Fcccatalystdesignmorphphysiooptimization 150107212315-conversion-gate01

FCC Catalyst Design Morphology, Physiology, Reaction

Chemistry and Manufacturing

Gerard B. Hawkins Managing Director, CEO

Introduction

FCC Catalyst Components - the Zeolite - the Matrix - Additives ( ZSM-5, other )

Catalyst Manufacturing

Reaction Chemistry - b scission (cracking) - hydrogen transfer - heat balance considerations

Selecting the Right Combination

FCC: POSITION IN REFINERY

In the FCC unit high mol. wt. feeds

(VGO / Residue) are converted to lighter, more valuable, products

C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG

C3=, C4='s, i-C4 for alkylation i-C4= for MTBE

Fuel Gas H2, C1, C2, C2=

Gasoline C5 - 221°C

Kerosene 150 - 250°C

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Crude Atmospheric Column

Straight Run Products

Atmospheric Residue Vac. Gas Oil

Vacuum Residue

Vacuum Column

Residue Hydrotreater

HT Resid

www.gbhenterprises.com

FCC Unit Operating Conditions : Typical Example

DISENGAGER

RISER REGENERATOR

190°C

735°C

720°C

Stripping steam

Produc ts

Regenerator flue gas

Regenerator Air

530°C

510°C

250°C

Catalyst Physical Properties

RETENTION / LOSSES - Attrition Resistance

FLUIDIZATION - Particle Size Distribution - Average Bulk Density

HEAT TRANSPORT - Specific Heat Capacity

FCC Catalyst Components

70 µm (avg.)

Pseudo crystalline Matrix Aluminas

Binder Zeolite Y

FCC Catalyst Components

Primary catalytic component for selective cracking Can be substantially modified to alter its activity,

selectivity and effect on product quality Generally rare-earth exchanged or ultrastable Y

zeolites More than 10,000 times more active than amorphous

catalysts used before the introduction of zeolite Y

Zeolite

Role of the FCC Catalyst Matrix

Forms the continuum that holds together the zeolite crystals

Acid sites on active matrix component catalyze cracking of feed molecules too large to enter zeolite pores

Matrix porosity facilitates diffusion of feed molecules to zeolite

Metals traps (e.g. for Vanadium or Nickel) may be incorporated in the matrix

Matrix

The Zeolite

Structure of Zeolite Y

Sodalite cage (β-cage)

Supercage (α-cage)

(Mn+)z/n {(SiO2)y (AlO2)-z} framework

Zeolites are crystalline microporous, alumino silicates

Framework alumina (AlO2)- units are associated with Acidic Active Sites

Cations within microporous cages and channels (Mn+ = H+, La3+, Ce3+, Ce4+)

Hydrocarbon conversion catalyzed at acid sites within microporous channels

Acid Site Activity and Acid Site Density determine the Activity and Selectivity of the zeolite

Zeolite Structure and Properties

Zeolite Acidity Brönsted acid

Lewis acid site

Al Si Si

Proton (H) donor

Trivalent Al - hydride ion abstractor

Brönsted Acid Site

Routes for Zeolite Y Stabilization

RE ion-exchange calcine NH4

+ ion-exchange

NaY REY CREY NH4CRE

+ ion-exchange ultrastabilize RE3+ ion-exchange

NaY NH4Y USY REUSY

Ion Exchange to Generate Acid Sites (H+)

Na+-Z- + NH4+ Na+ + NH4

+-Z- NH4

+-Z- H+-Z- + NH3 ↑

calcine

3Na+-Z- + RE(H2O)63+ 3Na+ + RE(H2O)6

3+-[Z]3-

RE(H2O)63+-[Z]3- RE(H2O)5(OH)2+ -H+-[Z]3-

hydrolysis

Ammonium Exchange

Rare Earth Exchange

Reaction Mechanism for Hydrothermal Dealumination and Stabilization of Y Zeolites

Framework Dealumination

Framework Stabilization

Al O Si O Si

O Si O Si

H H H H

(Steam) +Al(OH)3

O Si O Si

H H H H

Hydroxyl Nest

(defect site)

Si O Si O Si

(Steam)

Hydroxyl Nest

(defect site)

Unit-Cell Size and Si/Al ratio

Numerous relationships given in the literature

Breck and Flanigen relationship widely used

NAl / ucs = 115.2 [ ao - 24.191 ]

and: NSi / ucs = 192 - NAl / ucs

thus: Si / Alframework = NSi / NAl

Control of the equilibrium UCS

UCS (Å)

As-synthesized NaY 24.64 (54 Al / uc) Ultra stabilized Y 24.54 (40 Al / uc) Steam deactivated USY 24.21-24.30*(2-13 Al /uc)

*Depends on rare-earth level - (the higher the RE, the higher the UCS)

RE level vs UCS (Å)

0 10 20 30 40 50 60 70 80 90

24.21 24.26 24.31 24.36 24.41

UCS (Å)

Zeolite Active Site Distribution

Equilibrium US-Y Zeolite unit cell size 24.25 Å Framework Si/Al = 27 7 Al atoms / unit cell

Equilibrium CREY Zeolite unit cell size 24.38 Å Framework Si/Al = 7.8 22 Al atoms / unit cell

Dealumination Effect of Si / Al ratio on Zeolite

Properties

High Al Low Al

zeolite unit cell size thermal stability

hydrothermal stability

intrinsic cracking activity hydrogen transfer activity

low high high

low low

high low low

high high

Major Effects of Equilibrium Unit Cell Size

Increasing Unit Cell Size : Increases Active Site Density Decreases Active Site Strength

Hence, Increased Hydrogen Transfer vs. Cracking :

Increased Gasoline Selectivity Lower Gasoline Octane Numbers (RONc and MONc)

Decreased LPG (C3 and C4) Selectivity Lower LPG Olefinicity

Octane Response vs. Zeolite Unit-Cell Size

Gasoline

24.24 24.28 24.32 24.36 24.40

Zeolite Unit Cell Size, Å

elta Gasoline Yield, W

Increasing rare earth

Relative Coke Selectivity of Zeolite Types

Equilibrium Unit Cell Size

CREY unit cell size range for minimum coke 24.28 - 24.34 Å

CSSN CSX

The Matrix

Selective Active Matrices Catalytically active surface

Less selective in cracking than zeolite

Variable acid site strength and pore structure

Helps crack the bottoms to provide ‘feed’ for the zeolite component

Important for metals tolerance

Matrix Design Considerations

Crack bottoms with minimum coke and gas penalty Provide resistance to Nickel, Vanadium and Nitrogen Controlled porosity eliminates heavy feed diffusion limitations

The appropriate Matrix type depends upon feed characteristics (e.g. aromaticity, Concarbon, metals, nitrogen, etc.)

Optimize Zeolite / Matrix ratio for low coke and gas as well as low SA/K number

Matrix Requirements

Example Morphologies

Tuneable Matrix Alumina (TMA)

Matrix Technology

Matrix System Type 1 Type 2 Type 3

Bottoms Cracking

Coke/Gas Selectivity

Vanadium Tolerance

Nickel Tolerance

Optimal matrix system is selected depending on the main operating objectives / constraints as below

10 100 1,000 10,000

Catalyst A (steamed) REUSY High Matrix Activity

Catalyst B (steamed) REUSY Moderate Matrix Activity

Pore Diameter, (Å) www.gbhenterprises.com

Ni Ni Ni

Highly Dispersed - Poor Ni Tolerance Good Ni Support High Ni dehydrogenation activity

Nickel Tolerance - Matrix Consideration

Ni Ni Ni Ni Ni

Ni Ni Ni Ni

Nickel Agglomeration Chemical Reaction Poor Ni Support Low Ni dehydrogenation activity Å 100

NiAl2O4

Solid State Diffusion Chemical Reaction Strong Metal-Support Interaction Low Ni dehydrogenation activity

Ni trapping matrix

solid state

diffusion

SA/K Number

Lower SA/K number:

improves catalyst strip ability (decreasing occluded coke)

provides a poorer support for contaminant metals (decreasing contaminant coke)

Both the above contribute to improved coke and gas selectivity

AVOID EXCESS CATALYST SURFACE AREA - ONLY NEED SURFACE AREA THAT CONTRIBUTES TO PRODUCING DESIRED

CONVERSION PRODUCTS

SA/K number = Total ECat Surface Area Kinetic Conversion

= Total ECat Surface Area MAT Conv. / (100 - MAT Conv.)

Major Effects of Increased Z/M Ratio

Increasing Z/M : Increases Selective Zeolite Cracking Lower Coke and Fuel Gas (C2-) Yields Increased Gasoline Selectivity

But, Lower LCO Selectivity Increased Bottoms Selectivity

Effect of Zeolite/Matrix Ratio on Product Selectivity's

MAT Reaction Conditions: 60 wt% conversion Feed: 0.919 g/ml, 11.5 Watson K

Zeolite / Matrix Surface Area Ratio of Steamed Catalyst

Amorphous Cracking

Zeolite Cracking

44.0 G

FCC Additives

ZSM-5 Additives

ZSM-5 Additive Particle

MICROSTRUCTURE MESOSTRUCTURE

MACROSTRUCTURE

75 µm

Zeolite ZSM-5

Binder

Filler

ZSM-5 framework structure ZSM-5 pore structure

Zeolite ZSM-5 Crystal Structure

ZSM-5 Shape Selectivity

Products

Reactants

Non-reactants

Selective Conversion of Low Octane Species

The relative cracking for various hydrocarbons are:

Rel. rate Rel. octane Hydrocarbon Type

Straight chain paraffins & olefins

Moderately branched paraffins & olefins

Highly branched paraffins & olefins

Naphthenes

Aromatic side-chains

Moderate

ZSM-5 Additive Technology Cracking Mechanism

Hydrogen Transfer

Low active site density of ZSM-5 (relative to H-Y) results in low hydrogen transfer activity thus products have a high degree of olefinicity

Isomerization

Isomerization of lower to higher branching is favored due to the relative stabilities of carbo-cation intermediates (tertiary > secondary > primary)

Commercial Data: Unit Response to 3 wt% Additive Addition

-40 -30 -20 -10 0 10 20 30

Days into ZSM-5 Usage

ZSM-5 Additive Provided an Immediate

1.8 RON Gain

64 68 72 76 80 84

Conversion (wt%)

ECAT 521°C ECAT 543°C ECAT 566°C 4% Additive 521°C 4% Additive 543°C 4% Additive 566°C

DCR Testing of ZSM-5 Additive: Propylene Yield

64 68 72 76 80 84

Conversion (wt%)

) DCR Testing of ZSM-5 Additive: Alky

Feed Yield

ECAT 521°C ECAT 543°C ECAT 566°C 4% Additive 521°C 4% Additive 543°C 4% Additive 566°C

Yield and Octane Shifts With ZSM-5 Additives

Low octane gasoline components are converted to LPG olefins Gasoline composition changes:

decreased paraffins and olefins in "octane-dip" range increased light iso-paraffins increased light olefins increased aromatics (via concentration)

No change in coke, dry gas, or bottoms yield

Gasoline RONc and MONc increased

Environmental Additives

Sulfur Balance in an FCC Unit

Feed Sulfur Sulfides Thiophenes Benzothiophenes Multi-ring Thiophenes

Light Gases, H2S 20 - 60%

Gasoline 2 - 10%

Light Cycle Oil 10 - 25 %

Heavy Cycle Oil 5 - 35 %

Coke, SOx 2 - 30 %

• FCC gasoline typically contributes >90% of the total gasoline pool sulfur • Up to 50% of FCC gasoline sulfur is usually concentrated in the back end of the gasoline

Catalytic SOx Reduction

PRODUCTS ( with H2S )

MeSO4 (s) + 4 H2 (g) = MeS (s) + 4 H2O (g)

RISER: Reduction of Metal Sulfate

MeSO4 (s) + 4 H2 (g) = MeO (s) + H2S (g) + 3 H2O (g)

Stripping Steam

STRIPPER: Hydrolysis of Metal Sulfide MeS (s) + H2O (g) = MeO (s) + H2S (g)

FEED ( with Sulfur )

FLUE GAS ( with SOx )

Regenerator Air

REGENERATOR: Formation of SOx S (coke) + O2 (g) = SO2 (g)

SO2 (g) + ½ O2 (g) = SO3 (g)

Formation of Metal Sulfate SO3 (g) + MeO (s) = MeSO4 (s)

FEED SULFUR IN GASOLINE vs GASOLINE CUT POINT

180 185 190 195 200 205 210 215 220 225 230 Gasoline C.P. (ºC)

W/O Additive Comp X

Comp X Allowed Refinery C to Reduce Sulfur by ca. 20-25%

NOx Emissions: XNOx vs. Pt. Promoter

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

Addition of 0.5% XNOx

Addition of Pt based Promoter

60% Reduction

Catalyst Manufacturing

Synthesis of Zeolite Y

NaSiO3 NaAlO2

Al2(SO4)3 Seeds

ca. 100°C, 1-2 days www.gbhenterprises.com

Sulfate Aluminate

Silicate Aluminium

Sodium

Seeds ML-Gel

Sulfate

Beltfilter

Effluent

Aluminium

Beltfilter Na-Y Zeolite

ZEOLITE PLANT (Part 1)

RE-Y Zeolite

(NH4)2SO4

RECl3 /

Beltfilter

Effluent

NH4-Y /

Bag Filter System

Calciner

US-Y Zeolite CREY /

ZEOLITE PLANT (Part 2)

RE-Y Zeolite

NH4-Y /

Hot Air

Binder Water Clay

Mixing

Calciner

CATALYST FCC

FCC PLANT

Beltfilter LS-USY

(NH4)2SO4

Effluent

RECl3 /

WET END

Spray Drier

Hot Air

Scrubbing System

DRY END

Zeolite (e.g.. CREY/USY)

Mixing

Reaction Chemistry

Boiling Range Distribution of FCC Feed and Products

Boiling Point, °C

Gas LPG Naphtha LCO Slurry /

Feedstock 40

PRODUCTS

Hydrocarbon Types CHAIN STRUCTURES

Paraffin

H H H H

H H H H H H

RING STRUCTURES

Olefin

H H H H

H H H H H

Naphthene

Alkylaromatic H

H H H H

Crackability (Conversion): Paraffinic > Naphthenic > Aromatic

Coke-forming tendency (Heat Balance): Paraffinic < Naphthenic < Aromatic

Principles of Catalysis

Catalysts Lower Activation Energies of Forward & Backwards Reactions, Increasing the Rates of Both The Heat of Reaction is Unchanged by the Catalyst The Position of Thermodynamic Equilibrium is Unchanged by the Catalyst Non-Equilibrium Distributions Occur Under Kinetic Controlled Conditions

Reaction Co-ordinate

ECatalytic

∆ Hreaction

EThermal

Thermal vs Catalytic Cracking n-Hexadecane @ 500°C

Carbon Number

C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14

Catalytic Cracking

Thermal Cracking

Principle Reactions in FCC

Olefins Cracking Light Olefins

Isomerisation other Naphthenes

Naphthenes Cracking Olefins

Transalkylation other Aromatics

Aromatics Side-chain Cracking

unsubstituted Aromatics + Olefins

Dehydrogenation poly-Aromatics

Dehydrogenation Coke

Condensation Condensation

Dehydrogenation cyclo-Olefins

Dehydrogenation Aromatics

Cracking Paraffins + Olefins Paraffins

H Transfer Paraffins

Condensation Cyclisation

Naphthenes Dehydrogenation

Olefins Paraffins Isomerisation H Transfer Branched Branched

β - Scission (cracking) Reactions

Cracking Reaction Mechanism

Si O -

Catalyst (Acid Site)

H H H H

Carbenium Ion H

H H H H

Protonation

H H H H

ß-scission

Olefin Product

H H H H

Intermolecular Rearrangement

Deprotonation

H+ www.gbhenterprises.com

Thermal Reaction Mechanism

Thermal cracking gives high yields of methane, alpha-olefins and ethylene, no increased branching

H H H H H

H H H H

Free radical formation

- H . Secondary Free radical

H H H H

ß-scission (Cracking)

Primary Free radical

alpha- Olefin Product

ß-scission (cracking) Ethylene

New free radical

homolytic fission

C H homolytic fission

C C homolytic fission

Summary of Cracking Reactions

Relative Cracking Rates: Olefin > Naphthene = Alkylaromatic > Paraffin

Olefins most readily form carbocations

Aromatic side-chains readily undergo cracking reactions, however, aromatic rings do not crack

Alkylaromatic Alkylaromatic + Olefin

Naphthene Olefin

Paraffin Paraffin + Olefin

Olefin Olefin + Olefin

Hydrogen Transfer Reactions

olefin + naphthene paraffin + cyclo-olefin

Hydrogen Transfer Reactions

olefin + cyclo-olefin paraffin + cyclo-diolefin olefin + cyclo-diolefin paraffin + aromatic

CH - CH2

CH2 - CH2 CH - R” H2 C

R - CH - CH2 - R’ +

H+ R - CH = CH - R’

olefin protonation

R - CH - CH - R’ H

hydrogen transfer

R - CH - CH2 - R’

CH - CH2

CH - CH

+ CH = CH

CH2 - CH2 CH - R” H2 C - H+

proton loss

Heat Balance Considerations

FCC Heat Balance Considerations

Most FCC process variables have an effect on the heat balance - which, in turn, affects: Conversion, Yields and Product Qualities

The FCC unit will always adjust itself to remain in heat balance by burning enough coke for the energy requirements

Heat Demands are Satisfied by Burning Coke

∆H air

ENERGY IS REQUIRED TO

HEAT AIR

∆H cracking

ENERGY IS REQUIRED TO CRACK FEED

∆H vaporization

ENERGY IS REQUIRED TO

VAPORISE FEED

∆H losses

ENERGY IS REQUIRED FOR

HEAT LOSSES TO ATMOSPHERE

FCC Delta Coke Types

Occluded Feed Metals Catalytic

unstripped hydrocarbons (product to regenerator) high hydrogen content uncracked heavy feed components e.g. asphaltenes, Conradson carbon residue Formed via dehydrogenation activity of contaminant metals e.g. nickel, vanadium formed as a bi-product of desired catalytic cracking

VGO 14%

Feed Dependence of Delta Coke

Contaminant Coke (Metals Coke) Increases

Feed Residue Coke (Conradson Carbon) Increases

Occluded Coke (Cat/Oil Coke) Same / Slight Increase

Catalytic Coke (Conversion Coke) Decreases

Contaminant Coke

Feed Residue Coke

Occluded Coke 0.10

Catalytic Coke

Decreasing Feed Quality Increasing: Density, ConCarbon, Metals, S, N.

Increasing Resid Content Increasing Ca/Cp ratio, Endpoint

Conversion Dependence on Delta Coke

Lower conversion by :

higher regen. temperature

lower cat/oil (lower severity)

Lower effective activity due to :

coke blockage of pores

metals contamination

increased nitrogen poisoning

ion Regen T

Cat/Oil Ratio

Unit Conversion

Delta Coke, wt.%

Increasing Resid content

Constant Riser Outlet Temp. Constant Coke Operation (Unit at Max. Blower Capacity)

Selecting the Right Combination

Gasoline Mode Operation

FCC Optimization for Gasoline Production

high Zeolite / Matrix ratio (Z/M) high Hydrogen Transfer (high ucs) high Catalyst Activity (Conversion)

Gasoline C5 - 221°C Kerosene 150 - 250°C

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Gasoline Selectivity is favored by:

FCC Optimization for Gasoline Production

high Catalyst / Oil ratio moderate Riser Outlet Temperature high ECat Activity (MAT)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Gasoline Selectivity is favored by:

Distillate Mode Operation

FCC Optimization for Middle Distillates

Production

high Matrix Activity (lower Z/M) high Hydrogen Transfer (high ucs) low Catalyst Activity (low Conversion)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Middle Distillate Selectivity is favored by:

FCC Optimization for Middle Distillates

Production

low Catalyst / Oil ratio low Riser Outlet Temperature low ECat Activity (MAT) use of Recycle (HCO/Slurry)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Middle Distillate Selectivity is favored by:

Light Olefins Mode Operation

FCC Optimization for Light Olefins Production

low Hydrogen Transfer (low ucs) use of ZSM-5 Zeolite containing additives high Catalyst Activity (very high Conversion)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Light Olefin Selectivity is favored by:

FCC Optimization for Light Olefins Production

high Riser Outlet Temperature high Catalyst / Oil ratio high ECat Activity (MAT)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Light Olefin Selectivity is favored by:

Short Contact Time Operation

FCC Optimization for Short Contact Time

Operations

high Catalyst Activity balanced Zeolite/Matrix ratio (Z/M) high Hydrogen Transfer (high ucs)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Short Contact Time Operation is favored by:

FCC Optimization for Short Contact Time

Operations

high Riser Outlet Temperature high Catalyst / Oil ratio high ECat Activity (MAT)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Short Contact Time Operation is favored by:

Gasoline Olefins Reduction

FCC Optimization for Gasoline Olefins

Reduction

high Zeolite / Matrix ratio (Z/M) high Hydrogen Transfer (high ucs) moderate Matrix Activity (SAM-700) high Metals Tolerance (e.g. Ni and V)

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Gasoline Olefins Reduction is favored by:

FCC Optimization for Gasoline Olefins

Reduction

high Catalyst / Oil ratio low Riser Outlet Temperature high ECat Activity high Conversion

Cat. Heating Oil

Diesel 200 - 350°C

FCC UNIT

Vacuum Residue

Vacuum Column

HT Resid

Gasoline Olefins Reduction is favoured by:

Questions ?

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