts into the specifications of the market To handle the environmental features

A 8 Mt/year refinery (medium size) is :


500 to 650 MW of self consumption 1000 tons/hour of crude oil 35 000 m3 gasoline and diesel per week About 20 operating units A shutdown for maintenance every 4/5 years An operation permit given for 10 years

80 % OF REFINED MOLECULES HAVE BEEN IN CONTACT WITH A CATALYST

Composition of crude oils

CARBON
Hydrocarbons :

84 to 87 weight % 11 to 14 weight %

HYDROGEN
Impurities : SULPHUR OXYGEN NITROGEN
Heavy Metals
Water and sediments

0.04 to 6

weight %

0.1 to 0.5 weight % 0.1 to 1.5 weight %


50 to 150 g/t 0.1 to 0.6% volume 20 to 200 g/t

Heavy crude

Light crude
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Mineral salts

These values are usually observed for the global composition of crude oils

The specific gravity of a crude oil generally ranges between 0,7 and 0,95 . Metals that can possibly been encountered are combined in complex compounds containing carbon, hydrogen, sulfur, nitrogen, .Vanadium generally accounts for more than 75% of the metal content. Crude oils also include non organic compounds such as water, sediments and mineral salts. .

Saturated
Hydrocarbons

No double or triple bonds All bonds are saturated with hydrogen

Paraffins (alcanes) Naphthenes (cycloalcanes)

Unsaturated
Hydrocarbons

Double or Triple bonds Some bonds are not saturated with hydrogen

Olefinics (alcenes) Aromatics


Acetylenics (alcynes)

Composition of crude oils


Ponca city crude OKLAHOMA Boiling point C

Arom

atic on

Aromatic polycyclics
e rin g

% volume

Naphthen one cycle Naphthen polycyclics Isoparaffin


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N-paraffins

Extra light crude

Light crude from North Sea

Heavy crude: Venezuela

Extra heavy crude: solid at 20 C

Volatility of petroleum products : ASTM Distillation D 86


Equipment used to measure the distillation temperatures of the sample product under atmospheric pressure.

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This standard test is applied to all the main petroleum products except liquefied petroleum gases and bitumen. It consists in distilling 100 ml of product in standardized conditions and noting the temperatures corresponding to the different volumes either evaporated or condensed and collected. Two important temperatures are recorded: initial boiling point (IBP) , recorded when the first liquid drop is observed final boiling point (End Boiling Point: EBP) which is the maximum temperature observed during the test

Boiling intervals of hydrocarbons present in the main petroleum products

GAZ GAS+LPG

LNG LNG
LPG LPG FUEL FUEL PETROCHEMICAL PETROCHEMICAL NAPHTHA NAPHTHA COMMERCIAL PROPANE COMMERCIAL PROPANE COMMERCIAL BUTANE COMMERCIAL BUTANE

C1 C3 C4 C5 C8 C11 C13 C20 C25

- 200 C - 100 C 0 C

ESSENCES GASOLINES

MOTOR MOTOR GASOLINE GASOLINE


JET A1 JET A1

+ 100 C

+ 200 C

PRODUITS INTERMEDIATE INTERMEPRODUCTS DIAIRES

AUTOMOTIVE DIESEL OIL AUTOMOTIVE DIESEL OIL HOME HEATING OIL HOME HEATING OIL
PARAFFINS PARAFFINS

+ 300 C

+ 400 C + 500 C +600 C


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HEAVY PRODUCTS

BASE OILS BASE OILS

HEAVY FUEL OILS


BITUMEN

C35 C55

Microwaxes Microwaxes

PRODUCTS

Number of carbon atoms and boiling points

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Petroleum cuts are characterized with the number of Carbon atoms or boiling temperatures. The shape of the ASTM distillation curve indicates the volatility of the petroleum product components when high volatility is required, the results must indicate a minimum distilled percentage at a given temperature heavy components can be limited by fixing the End Point at a maximum temperature. In this case, R (residue %) can also be limited to a given amount The cuts containing less than 30 carbon atoms are separated in the crude atmospheric distillation column ("topping"). The most "heavier" are separated in the vacuum distillation column. Every crude oil is characterized by the potential yield in main oil cuts that can be reached. Two important parameters, reflecting the essential characteristics, are the density and the content in Sulfur

Change of world petroleum demand structure


100 % weight

29,5 30
50

30,5

36

40

Light products
GPL, naphtha, gasolines,..

31

38

45,0

Middle distillates
JET-A1 Diesel and heating fuel

40,5
0

38,5
1980

26
1995

15,0
2020

Heavy Products
Heavy fuels Bitumens,

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1973

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In the 1990s, the conversion units became to be more and more numerous, in order to satisfy the demand, especially since the crude oils used are more and more heavy.

PETROLEUM PRODUCTS CHARACTERISTICS

CATALYSTS IN THE REFINING INDUSTRYCATALYSTS IN THE REFINING INDUSTRY

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REFINING

CRUDE OIL (C, H, O, N, S, Metals : Ni, V)

REFINING

To meet the requirements on quantities (market) on quality (specifications) And to take into account the environmental challenges

PETROLEUM PRODUCTS at SPECIFICATIONS LPG gasoline jet fuels diesel oil fuels wax

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CATALYTIC PROCESSES

THERMAL PROCESSES

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Definition of a petroleum product : It is a mixture of hydrocarbons ; its composition is characterized by a set of limit values fixed for a certain number of factors which determine its optimal implementation in its conditions of use, the specifications The specifications can change depending on : The season The region the politico-economic context (Pb in gasoline, S in diesel oil, benzene in gasoline...) The economically affordable cost of production The specifications can be related to:
Volatility : IP, FP, ASTM distillation intervals, flash point (jet fuel, diesel,..) Combustion : octane number, cetane number Cold condition behavior and flowing : freezing point, viscosity (gas oil and jet fuels) Atmospheric pollution : sulfur content, benzene or (poly-)aromatics content, . corrosiveness : Copper and silver strip tarnish tests Stability and chemical type : existing gum content, oxidation and thermal stability, behavior at water presence (jet fuel), insoluble content (heavy fuels n 2)

Main quality criteria of petroleum products


Petroleum product Main quality criteria Incidences

Volatility GASOLINE OCTANE NUMBER RON and MON

Start-up, warm up, fouling engine Combustion without knocking

JET FUEL JET A1

Composition Quality of combustion RESISTANCE TO COLD CONDITIONS SULPHUR CONTENT

Safety No risk of HP turbine deterioration Ability to remain liquid at low temperature Depollution of Diesel engines Ability to remain liquid at low temperature Quality of combustion in a Diesel engine
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DIESEL FUEL

RESISTANCE TO COLD CONDITIONS CETANE INDEX

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Main quality criteria of petroleum products


Produits Petroleum ptroliers product LPG Critres de qualit Main quality criteria principaux Composition Signification Safety of operation
Incidences

HEAVY FUELS

SULFUR CONTENT Viscosity PENETRABILITY

Environnement protection Quality of combustion Hardness of bitumen Resistance to temperature

BITUMEN

SOFTENING POINT

Viscosity BASE OILS Viscosity index Behavior in cold conditions

Lubrification ability Viscosity control at varying temperatures on use Ability to remain liquid at low temperature
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Different type of technologies for catalytic reactors


Thermal processes Catalytic processes
Fixed beds Moving beds Fluidized beds

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THERMAL PROCESSES

Few thermal processes in the refinery:


visbreaking, coking, steamcracking (petrochemistry) A significant energy input
is necessary to activate chemical bounds

The reaction intermediate :


radicals created by chemical bond breaking A B A + B
these radicals will initiate reactions in series

Thermal processes are not selective, they are industrially used when :
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there is no other economic way to obtain corresponding products selectivity is not essential

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The thermal processes operate at very high temperature (>500C to breaking C-C bond). At such high temperatures, high selectivities can't be obtained because side reactions, especially coking, are not negligible.

CATALYTIC PROCESSES

Most of the refining processes are catalytically promoted Catalyts activate chemical bounds / molecules
Promoting interactions between reactant and catalyst sites

Catalysts :
make operations possible and/or enhances the desired reactions orientate reactions has to be stable :
catalyst deactivation inducing loss of performances

In several catalytic processes, feedstocks :


have to be pre-treated for impurities removal and/or catalyst protection

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Depending on the catalyst, the feed must reach specifications in terms of impurities content

DIFFERENT TYPES OF CATALYSTS


In refining, depending on the kind of bond which has to be activated, catalysts can be divided into three families:
ACTIVATION OF C-C BOND (85 Kcal/mol)
Ex : paraffins alkylation, catalytic cracking

acidic catalysts (acidic sites = H+) ACTIVATION OF C-H (95 Kcal/mol) or H-H (104 Kcal/mol) BONDS
Ex : Hydrotreatments

metal catalysts

(metal sites : group VIII Pt, Rh, Pd)

ACTIVATION OF THE 3 KINDS OF BONDS


Ex : Hydrocracking, catalytic reforming

bifunctional catalysts (metal on acidic support)


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Both types of sites are present simultaneously


modification of carbon skeleton modification of H/C ratio

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Some basic catalysts can also been encountered, for example for esters hydrolysis reactions

Different types of catalysts in refining

Acidic catalysis Bond to activate


Kcal/mol

Metal catalysis C-H (95) H-H (104)

Bifunctional catalysis C - C ; C-H H-H

C-C (85) Carbocation

Intermediate

H Metal

H Metal
Metals + acidic carrier

C
Catalyst

H+ from carrier (alumina, zeolite)

Group VIII metals (Pt, Rh, Ru)


Hydrotreatment Hydrogenation

Example

Catalytic cracking Paraffins isomerization Alkylation Etherification Oligomerisation

Reforming Isomerization Hydrocracking Acid catalytic process with sensitivity to coke deposition

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IMPLEMENTATION OF CATALYSTS

Industrially, three kinds of catalytic reactors are generally used:

Fixed bed Moving bed Fluidized bed


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Example of fixed bed : catalytic reformer


Example : HDS

The feed can be liquid or gaseous The particles morphology must not create pressure drops extrudates, beads Intra particle diffusion limitations have to be limited CAUTION with temperature control for endo- or exo-thermal reactions (adiabatic behavior)
Several beds in series with intermediate heating or cooling

The shorter the contact time, the lower the reaction conversion
Contact time = Catalyst Volume (m 3 ) Feed flowrate (m 3 /h )

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Fixed bed are adiabatic , the control of the temperature increase or decrease has to be carefully considered, taking into account the possible gradients inside the catalyst grain

In a fixed bed, the activity of the catalyst is decreasing with time, mainly due to coke deposit on the active sites. Operating parameters have to be adjusted : Higher temperatures to get the same conversion As a consequence, the yield very often decreases. When the temperature becomes too high, the unit has to be stopped to regenerate the catalyst . The catalyst regeneration usually consists in gradually burning the coke, by feeding the reactor with pre-heated oxygen diluted into nitrogen
Examples of fixed bed operation : Hydrogenation, Hydrodesulfuration, Hydrocracking, Isomerization Flow behavior in such reactors is : plug flow all the molecules are moving downwards, at the same velocity at a given height, all the molecules have had the same contact time with the catalyst

Example of fixed bed: catalytic reformer


Highly endothermic process
Interheaters

Export H2
R3
Separator Fuel Gas

R1

R2

H2
Hydrotreated Naphtha
Recycle Compressor

LPG

Reactor Temperature

Stabilized

T0
T0-25C T0-50C R1 R2 R3

Reformate

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The overall amount of catalyst needed for the transformation is distributed not equally among several adiabatic reactors in series with intermediary heaters providing the required heat energy input

MOVING BED TECHNOLOGY

If the catalyst deactivates quickly, due to coke build up, a moving bed technology can be implemented :
Periodic or continuous catalyst removal regeneration Injection of the regenerated catalyst at the top of the reactor

Example : Regenerative reforming ("slow" moving bed)


The catalyst shape : often spheres The feed flow and thermal transfer aspects are not much modified compared to a fixed bed reactor
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Example : Regenerative reforming ("slow" moving bed) Catalyst shape : spheres (oil drop made) the cycle time of the catalyst is about 1 week

Example of moving bed : Regenerative reforming (CCR or RR )

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FLUIDIZED BED TECHNOLOGY

Usually used when thermicity problem in fixed bed can't be solved Easy implementation of the catalyst, if its mechanical and morphological characteristics are correct Example : FCC Fluidized Catalytic Cracking Catalyst formulated by spray drying (50 m)

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FLUIDIZED BED TECHNOLOGY


Example : FCC
Catalyst circulation 930 t/h= 15.5 t/min Coke on used catalyst = 7,5/930 = 0.8% wt Air rate = 120/7,5 = 16 tons per ton of coke Flue gas to treat 120 + 7.5 = 127.5 t/hr Fluidized bed

Duration of cracking several seconds


RPCI - Rev. 4

CRACKED PRODUCTS SENT TO FRACTIONATION

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The catalytic section consists of: a reactor or riser in which the cracking chemical reactions of the feed in contact with the catalyst take place at temperatures in the 500 to 530C range and at low pressure (2 - 3 bar). Coke is deposited on the catalyst, which destroys its catalytic activity. a regenerator in which the coke deposited on the catalyst is burned with the injection of combustion air. The heat thus released reheats the catalyst to a temperature generally in the 670 -750C range. The regenerated, coke-free catalyst can thus be re-used in the reactor. reactor-regenerator connections allowing circulation of the catalyst from one vessel to another. The heat recovered by the catalyst in the regenerator is restored, so to speak, to the reactor.

How to get to specs gasoline from crude oil?


The targeted specifications The chemical transformations The refining processes

RPCI - RA GEN - 06944_A_A - Rev. 0 CATALYSTS IN THE REFINING INDUSTRYCATALYSTS IN THE REFINING INDUSTRY

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THE OCTANE NUMBER FOR GASOLINE

The octane number is linked to knocking. The chances of knocking are increased if the gasoline presents a poor resistance to self ignition. It is measured with a CFR engine : single cylinder engine running at constant speed. To start or to stop the knock, the rate of compression can be modified.
Air + gasoline

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Example of specifications for unleaded gasoline :


unleaded Color Specific gravity et 15 C Vapor pressure % distillated at 70 C Final point RON MON Sulfur Pb Existent gum MTBE Benzene ( ppm wt) (g/l) (mg/100 cm3 (% volume) (% volume) )

No color (kg/dm3) kPa (mbar) (volume) ( C)

0,720 - 0,775 45 -90


(depending on season)

20 -50 210 95 85 10 0,005 5 15 1

OCTANE NUMBER : THE KNOCK


Combustion in a 4 cycle spark ignition combustion engine
Park plug

P max 35 to 50 bar

ignition

Combustion without knock

Burnt mixture

Flame front

Self combustion Vibrations Knocking

ignition

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Combustion with knock


Duration of combustion : 1 to 2 milliseconds

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Scale for RON and MON :

ISO OCTANE N - HEPTANE

C C-C-C-C-C C C C-C-C-C-C-C-C

RON=100, MON=100 RON=0, MON=0

Definition : the octane number is given by the equivalent volume percentage of isooctane in a reference mixture of normal - heptane and of isooctane, trigging an identical knocking in the CFR engine.

STANDARD METHODS (NF M 07-026)


Two main methods are used for gasoline. They differ in the rotational speed of the C.F.R. engine and the temperature of the mixture at the intake Research Octane Number (RON) : the rotational speed is 600 rpm and the fuel mixture temperature is ambient. Motor Octane Number (MON) : The rotational speed is 900 rpm and the fuel mixture temperature is about 150 C. SENSITIVITY OF THE GASOLINE : Considering the more severe conditions of the measure, the MON is generally lower than the RON. The difference RON-MON is called sensitivity of a gasoline. A specification of MON or of sensitivity is a guarantee of good behavior of the gasoline in severe conditions of use.

OCTANE NUMBER OF HYDROCARBONS

RON
Sensitivity

Very low
Very low

High
Very low

Medium
Low

Very high
High

High
Very high

Straight-run heavy gasolines from crude oils: high normal paraffin content, low aromatic content, low RON-MON Reformate gasoline: high aromatic content, Very high RON - High MON Gasolines from Catalytic cracking: olefins, aromatics, saturated, medium RON - weak MON

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Additives to improve ON : Ban of lead requires higher octane number: production of high octane hydrocarbons, use of ethers. Replacement of lead by a potassium based additive to protect the seat of the valves (lubrication). Use of oxygenates : MTBE, ETBE, TAME, METHANOL, ETHANOL , for which oRON>110 ; MON>100 Biofuel super ethanol E85 contains up to 85% ethanol of organic origin and premium unleaded gasoline in addition Vehicles intended for use of E85 can work with premium unleaded gasoline or with any mixture E85/premium gasoline. They are FLEXIFUEL Origin of ethanol: cereals, maize, beet, sugar-cane. Future: Biofuels of second generation produced from non food vegetation (wood, seaweed.) Consumption (in litres/100km) + about 30% due to the lower Calorific Value of ethanol Interest: reduction of Green House Gas emissions but problem in the competition for use of cultivated soil

SIMPLIFIED REFINING SCHEME

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Main processes producing gasoline

1. 2. 3. 4. 5. 6.

Catalytic reforming Isomerization Catalytic cracking Alkylation Etherification Visbreaking

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Gasoline pool composition


FCC gasoline

3% 12% 2% 12% 40%

Reformate Isomerate Octane additives Naphta from distillation

30%
gasoline from Coker & others
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Additional bases: used to adjust RON and MON alkylate, MTBE, ETBE, ethanol
From R.V. Elshout and C.S. Bains, Hydrocarbon Engineering, p.71, Feb. 2005

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Octane numbers for each hydrocarbon types

Catalytic reforming for heavy gasoline

Isomerization for light gasoline

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1. catalytic reforming process


produces a base with very high octane number, from heavy straight run gasoline (RON 97-101, MON 86 - 88) high aromatic content produces hydrogen for the whole refinery (1,5-3% H2) produces BTX as bases for petrochemistry

n-Paraffins in C7 C10 Naphthens in C7 C10 500C 5 to 25 bar


With Coke deposition

AROMATICS
Light paraffins

AROMATICS
Light paraffins

On a specific platinum catalyst

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3 main chemical reactions Aromatization Reaction: Transformation of Naphthenes and Paraffins in Aromatics ohydrogen producers overy endothermic overy QUICK (for naphtenes) or SLOW (for paraffins) opractically COMPLETE (nearly all naphthenes are transformed in aromatics) or INCOMPLETE (for paraffins) Hydrocracking Reaction: Transformation of long paraffins in shorter paraffins ohydrogen consumers oexothermic oquite slow ogas producer: C1, C2 and mostly LPG C3, C4 odecreasing the reformate yield oa positive contributor to improve octane number Side reaction: Coke formation on the catalyst

2. Paraffins isomerization
Produces a base with high octane number, from light straight run gasoline (RON 80-90, MON 77-87) Reactions : operated at low temperature to maximize iso paraffins production
150 to 250C

n-paraffins
Catalysts :
Pt/chlorinated alumina (5-10%wt Cl) Pt/zeolite

isoparaffins + heat

Process : fixed bed


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The light straight-run gasoline (C5 C6) is used in: the petrochemical industry, especially in Europe. Under the name of naphtha, it is a feedstock for steam crackers the automotive gasoline pool. But since the lead additives suppression, it is necessary to improve the octane number by isomerization Isomerization reactions are slightly exothermic (approx.10 kJ/mole ). They are balanced. n-paraffins
nC5H12 ; nC6H14

i-paraffins mono-branched
i C5H12 ; iC6H14

i-paraffins di-branched
i C6H14

Aromatics + H2
benzene

Naphtenes
cyclohexane

+ H2

n-paraffins
n-C6H14

Benzene hydrogenation is very exothermic Some hydrocracking occurs Example : C7 H16 n-paraffin C4H10 + C3H8 n-paraffins

3. CATALYTIC CRACKING

Gives value to vacuum distillates VGO towards:


Gas (<20%) rich in C3=, C4= petrochimistry and other processes : alkylation, etherification Gasoline (40-60 %) RON ~ 92 MON ~80 Diesel oil (10-20%) LCO of low cetane index < 25 diluant of heavy fuel oils HCO
coke production (5%)

Reactions :
acidic catalysis Catalyst : zeolite Y (10-40 % wt) dispersed within an inorganic matrix
example : C20H42 C8H16(Olefin) + C12H26 (Paraffin)

Process :
Fluidized bed with catalyst circulation from/to reaction zone 500 C /regeneration > 700 C. Continuous regeneration of coke built up onto catalyst

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Operating conditions : P 3 bar, without H2, catalyst/oil = 5 t/t feed


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Other features of FCC : Produces mainly gasoline (50 %) and LPGs (of which 6 % of propylene). Feeds : mainly vacuum distillates, also visbroken distillate and some residu (low metals content). Gasoline produced is made up of aromaticsand olefins mainly, giving it a high octane number. Needs to be desulfurized (Merox or hydrotreatement), due ti high content in gum and sulfur. Desulfuration conditions need to be chosen in order to minimize hydrogenation of olefins, in order to avoid octane number loss (example : Prime G+ process Axens or Powerforming - Exxon) gas oil cut (called LCO) : low cetane number, desulfurization compulsory C4 cut : rich in olefines . Allows to feed the alkylation unit which produces gasoline with high MON from LPG ; and (or) an oxygenated compound unit like MTBE or ETBE. Thje margin essentially depends on the difference between VGO cut price and gasoline price, and also the difference of price between light and heavy crude oils. Propylne value also has an importance .

4. Aliphatic alkylation

ISOBUTANE
C4H10
Isobutane from C4 cut of atmospheric distillation and catalytic reforming

BUTENE
C4H8
Butenes from C4 cut of FCC (50 %) : 1-butene, 2-butenes, isobutene

H2SO4 or HF strong liquid acidic catalysts

ISOOCTANES increase RON and MON

C8H18
At the same time increase the production of automotive fuel bases

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This process uses liquid acid catalysts : fluorhydric acid ( HF) or the sulphuric acid ( H2SO4). The feed of the unit is made up of : the " C4 cut out of FCC, rich in olefins Isobutane, obtained by distillation from the C4 cut of the straight run distillation of crude oil and from catalytic reforming

FCC

5. Etherification : MTBE or ETBE


Ethers : high octane number, that can be directly blended to gasoline
iC4= + Methanol MTBE (Methyl-Tertio-Butyl-Ether) iC4= + Ethanol ETBE (Ethyl-Tertio-Butyl-Ether) iC5= + Methanol TAME (Tertio-Amyl-Butyl-Ether) iC4= : gas from FCC or iC4 dehydrogenation

Catalyst : acidic resin Process : fixed bed Operating conditions : T = 80 C, P = 15-20 bar, LHSV 4-6 per hr
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The production capacities of MTBE, ETBE, TAME increased very fast considering the development of unleaded gasoline. Today the future of the MTBE is compromised because of troubles of groundwater pollution met in California. This pollution, linked to the strong smell of the MTBE, is the consequence of leaks and the high solubility of the MTBE in water. Thus, the use of the MTBE has been banned ban since January 1st, 2004. In reformulated gasoline marketed in certain zones of the United States, the MTBE is replaced by the ethanol today.

How to get on spec diesel oil?


The targeted main specifications The chemical transformations The processes
1. 2. 3. 4. FCC HYDROCRACKING and H2 production HYDROTREATMENTS SULPHUR RECOVERY

RPCI - RA GEN - 06944_A_A - Rev. 0 CATALYSTS IN THE REFINING INDUSTRYCATALYSTS IN THE REFINING INDUSTRY

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Diesel fuel cetane number and combustion in Diesel engines


The cetane number of diesel fuel is related to the ignition delay of the fuel which should be as short as possible (in order to avoid an uncontrolled combustion and so provide a silent and easy running of the engine, a cold start up, a reduction of the polluting emissions)
The cetane number is measured in a standard engine (CFR Diesel engine) by comparison with standard fuels: n cetane (C16H34) (n-paraffin): methyl naphtalene (aromatic compound): heptamethylnonane (isoparaffin): CETANE NUMBER CETANE NUMBER CETANE NUMBER 100 0 15

The cetane number of a diesel oil corresponds to the volume percentage of cetane in the mixture of the two reference fuels which has the same ignition delay in the CFR Diesel engine as that of the gas oil tested. The volume percentage of each reference fuel is given its cetane number.

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For example: If the same ignition delay is obtained with a mixture of: 51% volume of n-cetane 49 % volume of methyl naphthalene the cetane number is 51.

Cetane number for hydrocarbons

Cetane number

Very high

low

medium

low

low
2010 - IFP Training

Straight-run gas oil: rich in paraffins, high cetane number Cracked gas oil: rich in aromatics or olefins, low cetane number

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Specification for Diesel fuel :

ASTM cetane number >51 Calculated cetane number >46

Determined from a chart using diesel fuel density and 50% ASTM boiling point

Example : Sp.gr15 = 0.832 t50 = 250 C

CCI = 49

Main processes producing gas oils


ATMOSPHERIC DISTILLATION 1. FCC
LCO (15-25 %wt):
high aromatic content . low cetane number, high sulfur content in case of HS crudes, good diluent for heavy fuel oil when desulphurised, may be mixed with atmospheric gas oils for home heating oil production

HCO and SLURRY (6-10 %wt):


very aromatic products diluents for heavy fuel oils

2. HYDROCRACKING (as follows) 3. HYDROTREATEMENTS : can not be separated from gas oil cuts
2010 - IFP Training

RPCI - Rev. 4

45 45

Example of diesel fuel oil specification: Cetane number - 53-54 Sp. gravity < 840 T95 < 355 Aromatic polycyclic hudrocarbons < 5 Sulfur < 10 Flash point 55C (safety) Filtrability Temp - 15C (autumn-winter) Cloud point -5c (autumn-winter) 0C (spring-summer)

+5C (spring-summer)

2. Vacuum distillates hydrocracking


Target : give value to
vacuum distillates lighter products with very good quality

Feed: distillates, heavy metal absence Gas: rich in H2S, NH3 to be routed to amine washing and Claus units Light gasoline: quite good RON and MON gasoline pool Heavy gasoline: rich in naphtens, sent to reforming unit Kerosene: quite good smoke point and cold conditions Gas oil: quite good cetane index 55, sulphur content, cold condition behavior Global yield: 102-103% Hydrogen consumption: 2-3%wt

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2010 - IFP Training

Hydrocracking is aimed at fuel and diesel oil production, unlike the FCC which produces essentially some gasoline. Moreover, the resulting cuts are desulfurized. Considerations favorable to the hydrocracking : The evolution of the quality characteristics required by oil productions, in particular a very low content in sulfur. The increasing consumption of diesel oil in Europe : Western Europe imports a considerable part of the needed diesel oil. The consumption of heavy fuel oil which is in continuous decrease. Specific features of the process : 350-400 C 160 -180 bar Fixed bed reactor Several steps A purification step : Trap the asphaltens, the metals, hydrotreat (Remove S , N,), Hydrogenate the polyaromatics Catalysis with metal (Ni-Mo on alumina) A hydroconversion /cracking step acidic catalysis (Ni-Mo on zeolite) High H2 consumption : about 1,5% wt vs feed (depending on quality of feed and severity). Need for highly pure H2 (from SMR- Methane steam reforming unit).

Hydrogen balance in refineries


Hydrogen produced by the catalytic reforming is often sufficient for the conventional Hydrotreatments (gasolines and gasoils). But further H2 production units are necessary to supply the hydrotreatment units for the heavy feeds and hydrocracking. H2 purification units (75 99%) implementation of H2 producing SMR or POX

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S. M. R : Steam Methane Reforming CH4 + H2O CO + H2O CO + 3 H2 CO2 + H2 800C on a Ni catalyst 800C then 350C

Purification of H2 to get 99,9% of purity often uses PSA process (Pressure Swing Adsorption) : Separation and adsorption of the molecules on molecular sieves) POX : Partial Oxydation (methane or cracked residues) CxHy + O2 CO + H2O CO + H2 CO2 + H2

Purification of H2 to get 99,9% of purity

3. HYDROTREATMENTS objectives
Eliminate impurities containing sulphur, nitrogen, oxygen, metals with hydrorefining, in order to :
protect catalysts downstream (included catalytic converter), etc... reduce atmospheric pollution control the corrosion and fouling in the equipment

Hydrorefining requires Hydrogen source, available from reforming unit .


HYDROGEN H2

IMPURITIES TO ELIMINATE

Unsaturated compounds DIOLEFINS OLEFINS AROMATICS hydrogenated

Sulfur compounds H2S (gas)


Nitrogen compounds
Oxygen compounds

2010 - IFP Training

Metals (in residues) trapped by catalyst

NH3 (gas)

H2O

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Hydrorefining includes all the processes which aim at eliminating undesired compounds in the petroleum cuts by means of a catalytic treatment using hydrogen. The main impurities to be eliminated are, depending on the case, the sulfur, nitrogen, oxygen , the metals and unsaturated hydrocarbons such as diolefins, olefins and aromatics.

3. Hydrotreatments in the refinery


Fuel gas C1/C2 PROPANE C3 BUTANE C4 LIGHT GASOLINE C5 - C6 HEAVY GASOLINE C7 - C10

+
Cracked gasolines FCC VB

HYDROTREATMENT:
ELIMINATION of SULFUR, NITROGEN and olefins from LIGHT CUTS

DESULFURIZED LIGHT CUTS


towards LPG, ISOMERIZATION REFORMING

KEROSENE C10 - C13

+
Cracked gas oils FCC VB

ELIMINATION OF CORROSIVE COMPOUNDS by SWEETENING or HYDROTREATMENT

SWEETENED KEROSENE towards JET A1

LIGHT GAS OIL HEAVY GAS OIL HYDRODESULFURIZATION OF GAS OILS

DESULFURIZED GAS OILS


towards DIESEL FUEL and

HEATING OIL
DESULFURIZED DISTILLATES towards
CATALYTIC CRACKING
2010 - IFP Training

DISTILLATES C20/25 - C50

HYDROTREATMENT ELIMINATION of SULFUR and aromatics

VACUUM RESIDUE C50+


RPCI - Rev. 5

HYDROTREATMENT ELIMINATION of SULFUR and METALS

DESULFURIZED and DEMETALLIZED VACUUM RESIDUE towards


CONVERSION UNITS

49 49

The heavier the cut : The more sulfur content The more important H2 consumption The more severe conditions the hydrotreatment needs
CRUDE NAPHTHA KEROSENE GASOIL
DISTILLATE

RESIDU

OF S CONTAINING COMPOUNDS

S % wt

range

3. HYDROTREATMENT PROCESSES AND CATALYSTS


Support : alumina
Active species : metal sulphides Cobalt - Molybdenum (CoMo) Nickel Molybdenum (NiMo) for S removal for N removal and hydrogenation

FIXED BED
Contact time Contact time

Weight of catalyst for 100 t/hr feed Light cuts Gas oils Distillates Vacuum residues 30 75 200 300
2010 - IFP Training

Pressure

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4. Sulphur recovery : CLAUS process


Aim : To transform into elementary Sulphur H2S from acid gases generated in hydrotreatment, hydrocracking but also other cracking units

H2S
3 H2S

1100/1200C
H2S + 3/2O2
SO2 + H2O

3/

2O2

2H2S +
BURNER

SO2

S + 2H2O + heat

AIR

Combustion of only 1/3 of inlet H2S by controlling air (O2) quantity at burner inlet

CLAUS reaction between 1 formed molecule of SO2 and 2 unburned molecules of H2S
2010 - IFP Training

Balanced reaction, H2S and SO2 are just partly transformed in sulphur

Ratio H2S/SO2 = 2

Sulphur generated in the gaseous state


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In the burner : combustion of 1/3 of the H2S by controlling the admission of air and thus oxygen in the burner Reaction of CLAUS between the produced SO2 and 2 H2S which is not burnt. This reaction is balanced, H2S and SO2 are only partially transformed into sulfur.

4. Sulphur recovery - CLAUS Process


Reactions : 2 steps thermal step catalytic step
3 HEAT 1H2S + O 2 SO 2 + H2O 2 CAT 2 H2S + SO 2 3S + 2H2O (yield 96%)

Catalysts (fixed bed) : - CLAUS catalyst:


activated alumina high specific area (300 m2/g) + dopants TiO2, V2O5)
2010 - IFP Training

-Hydrolysis of COS, CS2


TiO2, BaO, CaO

52

The main reaction is very exothermic (H = 35 Kcal . mol1) Undesired reactions take place at the thermal step : production of COS and CS2 which have to be hydrolyzed As refineries have to follow : Stricter regulations on products sulfur content Stricter regulations on the SO2 discharged in the atmosphere A tail gas treatment is very often necessary : CLAUSPOL, SULFREEN, SCOT ,

yield of S recovery : 99,7-99,9 %


oCLAUSPOL ( IFP) : reaction at low temperature (125-135C, with catalyst dissolved in a solvent). The sulfur is separated by settling oSULFREEN ( Total-Lurgi): reaction at low temperature on a solid catalyst. The liquid sulfur obtained is adsorbed on the catalyst. The process is cyclic (to allow the desorption of the sulfur) oSCOT ( SHELL): reduction of the obtained SO2 in H2S, at 300C on Co-Mocatalyst . The H2S is absorbed (amine wash ) then recycled towards Claus.

PETROCHEMISTRY
The aims :
to produce high volumes of synthetic products that can substitute natural products COMMODITY PRODUCTS To provide synthetic products endowed with original properties, completing the natural products

SPECIALITY PRODUCTS
2011 - IFP Training

To produce molecules with a composition and a structure perfectly defined, starting from hydrocarbon coming from crude oil, natural gas or coal
RPCI - RA GEN - 06944_A_A - Rev. 0 CATALYSTS IN THE REFINING INDUSTRYCATALYSTS IN THE REFINING INDUSTRY

53

Petrochemistry products are gathered into chemical families :

ofine chemicals oplastics ofibers oelastomers odetergents osolvents ofertilizers


They can be devided into 2 groups :

Products that are used for their chemical properties : they correspond to molecules that have specific chemical functions
fertilizers, detergents, solvents

Products that are used for their mechanical properties : they correspond to macromolecules
plastics, elastomers, fibers

Petrochemical bases
They have to be : Reactives, simple, abundant, cheap They need to allow : Quick and easy reactions high productivity Selective reactions
Low amount of by-products economical target

EXAMPLES
Ethylene Propylene Butenes Butadiene B.T.X. :
Benzene Toluene Xylene

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Toluene is largely converted into benzene and / or xylenes, either by dismutation, or by hydrogenation. Paraxylene is an intermediate in the production of polyester fibers o-xylene can be oxidized into phthalic anhydrid, p-xylene can be oxidized to terephthalic acid and / or dimethyl terephthalate

PETROCHEMISTRY : MAIN INTERMEDIATES PRODUCTION UNITS

Olefins and aromatics


Steam cracking is a thermal process, flexible and efficient
The steamcracker is at the cornerstone of the petrochemical complex. This thermal process allows to get all the desired olefins, diolefins, aromatics

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2010 - IFP Training

But The produced olefins and aromatics contain unsaturated bonds, making the molecules less stable, that have to be selectively hydrogenated .
Other processes :
To get olefins :
FCC (especially C4=) dehydrogenation of paraffins (C3, C4 et C10 C12)

To get aromatics : high severity reforming (especially Xylenes)

PETROCHEMISTRY : THE AROMATIC COMPLEX


EXAMPLE :

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2010 - IFP Training

The aromatic come from the C5+ cut of the steamcracker, or from the reformer (high severity). The BTX has been split. The respective proportions of benzene, toluene and xylene are not in accordance with the market demand. Numerous processing units are needed. The benzene is separated by extractive distillation. Alkylated by the thylene, it leads to ethylbenzene then, by dshydrogenation, into styrene. Hydrogenated into cyclohexane, it gives nylon 6 (via caprolactame) or phenol. either de-alkylated into benzene + CH4 or dismuted into benzene and xylene (T = 450 C, zeolite) The toluene is:

Or transalkylated into xylenes (T = 450 C, No or / Mordenite) by reaction with aromatic C9 +.

Xylenes are isomerised on Pt/Zeolite, and then separated on molecular sieve (Eluxyl IFP, PAREX UOP). This separation leads selectively to orthoxylene , and particularly paraxylene. metaxylne has very few uses and is generally recycled to isomerization.

PETROCHEMISTRY : SELECTIVE HYDROGENATIONS (1)

THE ISSUE : need to selectively hydrogenate polyolefins or acetylenics towards olefins Impact on the choice of the technology and the catalyst C3 cut with MAPD
Methylacetylene (MAC) Propadiene (PPD)
H2

H2

Propylene
H2

Propane

2010 - IFP Training

C4 cut
Butadiene butenes butane

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SELECTIVE HYDROGENATIONS (2)


C2 Hydrogenation Demethaniser
C2 C=C=C CC-C

Hydrogen

Ethylene C3 hydrogenation (liquid or gas phase)


C=C

Deethaniser

Propylene
C-C=C

Depropaniser splitter

C4 total hydrogenation Butanes Butadiene C4 Selective hydrogenation


C4

C4 : hydrog residual BD , hydroisomrisation Butenes

Butadiene extraction
hydrogenation of pyrolysis gasoline

2010 - IFP Training

Debutaniser

BTX Gasoline

58

THE ISSUE : need to hydrogenate polyolfins or acetylenics AND STOP at the olefin step C3 cut: C=C=C ou CC-C C4 cut: Butadiene +H2 butenes without butane

+H2

C=C-C without C-C-C

Interactions between refining and Petrochemistry

H2

Pyrolysis gasoline REFINING PETROCHEMISTRY

Olefins (from FCC)

B,T,X (from catalytic reforming)


2010 - IFP Training

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Conclusions: Overview of catalytic processes


Catalysis is involved in most refining products and processes CATALYST = STRATEGIC MATERIAL
increase the desired reaction rates orientate selectively to desired products / yields

Besides thermal processes (visbreaking, coking, steamcracking), catalysts are widely spread in refining industry, mostly to:
meet product requirements: quantities (market) and quality (specs) take into account environmental challenges promote major refining processes
e.g. reforming, isomerisation, HDT, FCC, HCK, etherification and alkylation
2010 - IFP Training

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