ROLE OF CATALYSIS IN PETROLEUM

REFINING AND PETROCHEMICAL

INDUSTRY
INDUSTRY & CATALYSIS

GLOBAL SCENERIO
Chemical/Hydrocarbon industy: $ 1.5 Trillion global
enterprise
Catalysis: The key to economic & environmental viability
of the industry
More than 7000 products manufactured per year using
catalysts
Catalyst market: $ 10 Bill. Industry
Major segments Growth rates (%)
Refining & Petrochemicals 2
Hydroprocessing 5-7
Polymerization 7-10
Chemicals 5
Environmental 10
CATALYSIS IN CHEMICAL INDUSTRY:
APPLICATIONS

Petroleum
Petroleum
refining
refining
Environ-
Environ- Petro-
Petro-
mental
mental chemicals
chemicals
protection
protection

Catalysis
Catalysis

Fine
Fine&& Fertilizer&
Fertilizer&
Agro
Agro Inorganic
Inorganic
chemicals
chemicals chemicals
chemicals
Pharma-
Pharma-
ceutical
ceutical
DEVELOPMENT & COMMERCIALIZATION
OF CATALYSTS: KEY ELEMENTS
Research & Development

Innovation/Intellectual Property Rights

Pilot scale efforts, scale up & process economics

Product & Process technology development

Process engineering / Instrumentation/Construction

Process licensing

Manufacture

Marketing

Technical services
Catalyst Life-Reactor type
 FCC CATALYST
CLAY

Re-EARTHS ZEOLITE

MATRIX

Source Sobhan Ghosh, Managing Innovation, Feb07

 Matrix
Matrix - non zeolitic catalyst component, - clay & binder.
Can be silica or alumina or silica / alumina type.
1. Provide particle size & shape for fluidization.
2. Determine catalyst attrition characteristics
3. Accessibility to zeolite.
4. Embedding additives.
5. Has cracking activity.
6. Improved bottom cracking.
7. Zeolite to active matrix ratio carefully controlled
Source- J.Biswas and I. E. Maxwell, Shell Research, Recent process and catalyst related developments in FCC
 Additives
SOx reduction : Reduce sulfur oxide in flue gases.
Adsorbs SO3, reacts forming metal sulfates, carried to
reactor and reduced to H2S.
NOx conversion
Bottoms conversion; Catalyst particles containing
active matrix increasing yields of LCO/ gasoline at
the expense of MFB. (MFB: main fractionator
bottoms )
Metal Passivators: Liquid added to feed to reduce
-ve effects of metal deposited on the cat (Sb/Bi)
V traps: Collect V from feed & prevent from reacting
and destroying zeolites in cat
 Assessment of catalyst quality

1. Activity and selectivity

2. Metals analyses
3. Carbon on catalyst
4. Physical properties
5. Fresh catalyst analyses
MAT/FST Conversion (wt%) [FST: Fluid-Bed Simulation Test ]

The FST conversion, the indication of catalyst activity, is

calculated from the mass balance as:
% conversion = 100 LCO slurry = coke + gas + LPG +
gasoline
The E-cat activity is measured at standard conditions of cat/oil
ratio, contact time, reactor temperature, and so on. It can be
related to the commercial unit performance, allowing the refiner
to distinguish between catalyst activity effects and process or
feed quality influences. A detailed study of unit performance is
needed to find the optimum catalyst activity.
In general, a higher catalyst activity results in:
improved conversions
higher regenerator temperatures
lower cat/oil ratios
Hydrogen Factor (HF)

The hydrogen factor is a relative number, proportional to the specific hydrogen yield.
Specific hydrogen is defined as:
Specific H2 = H2 yield x (function of FST conversion)
The hydrogen factor depends on the catalyst quality and is affected by the nickel (and
other metals to a lesser extent) deposited on E-cat. Only the trend of HF is important,
and it can be correlated with the H2/CH4 ratio in the FCC unit.

Coke Factor (CF)

The coke factor is also relative, proportional to specific coke, defined as:
Specific coke = coke yield x (100 conversion) / conversion
Like the hydrogen factor, CF is affected by metals on the E-cat. The trend indicates
the contribution of the E-cat quality to the delta coke (coke on spent coke on
regenerated catalyst) in the commercial unit. However, delta coke depends mostly on
the feed quality and catalyst activity. It can also be calculated from unit data as:
Delta coke = coke yield (wt% on feed) / cat/oil ratio
CARBON ON CATALYST

In order to monitor the regenerator efficiency of an FCC unit, the residual

carbon on the regenerated catalyst is measured. In addition, the carbon on
the catalyst flowing from the reactor stripper to the regenerator (spent
catalyst) can be measured, which permits calculation of delta carbon,
proportional to the delta coke level.

The carbon is burned to carbon dioxide, which is analyzed using an infrared

detector. Apart from measuring the carbon on regenerated catalyst (CRC),
the carbon content can be estimated by the refiner, by comparing the color of
the E-cat with colors of reference samples from the same unit.
High carbon levels on E-cat do not affect the measured activity, since
samples are tested after calcining. But a higher level does reduce the
effective catalyst activity in the unit, requiring higher C/O ratio to maintain
conversion. At some level, yield selectivities will also start to suffer.
 Fresh catalyst analyses

Loss on ignition (LOI, wt %)

Weight loss upon heating at 600 oC for one hour

Attrition index (AI, wt %)

A sample of fresh catalyst is fluidized by high velocity air jet. Wear of the
particles occurs as they blow against each other and the wall at velocity.
The fines generated are removed from the attrition zone and weighted.

A lower attrition index indicates higher attrition resistance. Low catalyst

loss can be expected under normal unit conditions with attrition index
levels upto 10 %

Hot attrition test

Similar test with E-catalyst at 700 oC
 Particle Size Distribution
1. Circulation ability
2. Attrition Characteristics
3. Performance of Cyclones
4. Circulate effectively catalyst to have >100 micron
and < 40 micron (5 to 10 %)
5. An increase in catalyst fines in <20 / <40 micron
range,
6. Problems in regenerator air grid, large amount of
steam in regenerator, excessive velocities in feed
nozzle (>300fps) etc can cause increased attrition
 Surface Area
Monitors catalyst activity & stability.
Determined by nitrogen adsorption of decoked sample.
Total surface area associated with zeolites & matrix
Zeolite surface area primarily cracks gas oil range
molecules. Major product selectivity factor.
Matrix surface to crack heavy molecules & pre cracking of
oil to feed zeolites.
Surface area loss accelerated by high regenerator temp,
steam in regenerator & catalyst poisons (vanadium, sodium
etc.) (MAT: Micro Activity Test)
10 m2/ g surface area loss, drop in MAT activity by ~ 5
The main characteristics of a catalyst other than its physical and
mechanical properties are :

The activityo catalyst ability to increase the rate of desired reactions

o Is measured in terms of temperature

The selectivityo Catalyst ability to favor desirable reactions

o Practically measured by the C5+ Reformate and Hydrogen yields

The stability
o Change of catalyst performance ( activity, selectivity )with time
o Caused chiefly by coke deposit and by traces of metals in feed
o Measured by the amount of feed treated per unit weight of catalyst. C5+ wt
reformate yield is also an indirect measure of the stability
 R1

+ R2OH

R1

R1 R2 R1
R2

R2

R1

R2

Fig.2 Selective alkylation reactions over pore size

regulated zeolite
Prepr. Pap.-Am. Chem. Soc.,
Div. Fuel Chem. 2004, 49(2),
507
 Scientific challenges

The scientific challenges that relate to the design and

realization of catalysts for specific transformations
include the following:
Control of catalyst structures at the atomic and nanometer length scale
Understanding how catalyst structure evolves in a reactive
environment
Integration of multiple catalytic functions
Synthesis of three-dimensional nano-structured catalysts
Development of non-precious-metal catalysts with superior
performance
Combinatorial and high-throughput strategies for catalyst synthesis
and evaluation
 Nano scale-design:
The Ultimate art of Engineering

2.4 A - (111)Pt

2.0 A - (111)Ni

3-5 nm

TEM Image of TNR Catalyst

showing core-shell structure
[US7,700,005]
 Dream reactions waiting for a catalyst

Jens Rostrup-Nielsen: XVII Sympsio Iberoamericano de Catlisis, July

16-21, 2000
 PRIME APPLICATION AREAS FOR
IMPROVED CATALYSTS

REFORMING
Higher H2/C5 + Yield
HYDROTREATING
Higher HDS activity
More hydrogenation
HYDROCRACKING
Higher HDS/HC activity
RESIDUE CONVERSION
 REFORMING

Reforming is the main hydrogen producer in a

refinery; the continuous need for hydrogen favours
the implementation of continuous regeneration units.

On the other hand, the severe reduction of aromatics

in gasoline would oblige refiners to find new
hydrogen source.

Benzene management and C5 / C6 isomerisation are

the two immediate solutions.
 Catalytic Reforming in a Nutshell
Purpose Increase heavy-naphtha octane
Other Produce aromatics (BTX) for petrochemical plants
Produce hydrogen

Licensors Axens (IFP) BP

ExxonMobil UOP
Catalysts Pt on -alumina Pt-Re on -alumina
Pt-Re-Sn on -alumina
Promoters HCl

Feeds Hydrotreated heavy naphtha, 40 to 62 RON

Typical Process Conditions

H2/HC ratio up to 6.0
Reactor inlet temperature 900-970oF (482 521oC)
Pressure (Semi-regen., Cyclic) 200 500 psig (1480 - 3549 kPa)
Pressure (CCR) 100 150 psig (791 - 1136 kPa)

Typical Product Yields and Properties

Total C5-plus 84 to 85 vol%
H2 production 650-1100 scf/bbl (115-195 Nm3/m3)
RONC (Semi-regen., Cyclic) 85 to 95
RONC (CCR) Up to 105
 List of Catalytic Reforming Reactions

Naphthene Reactions Paraffin Reactions

Dehydrogenation to form aromatics Dehydrocyclization to form aromatics
Isomerization to form different naphthenes Isomerization to form other paraffins
Hydrocracking to form C4-minus

The catalyst affects reaction rates through its two different

functions/type of sites:
o Metallic, and
o Acidic

Different types of reactions are promoted by these sites as:

o Dehydrogenation - Metallic
o Dehydrocyclisation - Metallic + Acidic
o Isomerisation - Metallic + Acidic
o Hydrogenolysis - Metallic
o Hydrocracking - Metallic + Acidic
 Catalyst Chlorinated gamma alumina with nanao particle of Pt
The chlorinated gamma alumina has too strong acid sites
The Pt promotes hydrogenolysis

The stability of Pt has been improved by addition of promoters (Re, Ir)

The hydrogenolysis of Pt has been reduced by addition of promoters
The acidity of the chlorinated gamma alumina has been tuned by
addition of promoters
To improve the catalyst stability the Pt sintering has to be hindered
Addition of promoters
Rhenium or Iridium

Explanation
Re and Ir is alloyed with Pt , the boiling pointof Pt is increased ,
Sintering reduced
Reforming catalysts are bimetallic catalyst consisting of
platinum plus promoters on an alumina support, Rhenium
and Tin being essentially one of the promoter besides the
others.

The main features of these catalysts are :

o High purity alumina support - High mechanical resistance
o Platinum associated with Rhenium - high stability &
selectivity
o Platinum associated with Tin high selectivity
o High Regenerability

The combination of these qualities give the following

advantages:
o High Reformate yield
o High hydrogen yield
o High on - stream factor
o Low catalyst inventory
 REFORMING

SEMI REGENERATIVE REFORMER

PROMOTED BIMETALLIC CATALYSTS
(TRIMETALLIC CATALYSTS).
Moderate hydrogenalysis activity
H2 and gasoline yield are more
SKEWED CATALYSTS
Staged Loading
Lead Reactor : Dehydrogenation
Tail Reactor : Dehydrocyclisation
Higher hydrogenation activity of skewed catalysts
significantly decreases ring opening.
 CCR UNITS

Low Pressure
Cyclic Operation
Pt / Sn / Al2O3 Bimetallic Catalysts
Higher Product Selectivity
Low Benzene
High LHSV, Low H2 / HC Ratio
Higher Octane, H2 yield
 CCR catalysts face harsh conditions during
regeneration (~150 times / a year)
IMPROVEMENTS NEEDED
Hydrothermal stability need
Life of the catalyst need to be improved
Ability to retain chloride ion
Attrition resistance

FUTURE CHALLENGES
To develop a catalyst without chloride use.
 SCIENTIFIC CHALLENGES

Besides the other future plans in catalytic reforming,

the user industry demands the following
Get away from chlorination step
Developing catalyst with in situ acidity
Developing sulfur resistant catalyst
Developing catalyst with less platinum, if not no
platinum
These are perhaps the greater challenges not only
before Indian scientist but all over the world.
 ETHERIFICATION BY
CATALYTIC DISTILLATION

Offers a number of benefits such as reduced capital and

operating cost, economical use of low purity feedstocks,
simplicity of operation due to standard distillation controls.
The key to catalytic distillation technology is the catalyst
container system, i.e., structural catalyst packing.
There are many types of structural packing :
Cloth belt with catalyst filled in pockets
Fluidizing the catalyst on the tray etc.
Zeolite such as ZSM-5, ZSM-11 beta etc., have also been tested
to catalyse the reaction for MTBE production
Studies for the development of zeolite coatings on the distillation
packing are progressing to improve the thermal stability of the
catalysts.
 ALKYLATION

Production capacity 70 x 106 T/A

Alkylates are good blending stocks
High octane number
Low reid vapour pressure
PROCESSES
Liquid acids using HF or H2SO4
Corrosion
Disposal of large amount of acids
APPROACHES TO OVER COME
DISADVANTAGES

Supported liquid acids CF3HSO3/SiO2 (Tested pilot

plant level)
Solid acids
RE-Y, H-Y, , MCM, Super acids like SO4/ZrO2
Disadvantages
Low abundance of acid sites
Speeding up of olegomerisation reaction at reaction
temperatures.
FLUID CATALYTIC
CRACKING
FIG 1 - RISER CRACKER
 FCC in a Nutshell
Purpose Converts heavy oils into gasoline and/ or light olefins
Licensors Axens (IFP) ExxonMobil
KBR Stone & Webster
UOP
Catalyst and Additives
Zeolites (highly acidic, catalyzes cracking)
Rare-earth oxide (increase catalyst stability)
ZSM-5 (increase octane and production of light olefins)
Pt (promotes combustion of CO to CO2 in regenerator

Feeds Atmospheric gas oil Vacuum gas oil

Coker gas oil Deasphalted oil
Lube extracts Vacuum resid (up to 20 vol%)
Typical Feed Properties
Nitrogen <3000 wppm
Carbon residue <5.0 wt%
Nickel + Vanadium <50 wppm
90% boiling point <1300oF (704oC)
Typical Process Conditions
Feed temperature 300 700oF (150-370oC)
Reactor temperature 920 1020oF (493-550oC)
Regenerator temperature 1200 1350oF (650-732oC)
Catalyst/ Oil ratio 4.0 10.0
Reactor pressure 10 35 psig (170 343 kPa)

Typical Product Yields

Conversion 70 84 vol%
H2, H2S methane, ethane 3.0 3.5 wt%
Propane and propylene 4.5 6.5 wt%
Butane and butenes 9.0 12.0 wt%
Gasoline 44 - 56 wt%
LCO 13 20 wt%
Slurry Oil 4 - 12 wt%
Coke 5 6 wt%
TYPICAL FCC PROCESS CONDITIONS

PROCESS PARAMETER VALUE

Catalyst Inventor 200 Ton

Fresh Catalyst Rate 2-3 T/d
Feed Rate 3,300 T/d
Cat / Oil Ratio (W/w) 5-6
Linear Velocity 10 M/sec
Temperature In The Riser 525oC
Temperature Of The Feed 530oC
Temperature In The Regenerator 725oC
 Breakdown of FCC Heat Requirements
Heat Consuming Event Percent of Total

Heat up and vaporize fresh feed 40 50%

Heat recycled oil 0 10%

Heat of reaction (endothermic) 15 30%

Heat steam 28%

Heat losses 2 5%

Heat air to regenerator temperature 15 25%

Heat coke from the reactor to regenerator 1 2%

temperature
Total Heat Duty 500 1000 Btu/lb
1160 2325 kJ/kg
 IMPORTANT CHARACTERISTICS
OF FCC CATALYST
Bulk Density
Porosity and Pore Size Distribution
Zeolite Area and Total Area of the Catalyst
Attrition Resistance
Zeolite Crystallinity, Si/Al Ratio, Acidity and Acid
Strength Distribution
Particle Size Distribution
Thermal and Hydrothermal Stability
 MODERN CRACKING CATALYST
COMPOENTS

Active Component : Re-Zeolite, Modified Y-zeolite

Matrix : Silica-Alumina, Clays, etc.
Binders : Kaolinites, Hallosites, etc.
Additives : ZSM-5, Pt on Al2O3, etc.
 FUNCTIONS OF A MATRIX

As a Binder to the Zeolite

As a Porous Medium for Feed and Products
As a Diluant for the Active Zeolite
As A Metal Trap and Soldium Sink
To Facilitate Heat Transfer and Protect the Zeolite
To Function as Precracking Catalyst
 ADVANTAGES OF ADDITIVES

The Relative Ease In Adding or Withdrawing

The Effect is Apprent in Reasonable Period of Time

Avoid Cumbersome Task of Having to Change the

Complete Catalyst Inventory
 ADDITIVES

(A) Combustion Promoter Additives

Active Metals : Platinum, Palladium

Supports : Alumina, Silica-alumina
Catalyst Inventory : 250 Gms/ton Of Catalyst

(B) SOx Reduction Additives

Alumina
Magnesium Aluminate Spinels
Cerium On Alumina
 Sources of Sulfur in Gasoline (before 2004)
Component Contribution to the Contribution to Sulfur
Gasoline Pool (vol%) in the Pool (vol%)
Alkylate 12 0
Coker Naphtha 1 1
Hydrocracker Naphtha 2 0
FCC Gasoline 36 98
Isomerate 5 0
Light straight-run naphtha 3 1
Butanes 5 0
MTBE 2 0
Reformate 34 0

Total 100 100

 CATALYTIC CRACKING

ISSUES
Cat-cracked gasoline (CCG) is low in
aromatics but high in sulfur
Main supplier of alkylation feedstock
CCG olefin content may become a constraint
if gasoline olefin specification is reduced to
16% vol or lower
 REDUCTION OF GASOLINE
SULFUR CONTENT
Main source of sulfur in gasoline is FCC gasoline
Conventional ways to reduce sulfur content;
Desulfurise FCC feed
Fractionate FCCG in a three (or two) cut splitter, then;
Light CCG :
MEROX treating with mercaptan extraction.
Heat Cut :

Hydrotreating and platforming or selective hydrotreatment

Heavy CCG :
Selective hydrotreatment
New technology for desulphurisation of FCCG with minimum
loss of octane offered by CD-tech.
 Isomerization in a Nutshell
Purpose Convert n-butane to isobutane
Convert n-pentane and n-hexane to branched isomers
Licensor (C4) ABB Lummus Global BP
UOP
Licensor (C5C6) Axens (IFP) BP
UOP

Catalysts (C4) Pt on -alumina, HCl promoter Pt on zeolite

Catalysts (C5C6) Pt on -alumina, HCl promoter Pt on zeolite
Feeds (C4) dry n-butane
Feeds (C5) Light straight-run, end point <160oF (71oC)
Light reformate Light hydrocrackate
Natural gasoline Light aromatics raffinate
Process Conditions (Pt on alumina, chlorided)
Reactor temperature 250-300oF (121 149oC)
Reactor pressure 400 450 psig (2859 3204 kPa)
Process Conditions (Pt on zeolite)
Reactor temperature 445-545oF (230 285oC)
Reactor pressure 190 440 psig (1411 3135 kPa)

Conversion and Product Properties (C5C6)

Conversion (with recycle) up to 97%
RON 85 to 90
 ISOMERISATION
Moderate growth rate 1.5% year mainly due to
benzene management.
C5/C6 isomerisation compensates for the octane loss
due to benzene reduction
CATALYSTS
Amorphous
Pt/Cl-Al2O3
Low temperatures 120-150oC (Higher octane gain)
Low H2/HC ratio
No need for H2 recycle
Very sensitive to O2, S, Oxygen, Ammonia
Chloride Usage
 ZEOLITE CATALYSTS
Pt/modernite Pt/omega zeolite
H2/HC ratio more than 1.0
Hydrogen recycle needed
Relatively more tolerant to H2O, S, O2
Modernite catalysts work 250-270oC
Omega zeolite catalysts 230-250oC (Still higher than
amorphous catalysts)
New environmental friendly catalysts to do away with
chloride use
MoO3/Sic
Pt/SO4-TiO2 promoters Mn, Fe, Ni
High activities claimed
Sulfate elution is a problem
HYDROCRACKING
 Hydrocracking in a Nutshell
Purpose Convert heavy hydrocarbons into lighter hydrocarbons
Used for unconverted oil
FCC Feed Lube base stock
Olefin plant feed Recycle to extinction
Other Reactions
Sulfur removal (HDS) Nitrogen removal (HDN)
Olefin Saturation Aromatic saturation
Licensors Axens (IFP) Chevron Lummus
ExxonMobil KBR
Shell Global Solutions UOP
Catalysts NiMo on -alumina (HDS, HDN, aromatic saturation)
NiMo or NiW on zeolite (hydrocracking)
NiMo or NiW on amorphous silica-alumina (hydrocracking)
Pd on zeolite (hydrocracking)
Feeds Heavy gas oil Vacuum gas oil
Coker gas oil Residual oils
Typical Process Conditions
Reactor temperature 600-800oF (315 425oC)
Reactor pressure 1200 2500 psig (8375-17,338 kPa)
Range of Product Yields
Conversion (once-through) 20 90 vol%
Conversion (with recycle) 90-00 vol% fresh feed
C4-plus naphtha up to 120 vol% fresh feed
Middle distillates up to 90 vol% fresh feed
Hydrogen consumption 1000 to 3000 scf/bbl
175 to 525 Nm3/m3
 HYDROCRACKING CATALYSTS
Hydrocracking : Bifunctional Catalyst
Dehydrogenation and hydrogenation
Cracking

EXAMPLES

Optimizing zeolites for tailored selectivity

Catalyst design through optimisation of both functions
Improved hydrogenation for stability and product
quality
AMORPHOUS VS ZEOLITE CATALYSTS
IN HYDROCRACKING
PROPERTY COMMENT

Activity Zeolite is more active

Stability Zeolite is more stable
Selectivity Zeolite gives maximum naphtha
Amorphous gives maximum middle
distillate
Yield Stability Zeolite shows faster decline as a function
of increasing temperature
Feed Flexibility Zeolite requires recycle oil blend heavy
feeds
Product Quality Can be adjusted by hydrogenation
component for both types
List of Hydrotreating and Hydrocracking Reactions

Hydrotreating
(C-C bond breaking is minimal)
Hydrodesulfurization (HDS)
Hydrodenitrogenation (HDN)
Hydrodemetallation (HDM)
Saturation of aromatics
Saturation of olefins
Isomerization
Hydrocracking
(C-C bond breaking is significant)
Dealkylation of aromatic rings
Opening of naphthene rings
Hydrocracking of paraffins
 Comparison of Hydrotreating, Hydrocracking
and Mild Hydrocracking
H2 Partial Pressure
Process, Feedstock Types psig kPa Conversion
Hydrotreating
Naphtha 250 300 1825 2170 0 5%
LGO (Kerosene) 250 600 1825 4238 0 5%
HGO (Diesel), LCO 600 800 4238 5617 5 15%
VGO, VBGO, CGO, HCO 800 2000 5617 13,890 5 15%
Residual Oil 2000 - 3000 13,890 20,86 5 15%

Mild Hydrocracking
VGO, VBGO, CGO, HCO 800 1500 5617 10,443 20 40%

Hydrocracking
VGO, VBGO, CGO, HCO 1500 2000 10,443 13,890 60 99%
Residual Oil 2000 3000 13,890 20,786 15 25%

LGO = Light Gas Oil VGO = Vacuum Gas Oil

HGO = Heavy Gas Oil VBGO = Visbreaker Gas Oil
LCO = FCC Light Cycle Oil CGO = Coker Gas Oil
HCO = FCC Heavy Cycle Oil
DIESEL DESULFURIZATION
 Hydrotreating in a Nutshell
Purpose Sulfur removal (HDS) Nitrogen removal (HDN)
Olefin saturation Aromatic saturation (HAD)
Metals removal
Licensors Axens (IFP) CDTECH
Chevron Lummus ExxonMobil
Haldor- Topsoe KBR
Shell Global Solutions UOP

Catalysts CoMo on -alumina for HDS

NiMo or NiW on -alumina zeolite for HDS, HDN, aromatic saturation
NiMo or NiW on amorphous silica-alumina (hydrocracking)
Pd on zeolite (hydrocracking)
Feeds Naphtha Kerosene
Heavy gas oil Vacuum gas oil
Coker gas oil Residual oils
Typical Process Conditions
Reactor temperature 600-800oF (315 425oC)
Reactor pressure 250 2000 psig (1825-13890 kPa)
Required increase in catalyst activity (or bed
temperature to achieve different reduction in the
sulfur content of the diesel productsa

Product sulfur Required catalyst Required increase

(wppm) activity (%) in temperature(oC)

500 100 0
350 130 + 7
200 190 +17
100 300 +29
50 420 +38

a : 500 ppm is chosen as the base case and LHSV is kept

constant. The data are for a typical Co-Mo catalyst
 Easy
R
R
Difficult
Relation reaction rate

S S

R R
S
Most Difficult
R R
S

Impact of Sulfur Species

Relative Volume of the Catalyst
Bed Required for Achieving
Various Levels of Sulfur
 1 9
2 8

3 7
4 S 6
Hydrogenation
Direct

REACTION PATHWAYS FOR HDS OF DBT

-dCS k - CSn * PH2
=
dt (1 + KH2S * PH2S)

K * CSm * PH2
+
(1 + KF * CF)

DEEP HDS KINETICS

 RESIDUES HDS
PROCESSING RESIDUES WITH HIGH METAL
CONTENT REQUIRES
High demetallation activity
Metal capacity
Required levels of HDS
This can be achieved by utilizing a composite catalyst
system that contains various degrees of above said
activities
I. Front end system high HDM activity and metal
deposition capacity (very wide pore, high pore
volume, high crushing strength)
II. * Next catalyst system
* High HDM activity, good HDS, HDN and CCR
removal activity.
* Moderate metal deposition capacity

III. Hydrotreating catalysts located in the middle and

tail end have
Narrow pore structure
Very high activity for HDS, HDN and CCR removal
activities.
 CATALYST PERFORMANCE
REQURIEMENTS IN RESID UPGRADING

Residue Hydrotreating (RHDT) Residue FCC (RFCC)

Mass transfer and diffusion of heavy or large molecules
into the catalyst
Demetallisation (metal removal) Deactivation of metals
by encapsulation
Conradson carbon reduction Conradson carbon
conversion and /or
handling
Catalytic conversion (metal Catalytic conversion
sites) [HDS, HD CCR] (acid sites) cracking
of large molecules
CLAUS SULFUR RECOVERY PROCESS
H2S + 3/2O2 SO2 + H2O

2H2S + SO2 3/nSn + 2H2O 3/nSn + 2H2O

Catalysts : -Al2O3 based catalysts

Problem : COS and CS2 hydrolysis

New Catalysts : Based on TiO2

 HYDROGEN PRODUCTION
m + 2n
CnHm + mH2O nCO + H2
2

Catalysts : Ni/Al2O3 (promoters rare

earth ions and alkali)

New Catalysts : Ni/MgO, Ni/MgAl2O4

(alkali and ZrO2 containing)
 Refining Issues : Refinery
Hydrogen Balance
kt H2

Hydrogen deficit
Refinery capacity : 8 Mt/y

Low sulfur product

Less heavy fuel oil

New Supply:
- Partial oxidation
- Steam reforming
- Other sources
1990 2010

Production (catalytic reforming) Demand

Natural Gas Upgrading : Chemical Conversion
of Natural Gas
Natural
Naturalgas
gas(CH
(CH4)4)

Hydrogen Synthesis gas N2 Ammonia

(H2, CO, CO2)

+Olefins
-H2O Dimethyl
Methanol Fischer-Tropsch
ether Synthesis
+iC4=
+O2 +CO +iC5=

Olefins Gasoline Acetic acid Ethers: Oxo Olefins

Alcohols Paraffins
Aldehyde MTBE, Alcohols
Alcohols TAME

Hydroisomerization
Gasoline Pool

Kerosene Gas Oil Pool

PROCESSESS INVOLVING ZEOLITES
 Oil Fraction Catalytic Process Zeolite Used
Aromatization of Paraffins,
Olefins *
Oligomerization Alkylation
Gas *
Light Ends
Isomerization *

Hydrotreating Reforming
Naphtha *
Hydrotreating Dewaxing
Middle Distillate *
Dewaxing
Lube Oils
Catalytic Cracking Hydrocracking
Flashed Distillate
*
Hydrodesulfurization
Hydroconversion
Residue

Catalytic Processes For Different Part Of The Crude Oil Barrel

 COMPARISON OF CLASSICAL & NEW ROUTES FOR THE
PREPARATION OF CAPROLACTAM STARTING FROM BENZENE

CLASSICAL ROUTE NEW ROUTE

Benzene Benzene
+ 3H2 + 3H2 Ru Cat.
Adipic acid (nylon 66)

Cyclohexane Cyclohexene

Adipic acid (nylon 66)

+ O2 + HO2 [H]-ZSM-5
Cyclohexanol,-one Cyclohexanol,-one
+ O2 Cu-Zn + O2 Cu-Zn
Cyclohexanone Cyclohexanone
+NH2OH +H 2O2 TS -1
- (NH 4)2S04
+ H2SO4 +NH3

Cyclohexanone oxime Cyclohexanone oxime

+ H2SO4 - (NH4)2SO 4 Zeolite
Nylon 6 -Caprolactam -Caprolactam Nylon 6
Polyolefins
 Drivers for catalyst development

MI : Melt index ; Weight of polymer extruded through capillary during a 10 minutes

period under specified temperature and load condition
MFR: Melt flow ratio; the atio of MI value under two loads
MWD: Molecular weight distribution
Key Catalysts attribute
Progress in catalysts for polyolefins
Polyolefins catalyst family
Polyolefin catalyst technology life cycle
Polyolefin catalyst and their Characteristics
Conventional polyolefin catalysts

-Chrome on Silica
-Ziegler
Chrome on silica catalyst
Ziegler catalyst
PE Catalyst market 2008
Commercial PE catalysts
Poly Propylene
PP catalyst
Ziegler Natta catalyst
Ziegler Natta catalyst
Ziegler Natta catalyst
Internal Donor
Ziegler Natta catalyst
Commercial PP catalyst
Metallocene catalyst
Metallocene catalyst Market
Metallocene catalyst commercial platform
Post Metallocene catalyst
Late transition metal