GRACE FIELD OPERATION SERVICESGRACE FIELD OPERATION … .pdf · 2011-08-09 · Gasoline Merox MTBE...

GRACE FIELD OPERATION SERVICESGRACE FIELD OPERATION SERVICESFCC CATALYST PTR

Ricardo DuarteTechnical – Sales Manager LA.

onve

rsio

n

Gas

Yie

ld

PG Y

ield

ctan

e

lefin

Con

tent

rom

atic

Con

tent

CO

Aro

mat

ic

Con

tent

oke

Yie

ld

egen

erat

or T

emp

atal

yst/O

il

atal

yst E

ntra

inm

ent

yclo

ne E

ffici

ency

eq’d

Stri

ppin

g St

eam

Rat

e

Affected Variable

Adjusted Variable

Gasoline

onve

rsio

n

Gas

Yie

ld

PG Y

ield

ctan

e

lefin

Con

tent

rom

atic

Con

tent

CO

Aro

mat

ic

Con

tent

oke

Yie

ld

egen

erat

or T

emp

atal

yst/O

il

atal

yst E

ntra

inm

ent

yclo

ne E

ffici

ency

eq’d

Stri

ppin

g St

eam

Rat

e

Affected Variable

Adjusted Variable

GasolineGasoline

Increased CombinedFeed Temperature Increased RecycleRate Increased ReactorTemperature Increased ReactorPressure IncreasedRegenerator Pressure

Co

G LP O O Ar

LC C Re

Ca

C Cy

ReVariable


Co

G LP O O Ar

LC C Re

Ca

C Cy

ReVariable

Regenerator PressureIncreased CatalystCirculation Rate atConstant ReactorTemperature(Increased CatCooler Duty)

Change in Affected Variable: –increases; – decreases



ntGasoline ntGasolineGasoline

In creased C om b inedFe ed T em pera ture In creased R ecy cleRa te I d R

Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

nt

Aro

mat

ic C

onte

nt

LCO

Aro

mat

ic

Con

tent

Cok

e Y

ield

Reg

ener

ator

Tem

p

Cat

alys

t/Oil

Cat

alys

t Ent

rain

me n

Cyc

lone

Effi

cien

cy

Req

’dSt

ripp

ing

Stea

m R

ate

A ffected Va riable

Adjusted Variable

Gasoline


Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

nt

Aro

mat

ic C

onte

nt

LCO

Aro

mat

ic

Con

tent

Cok

e Y

ield

Reg

ener

ator

Tem

p

Cat

alys

t/Oil

Cat

alys

t Ent

rain

me n

Cyc

lone

Effi

cien

cy

Req

’dSt

ripp

ing

Stea

m R

ate

A ffected Va riable

Adjusted Variable

GasolineGasoline

In creased R eactorTe m perat ure In creased R eactorPr essure In creasedRe generato r P ressure In creased C atalystCirculatio n R ate atCo nstant R eac torTe m perat ure(In creased C atCo oler Duty)

C han ge in Affected Variable: –increases; – d ecreases



Why is the FCC Important to Refiners?Average Sized FCC

PRODU CT S:44,000 BPD@ $ 25/BBL

FEED:40,000 BPD@ $20 /BBL

Low Value F eeds to High Value Products =

Int roduct ion to U OP FC C T ec hno log y 3uop

FEED-PRODUCT DIFFERENTIAL = $300,000/Day

•Salamanca FCC PEMEX 2010

R efin ery Process F low

to 60 revamp engineering projects undertaken each year for the last 15 years

Cru deC o lu m n

C 4 a nd L ig h ter

St raig ht R un G a so line

K ero sin e

G a so lin ea n d L ig ht er

P ro duct sCo ker

G a s O ilH ea vySlo ps

V G O

Cru deO il

A G OF C C

D em ex

V acu umCo lum n

H y dro t rea t er

i

C y c le O ils

In t rod u ct ion to U OP FC C T ec h no log y 1u op

V a cuum R es id ue

•Salamanca FCC PEMEX 2010

Down stream Processing

to 60 revamp engineering projects undertaken each year for the last 15 yearsR eac tor

&R ege n

LP G P ool

Flu e G as

F u el G as A lk ylation A lk l t

C 3 /C 4Pa raffin s

R ege n .

G asolin eP ool

L PG

F u el G as

C 3 /C 4S p litter

A lk ylation A lk ylate

M ainC olu m n

&G as C o n

D ie selP ool

H eavy Fu el

M erox

G asolin eM erox

M TB E

D istillateH yd rotreaterL C O

G as olin e

In t rod u ct ion to U OP FC C T ec h no log y 2u op

H eavy Fu elO il P ool

H yd rotreaterL C O

C LO

PERFORMANCE TEST RUN FCC CATALYST

EQUIPMENTS

OPTIMIZATIONFeed NozzlesStripperC l I l t V l itCyclones Inlet VelocityRegenerator Temp ProfilePressure BalanceAdditives C0 / SOX/ NOX/ Olefins Promoter

Basic Unit Overview

FCC Technology Workshop - November 8 - 11, 2010 6

Reprinted with permission from The Shaw Group

Basic Unit OverviewV t S ti S t (VSS)Vortex Separation System (VSS)

Equipment 129uop


Reprinted with permission from The UOP

Main Column Overview

Reactor vapor is separated into products

LCN, LPG, Offgas

(Slurry, LCO, HCN, and overhead)HCN

HCO is also pulled but

LCO

HCO is also pulled, but pumped back to the Main Column.

Reactor Overhead Products

HCO PA

Slurry Bed

Slurry PA


Slurry

Gas Concentration Unit Overview

Note:WGC Wet Gas CompressorIR Interstage ReceiverHPR High Pressure ReceiverPA Primary AbsorberSA Sponge AbsorberS StripperD Debutanizer Dry Gas

LPGLiquid fromMC Overhead

Receiver

WGC

Gas fromMC Overhead

Receiver

Receiver

PA

SA S D

NaphthaWashWater

WGC HPRIR

LeanOil

RichOil

Sour Water


Oil and Catalyst Contacting

UOP High Efficiency FCC


•JORNADAS TECNICAS MADERO PEMEX 2010

El d N l f F d I j iElevated N ozzles for Feed Injection


uop•Ref UOP / NPRA

Equipm ent 13 7uop

Typical Radial Feed Nozzle Layout

Nozzles spread around riser to pallow full coverage of oil in the riser cross-section

This assures all the oil sees some catalyst, this helps vaporization and conversionvaporization and conversion


Reprinted with permission from Lummus Technology


Optimix Feed Distributor


Work Point

High DensityRefractory L ining

W elding NeckFlangeAbrasion

ResistantLining

SteamConnection

Ceram ic Fiber

g

uop

FeedConnection

B lanket InsulationR eactor R iser

Feed Distributor

•Ref UOP / NPRAEquipm ent 14 2uop

Radial Feed Distribution



Elevated Feed Nozzle Installation



Equipm ent 14 4uop

Feed Nozzle Spray Pattern

Steam is injected with the oil to break it up into small drops


Air and water test


Optimix Nozzle Spray Pattern



Equipm ent 14 1uop

Droplet Size vs. Catalyst Size

Poor Atomization

Oil

Catalyst


P At i ti G d At i ti

Droplet Size vs. Catalyst Size

Poor Atomization Good Atomization

Oil

Smaller drops prevent catalyst from getting

Catalyst

catalyst from getting overwhelmed



Incorrect Nozzle Installation



Equipm ent 14 6uop


E f f e c t o f F e e d D i s tr i b u to r

1 2 0 0

B ef o r e(S i n g l e N o zz l e)

A fte r(M u l t i p le N o z zl e )


1 7 F e e tA b o v e

F ee d I n l et

1 2 0 0

1 0 0 0

8 0 0

6 0 0

T e m p er a tu re , ° F

1 2 0 0

1 0 0 02 F ee tA bo v e 1 0 0 0

8 0 0

6 0 0

R is e r D ia m e te rR is e r D ia m e te r

F e ed I n le t

E q u i p m e n t 14 8u o p U O P 3 1 1 0 -9

•Ref UOP / NPRA


Oman, Sohar, OmanFCC Optimix Operating Chart

16000

Design Point at 2.50% SteamMinimum Steam During StartupUpper Boundary at 91.4 m/secLower Boundary at 45.7 m/sec


2.35b ar 2.64b ar 2.94b ar 3.26b ar 3.60b ar 3.94b ar 4.30b ar 4.68b ar 5.07b ar 5.47b ar 5.89b ar

13000

14000

15000

hr eam

)

Design PointMin. SU Steam

10000

11000

12000

Tota

l Ste

am, k

g/h

nclu

des

Split

Ste

1.98b ar 2.26b ar 2.54b ar 2.85b ar 3.17b ar 3.50b ar 3.84b ar 4.20b ar 4.57b ar 4.96b ar 5.36b ar

6000

7000

8000

9000(In

6000250 300 350 400 450 500 550 600

Feed, m3/hr (Standard)(Datalabel gives total pressure drop across Optimix feed distributor)

•Ref UOP / NPRA


D a m a g e d N o zz le T ip s


Eq u ip m e n t 14 7u o p

•Ref UOP / NPRA

Reprinted with permission of The Shaw Group

Riser Cyclone SystemsReprinted with permission of The Shaw Group

LD2Ramshorn RS2Inertial Tee

High P D

Large S t

Long R id Pressure Drop SeparatorResidence

Time



Riser Termination Technology

BASIS - MINIMIZE HYDROCARBON VAPOR RESIDENCE TIME AND CATALYST IN THE DISENGAGER VAPOR SPACE

VSSTM T h lVSSTM Technology

Minimize non-selective thermal reactionsthermal reactions Increased Gasoline Selectivity Increased LPG Olefin

A ASelectivity Reduce C2 - Lower Delta Coke


3040-15

Oil and Catalyst Separation

KBR OrthoflowKBR Orthoflow

CLOSED CYCLONE SYSTEMDISENGAGER

EXTERNAL FLUEGAS PLENUM

DYNAFLUX™ STRIPPING

REGENERATOR CYCLONESRISER QUENCH

REGENERATOR

SPENT CATALYSTDISTRIBUTOR

SPENT CATALYSTSTANDPIPE

AIR DISTRIBUTOR

REGENERATOR

ATOMAX-2™FEED INJECTION

REGENERATED CATALYST SLIDE VALVE

SPENT CATALYST PLUG VALVE

AIR DISTRIBUTOR

EXPANSION JOINT


Reprinted with permission of KBR

REGENERATED CATALYST STANDPIPE

Riser Termination Devices



Cyclone Basics

• Gas and Catalyst enter togetherINLET

CYCLONE VORTEX FLOWCLEAN GAS OUTLET

together

• Catalyst slows as it rubs

INLET DESCENDING GAS STREAM

GASES TRANSFER FROM DESCENDING STREAM TO EXITING against the cyclone wall

and falls into the diplegs

STREAM TO EXITING STREAM ALL ALONG INTERFACE BETWEEN THE TWO STREAMS

EXITING GAS

• Gas does not slow as much and flows out the top

STREAM CONE OUTLET

CONE APEX

TERMINATION OF GAS STREAMS IN HOPPER

CONE APEX


Reprinted with permission of Marsulex

Cyclone Basics


With permission of Martin Rhodes Monash University - “Fluidization of Particles with Fluids” www.erpt.org/012Q/rhod-00.htm

Cyclone Basics

R egenerator Cyclones

Equ ip m ent 10 6uop


With permission of Martin Rhodes Monash University - “Fluidization of Particles with Fluids” www.erpt.org/012Q/rhod-00.htm

Gas OutletWhy Are Cyclones So Important?

Gas Inlet

Gas OutletIF:Cat Circ = 80 TPM = 115,200 TPDRiser Termination = 75% Efficient8 Sets of Cyclones

THENTHEN:

1st Stage Cyclones (typically 99.95% Eff)

28 800 TPD Catalyst (3600 TPD each)Dipleg

28,800 TPD Catalyst (3600 TPD each)

2nd Stage Cyclones

14.4 TPD Catalyst ( 1.8 TPD each)Counter weighted flapper valve

14.4 TPD Catalyst ( 1.8 TPD each)


Cyclone Components

Splash Plate

Typically Found on:

Primary Regenerator Cyclones

Primary Direct Connect Rx Cyclones (stripper baffles serve as plate)(stripper baffles serve as plate)

Buried during normal operationg


Cyclone Components

Trickle Valve

(partially shrouded)

Can operate buried or unburied

Counterweighted Flapper Valve

Operate unburiedOperate unburied

Photo provided courtesy of Marsulex Environmental Technologies LLC


Cyclone Components

Regenerator Cyclone Dipleg Terminations

Equipment 11 1uop


“Typical” Cyclone Velocities

Cyclone Type Inlet Velocityft/sec

Outlet Velocityft/sec

Direct Connect Cyclone

55-60(Revamp – 60-65)

65 - 100

Primary 65(Revamp – 75)

80 - 100

Secondary 75 100 - 150Secondary 75(Revamp – 85)

100 - 150

Dipleg Flux, lb/ft2/sPrimary Riser Termination

60-70

Typical Cyclone Diplegs

100 - 150


60 70 100 150

Estimated C clone Performance

Fluidization Case StudyEstimated Cyclone Performance

50

Loss

, %

30

40

Cat

alys

t

5-Year Run

20

30

ncre

ased

3 Y R10

bilit

y of

In 3-Year Run

60 70 75 80 85650

Inlet Velocity, ft/sec

Prob

ab

UOP 2569G-02


Common Cyclone Problems



Catalyst StrippingReprinted with permission of The Shaw Group

SWEC-IFP R2R


Modern Stripper DesignsHigh Efficiency Trays PackingHigh Efficiency Trays Packing


Stripper Optimization

Periodic test runs should be conducted to assure the stripping steam ratio is optimizedsteam ratio is optimized

Step the steam rate down until the regenerator temperature starts to increase or the excess O2 drops

When a temperature increase is observed, increase the steam ~5% , %to provide flexibility


Stripper Optimization Example

1328

1330

1322

1324

1326

pera

ture

, °F

1318

1320

erat

or T

emp

1312

1314

1316

Reg

ene

1310 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

Steam To Catalyst Ratio, lb/1000 lbX X.1 X.2 X.3 X.4 X.5 X.6 X.7 X.8 X.9


Regenerator Dense BedDi t C l dDirect-Coupled

Cyclones

Reaction Riser(Short Contact Cyclone

Containment(Time) Containment

Vessel (CCV)

Turbulent Bed

MG Stripper

External Regenerated Catalyst Hopper

Regenerator

Micro-Jet Feed

Hopper

Spent CatalystTransfer Line


Reprinted with permission of Lummus Technologies

Micro Jet Feed Injection Nozzles

Regenerator Dense Bed

Coke formed from the reactions in the riser is burned in the regen dense bed

C + ½ O CO (H t R l 22%)C + ½ O2 CO (Heat Release = 22%)

CO + ½ O2 CO2 (Heat Release = 78%)

Proper coke burning depends on good mixing of the catalyst and air in the regenerator


Keys To Good Coke Burning

1. Temperature

2. Air distribution

3. Catalyst distribution

4. Excess O2

5. Time

• Bed Depth


Importance of Temperature


Air Distribution

BASIS - DISTRIBUTE COMBUSTION AIR IN THE REGENERATOR

Efficient Catalyst Regeneration

(Catalyst/Air Mixing)(Catalyst/Air Mixing)

Even Temperature Distribution

Proper Regenerator FluidizationProper Regenerator Fluidization


KBR Counter-Current Regeneration

low O2Spent Catalyst(high carbon) + Spent Catalyst Standpipe

Pipe Grid

Spent Cat Distributor

DENSEPHASE

BEDatal

yst

air

pAir Distributor

BEDca


high O2Regen Catalyst(low carbon) + Reprinted with permission of KBR

UOP Pipe Air Grid in Regenerator

AccessManway

Abrasion-Resistant

Li iHeader Arm

Lining

Extrusion90° ElbowM i H bMain Hub

UOP 2119-77UOP 2569H-33Reprinted with permission of UOP LLC


UOP 2569H 33p p

SWEC Regenerator Ring Distributors



Afterburning

When CO burns in the dilute phase increasing the temperature:

It is called Afterburn

CO

Two types of Afterburn

Uniform

Localized

Air


Air Inlet

Uniform Afterburn Controls

1. Add Promoter

2. Raise Regen Bed Temp2. Raise Regen Bed Temp

a. Increase feed preheat

b. Increase catalyst additiony

c. Use Slurry/HCO recycle

3. Increase excess O2CO CO

CO CO

4. Raise regen level

5. Increase regen pressure

Air Inlet


Localized Afterburn Controls

1. Verify Air Rate is high enough

2. Adjust air distribution (if possible)

3 Add Promoter3. Add Promoter

4. Raise Regen Bed Temp

a. Increase feed preheatCO

p

b. Increase catalyst addition

c. Use Slurry/HCO recycle

Air Inlet


Air Inlet

Regenerator Catalyst Coolers

Water In

Catalyst In Tubesheet

InnerTube Water &

Tubesheet

Tube Water &Steam Out

CatalystReturn

FluidizationAir

Tubesheet

SlideValve

ReturnScabbard --Outer Tube


Reprinted with permission of KBR


Examples of High EfficiencyRegenerators with Catalyst Coolers


uop

Cone MountedFlow Through

Side MountedHybrid

Cone MountedBackmix

•Ref UOP / NPRAEquipment 96uop

Regenerator Catalyst Coolers

2nd StageRegenerator

Catalyst Cooler

1st StageRegenerator





W hat Is RxCat?W hat Is RxCat?


DeDe --co up les catalyst coup les cataly st circu lation from hea t circu lation fro m h eat ba lan ce / co ke yieldba lan ce / co ke yie ld

High cat / oil up riserHigh cat / oil up riser

High conversionHigh conversion

Increased flexibilityIncreased flexibility

•Ref UOP / NPRA

•

•JORNADAS TECNICAS MADERO PEMEX 2010•TABLE 1Post Reva mp

•.•Yields, wt% Closed Cyclones ATOMAX� FLUX TUBES�

•H2S 0.0 0.0 0.0

•Dry Gas -0 4 -0 3 0 2


•Dry Gas -0.4 -0.3 0.2

•Propane -0.1 0.1 0.1

•Propene 0.0 -0.1 0.2

•n-Butane 0.3 0.1 0.1

•i-Butane 0.3 0.1 0.2

•Butenes 0.0 0.0 0.1

•Gasoline 0.8 1.4 0.2

•Light Cycle Oil 1.6 -0.9 -0.8

•Bottoms - 2 6 -0 4 -0 4Bottoms 2.6 0.4 0.4

•Coke 0.1 0.0 0.1

•Conversion 1.0 1.3 1.2

•Uplift, $/bbl 0.30 0.34 0.12


RxCat Yield BenefitsRxCat Y ield Benefits

to 60 revamp engineering projects undertaken each year for the last 15 years Add

RxCat

O ptimix / VSS /

A F Str ipperB ase

Case S tu dy – RxC at

18.11 8.619.3LP G, wt-%2.12.63.6C 2-, w t-%

5295325 32Reactor Te mp, C

pp

7016687 05Regene rator Tem p, C5.25.35.2Coke, wt-%

57.65 5.353.5Ga soline, wt-%

16.1 / 8.11 0.78.0Cat / O il Ratio, kg /kg

0.660 .500.6 5Delta C oke , kg /kg

•Ref UOP / NPRA


PROCESS CONDITIONS

OPTIMIZATION

nt nten

t

tic

Tem

p

rain

men

cien

cy

ng

te

Affected V i bl

Gasoline

nt nten

t

tic

Tem

p

rain

men

cien

cy

ng

te

Affected V i bl

GasolineGasoline

Max Reactor TemperatureMain Column profile Naphtha / ALCC3/C4’s Gascom recoveryLPG / Naftha separation RVP

Increased CombinedFe ed Temperature

Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

Aro

mat

ic C

o

LC

O A

rom

aC

onte

nt

Cok

e Y

ield

Reg

ener

ator

Cat

alys

t/Oil

Cat

alys

t E

ntr

Cyc

lone

Eff

ic

Req

’dSt

ripp

iSt

eam

RatVariable

Adjusted VariableIncreased CombinedFe ed Temperature

Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

Aro

mat

ic C

o

LC

O A

rom

aC

onte

nt

Cok

e Y

ield

Reg

ener

ator

Cat

alys

t/Oil

Cat

alys

t E

ntr

Cyc

lone

Eff

ic

Req

’dSt

ripp

iSt

eam

RatVariable

Adjusted Variable

LPG / Naftha separation RVP

Mass Balance Instruments RevisionEnergy BalanceH d B l

Increased RecycleRate Increased ReactorTemperature Increased ReactorPr essure IncreasedRegenerator Pressure

Increased RecycleRate Increased ReactorTemperature Increased ReactorPr essure IncreasedRegenerator Pressure

Hydrogen Balance gIncreased CatalystCirculation Rate atConstant ReactorTemperature(Increased CatCooler Duty)


g

Increased CatalystCirculation Rate atConstant ReactorTemperature(Increased CatCooler Duty)


•PEMEX- GRACE PLAN ESTRATEGICO 2010- 2012

MERCADO / SERVICIO TECNICO / CAMBIOS / LOGISTICA

Why is the FCC Important to Refiners?Why is the FCC Important to Refiners?Average S ized FCC

F EED:40 000 BPD

PRODU CT S:44,0 00 B PD@ $ 25/BB L

Low Value F eed s to H igh V alue Products =

ion

ld eld

Con

tent

ic C

onte

nt

rom

atic

en

t

eld

rato

r Te

mp

t/Oil

t Ent

rain

men

t

Effic

ienc

y

trip

ping

m

Rat

e

Affected Variable

Gasoline

ion

ld eld

Con

tent

ic C

onte

nt

rom

atic

en

t

eld

rato

r Te

mp

t/Oil

t Ent

rain

men

t

Effic

ienc

y

trip

ping

m

Rat

e

Affected Variable

GasolineGasoline

Int rodu ct ion to U OP FC C T ec hno log y 3uop

40,000 BPD@ $20 /B BL

FEE D-PRODUCT D IFFERE NTIAL = $300,000/Day

Increased CombinedFeed Temperature Increased RecycleRate Increased ReactorTemperature Increased ReactorPressure IncreasedRegenerator Pressure Increased CatalystCirculation Rate atConstant ReactorTemperature(Increased Cat

Con

vers

Gas

Yie

l

LPG

Yie

Oct

ane

Ole

fin C

Aro

mat

i

LCO

Ar

Con

te

Cok

e Y

ie

Reg

ener

Cat

alys

t

Cat

alys

t

Cyc

lone

Req

’dSt

Stea

m

Adjusted Variable


Increased CombinedFeed Temperature Increased RecycleRate Increased ReactorTemperature Increased ReactorPressure IncreasedRegenerator Pressure Increased CatalystCirculation Rate atConstant ReactorTemperature(Increased Cat

Con

vers

Gas

Yie

l

LPG

Yie

Oct

ane

Ole

fin C

Aro

mat

i

LCO

Ar

Con

te

Cok

e Y

ie

Reg

ener

Cat

alys

t

Cat

alys

t

Cyc

lone

Req

’dSt

Stea

m

Adjusted Variable


(Cooler Duty)

Change in Affected Variable: increases; decreases(Cooler Duty)

Change in Affected Variable: increases; decreases

73

•SERVICIOS TECNICOS FCC PEMEX 2010

tt

ersio

n

Yie

ld

Yie

ld

ne n C

onte

nt

mat

ic C

onte

nt

Aro

mat

ic

nten

t

Yie

ld

nera

tor

Tem

p

yst/O

il

yst E

ntra

inm

ent

ne E

ffici

ency

dSt

ripp

ing

eam

Rat

e

A ffected V a riab le

A d ju sted

Gasoline

ersio

n

Yie

ld

Yie

ld

ne n C

onte

nt

mat

ic C

onte

nt

Aro

mat

ic

nten

t

Yie

ld

nera

tor

Tem

p

yst/O

il

yst E

ntra

inm

ent

ne E

ffici

ency

dSt

ripp

ing

eam

Rat

e

A ffected V a riab le

A d ju sted

GasolineGasoline

In creased C om b inedFe ed T em pera ture In creased R ecy cle

Con

ve

Gas

Y

LPG

Y

Oct

an

Ole

fin

Aro

m

LCO

AC

o

Cok

e

Reg

e n

Cat

aly

Cat

aly

Cyc

lon

Req

’d SteA d ju sted

V a riab leIn creased C om b inedFe ed T em pera ture In creased R ecy cle

Con

ve

Gas

Y

LPG

Y

Oct

an

Ole

fin

Aro

m

LCO

AC

o

Cok

e

Reg

e n

Cat

aly

Cat

aly

Cyc

lon

Req

’d SteA d ju sted

V a riab le

R a te In creased R eact orT e m perat ure In creased R eact orPr essure In creased

R a te In creased R eact orT e m perat ure In creased R eact orPr essure In creased R e generato r P ressure In creased C atalystC irculatio n R ate atC o nstant R eac torT e m perat ure(In creased C at

C han ge in Affec ted Var iable : –increases; – d ecrea ses

R e generato r P ressure In creased C atalystC irculatio n R ate atC o nstant R eac torT e m perat ure(In creased C at

C han ge in Affec ted Var iable : –increases; – d ecrea ses

(C o oler D uty)

C han ge in Affec ted Var iable : increases; d ecrea ses(C o oler D uty)

C han ge in Affec ted Var iable : increases; d ecrea ses

FCC Process Variable StudyFCC Process Variable StudyProcess Modeling Framework

Uncontrolled VariablesUncontrolled Variables

Feed Injection PointProduct Yields

GasolineFCC UnitReactor Temp

Feed Preheat T

Gasoline Octanes

Conversion

Profit

Objectives: To show the cause and effect of the process

(Cat/Oil, Reg. Temp., ...)Temp Profit

OUTPUT

INPUT

To show the cause and effect of the process variableson the profit, conversions and yields

To determine direction on how to optimize


poutputs

Statistical Design forFCC Process Development Study

A 2 x 3 x 2 factorial design (with one missing corner point)

101

119

10

530528em

p., o C

5 4

8 126Upper

528525

520

eact

or T

e

2,7 3 Lower

260200

508R


Feed Preheat Temp., oC260200

FCC Unit Matrix TestUnit A Gasoline Yield Response Surface

51850

482446

410 941 950 959 968 977 986

50

, wt-

% 48

46Upper

asol

ine Y

ield

, 46

44Lower

G 42

40505 510 515 520

240220

200


UOP 2569i -10

515 520 525 530260

Refineries Technical supportR E D U C C I O N D E C O N V E R S IO N Y P R O D U C C IO N

D E G A S O L I N A E N L A U N I D A D P E R I O D O J U L I O - A G O S T O

EVALUACIÒN INDUSTRIAL DEL CATALIZADOR GEMINI HP-414 UNIDAD FCCII, REF. "ING. ANTONIO M. AMOR"

GASOLINA %Vol

GRAF RP5REP AGO/2010 SLM FCC UNIT IILow Gasoline Yield

50 00

55.00

60.00

65.00

70.00

%Vol

Low Gasoline Yield

45.00

50.00

1-Jan-10 31-Jan-10 2-Mar-10 1-Apr-10 1-May-10 31-May-10 30-Jun-10 30-Jul-10 29-Aug-10

FECHA

6 5 - 6 8 % V o l 5 9 - 6 0 % V o l 5 3 - 4 8 % V o l

1.5 %p 3%pC3= % Vol 0.91 1.83C3 % Vol 0 0IC4= % Vol 0 58 1 08

% ZSM5Producto Delta Vs Base

CD FCC UNIT IICatalyst

IC4 % Vol 0.58 1.08nC4 % Vol 0 0IC4=/C4 Tot % Vol 2.56 4.57

Gasolina % Vol -1.24 -2.42

Reformulation PEMEX General Director

78

RONC 1 1.7

Refineries Technical support

TULA FCC UNIT IIStart Up New Project

SLC FCC UNIT ICatalystyPerformance

79

Refineries Technical support

Zeolita Y

RRRZSM-5 no craquea

430°F + LCO

CargaCarga

PropilenoButilenoPropilenoButilenoGasolina

R

ACL

Gasolina

RR

ACL

CargaCarga

(ZSM-5)ButilenoPropilenoButilenoPropileno

PEMEX FCC UNITSPERFORMANCEPERFORMANCEEVALUATION vs

80

Analisis Y Vs X En el anterior análisis histórico se observa que hay tres factores principalmente: Menor calidad de la carga Mayor contenido de metales contaminantes en el ECAT

Menor temperatura de Reacción que han ocasionado que el Rendimiento de Gasolina se vea afectado de manera negativa por lo tanto a continuación se revisa a Menor temperatura de Reacción, que han ocasionado que el Rendimiento de Gasolina se vea afectado de manera negativa, por lo tanto a continuación se revisa através de un análisis multivariable cuales de estos factores son los de mayor impacto y se comprueba cómo la situación actual es resultado de dichas condiciones,teniendo en cuenta los siguientes principios:

Causas

Caida en Rendimiento a Gasolina / Conversión

Cambios en la calidad de la

carga

Cambios en las propiedades del

catalizador

Cambios en las condiciones de

operación

Cambios en las condiciones mecánicas

• Disminución del factor K • Diminución Mat y Area • Disminución en la • Deterioro en las

• Menor API

• Incremento el % de residuo - carbón

• Mayor contenido de metales

•Bajo UCS

•Alto contenido de CRC

temperatura de reacción

• Menor relación C/O

•Altas temperaturas en el regenerador

• Bajo punto final de la gasolina

boquillas de carga

• Limitación en circulación

• Otros

Solucionesgasolina

•Bajo RVP

• Graficar propiedades de la carga para analizar tendencias : API KUOP

• Analizar tendencias de actividad, metales, RE y UCS

• Revisar las condiciones mecánicas de la unidad

• Aumentar T de reacción

•Verificar el balance de materiatendencias : API, KUOP,

etc.UCS

• Revisar Tasa de adición

materia

• Revisar el perfil de la torre

Analisis Rendimiento Gasolina - Y Vs X

67

66

516513510 800070006000

Matrix Plot of GASOLINA vs KUOP, TRX, C/O, V+Na

66

65

64

63

LINA

62

61

60

GA

SO

11.7011.4511.20

59

581098

KUOP TRX C/O V+Na

R2 = 0.0277 R2 = 0.3819 R2 = 0.0427 R2 = 0.1982

• Con base en el anterior análisis gráfico se determinó que las variables que mejor correlacionan con el rendimiento a Gasolina son: La Temperatura de Reacción y elcontenido de metales desactivantes

• El Factor KUOP, correlaciona de manera adecuada, pero como parece no representar muy bien el deterioro de la carga su impacto no se ve tan grande, y la relaciónC/O que ha tenido cambios algo erraticos ultimamente (asociados al análisis ORSAT), NO CORRELACIONA de manera adecuada con el comportamiento de lagasolina, pues a mayor C/O deberia tenersemayor gasolina y aquí vemos que su pendiente es negativa.

GRACE GRACE GRACE COMPETITOR MEXICO

SALAMANCA CADEREYTA I CADEREYTA II

ACTUAL YIELDS % Vol %Peso ACTUAL YIELDS % Vol %Peso ACTUAL YIELDS % Vol %Peso ACTUAL YIELDS % Vol %Peso

Gas Seco 3.43 Gas Seco 266309 1.5 Gas Seco 4.08 Gas Seco m3/d 5.56

Gas Acido 0.99 Gas Acido 38019 0.1 Gas Acido 0.92 Gas Acido

Propane 3.03 1.73 Propane 2.4 1.3 Propane Propane 1.43 0.81

P l 2 03 1 19 P l 6 8 3 4 P l P l 5 86 3 34Propylene 2.03 1.19 Propylene 6.8 3.4 Propylene Propylene 5.86 3.34

Butane Butane 8.2 Butane Butane 0.55 0.35

Butylenes Butylenes 11.5 Butylenes Butylenes 1.78 1.13

Isobutylene Isobutylene 11.1 Isobutylene Isobutylene 1.88 1.19

Total C4/C4= 12.91 8.36 Total C4/C4= 20.3 12.4 Total C4/C4= 17,46 12.1 Total C4/C4= 11.7 7.5

Gasoline (C5-221) 64 3 47 6 Gasoline (C5-221) 57 1 49 6 Gasoline (C5-221) 58 27 46 74 Gasoline (C5-221) 59 7 48 1Gasoline (C5-221) 64.3 47.6 Gasoline (C5-221) 57.1 49.6 Gasoline (C5-221) 58.27 46.74 Gasoline (C5-221) 59.7 48.1

RON 91.5 RON 93 RON 92.2 RON 90

(RON+MON)/2 85.6 (RON+MON)/2 87 (RON+MON)/2 56.53 (RON+MON)/2 85

S % Peso 0.71 S % Peso 0.13 S % Peso 0.11 S % Peso 0.25

Heavy Naphtha Heavy Naphtha 2 2 Heavy Naphtha 2.11 2.03 Heavy Naphtha

ALC 17.75 21.32 ALC 14.1 15.6 ALC 17.44 17.93 ALC 14.6 14.8

SLURRY 8.13 11.44 SLURRY 7.3 9.6 SLURRY 6.61 7.75 SLURRY 15.27 15.27

COQUE 3.94 COQUE 4.5 COQUE 3.5 COQUE 3.32 3

Total 108.15 100 Total 110 100 Total 111.34 100.3 Total 110 100


FEED PROPERTIES

REVISIONSample pointsFeed properties Lab MethodsFeed properties Lab MethodsMass Balance Program 3-5 /week

E ti t i t tiEstimates impact on propertiesOut of ranges

Feed Rate as per Designp g

Sources of FCC Feedstock

c

CrudeAGOHVGOH

AGO

AGOVGO

VSVGODCVGO

Furf. Ext. Atm

osph

eric

Dis

tilla

tion

ATB

VGO

VGOHVSVGOHDCVGOHATB

um atio

nVa

cuu

Dis

tilla

urfu

ral

xtra

cts

HYDROTREATER

VTB

VSVG

O

er G

O

DA

O

DA

OH

FurfuralUnit

Fu Ex

Visbreaker

CokerVTB

Cok

e

VTBD DSlops

DAU

FCC Technology Workshop - May 16 – 19, 2011

VTB DAU

HYDROTREATER

PEMEX Refineries Technical supportSERVICIOS TECNICOS FCC PEMEX 2010

PANORAMA DE CARGAS PEMEX MEXICO

SLC FCC UNIT ICatalystyPerformance

86

•SERVICIOS TECNICO PEMEX 2010

COLUMNAS

Sinergía entre diferentes procesos

Diesel

ETBE / TAME

DieselDestilación atmosférica

HDS de DieselCrudoDIPE

HDS de GasoleosFCC

ETBE / TAME

PoolGasolina

GOPP

Alquilacion

HDS de Gasolina

Destilación al vacío

GOLV

GOPVHidrocraqueo

Gasoleo noconvertido

CoquizadoraResiduode vacío

Gasoleo de Coquizadora

Refineries Technical support3 003 00 IMPACT l t ki th

SERVICIOS TECNICOS FCC PEMEX 2010

1.50

2.00

2.50

3.00

wt%

of F

eed

1.50

2.00

2.50

3.00

wt%

of F

eed

IMPACT excels at cracking the 650-750° bottoms.

MIDAS excels at cracking the 800° b tt

RESID

0.00

0.50

1.00

650-700 700-750 750-800 800-850 850-900 900-950 950-1050

Yiel

d, w

0.00

0.50

1.00

650-700 700-750 750-800 800-850 850-900 900-950 950-1050

Yiel

d, w 800°+ bottoms.

The GENESIS blend reflects the best of both catalysts.

650 700Yields

700 750Yields

750 800Yields

800 850Yields

850 900Yields

900 950Yields

950 1050Yields

Boiling range F

IMPACT GENESIS MIDAS

650 700Yields

700 750Yields

750 800Yields

800 850Yields

850 900Yields

900 950Yields

950 1050Yields

Boiling range F


3.003.00200

2.50

200

2.50

1.50

2.00

2.50

ield

, wt%

1.50

2.00

2.50

ield

, wt%

1.00

1.50

2.00

Yiel

d, w

t%

1.00

1.50

2.00

Yiel

d, w

t%VGOHydrotreated

0.00

0.50

1.00

650-700 700-750 750-800 800-850 850-900 900-950 950-1050

Yi

0.00

0.50

1.00

650-700 700-750 750-800 800-850 850-900 900-950 950-1050

Yi

0.00

0.50

650-700Yields

700-750Yields

750-800Yields

800-850Yields

850-900Yields

900-950Yields

950-1050Yields

Boiling range F

0.00

0.50

650-700Yields

700-750Yields

750-800Yields

800-850Yields

850-900Yields

900-950Yields

950-1050Yields

Boiling range F

89

650 00Yields

00 50Yields

50 800Yields

800 850Yields

850 900Yields

900 950Yields

950 050Yields

Boiling range F


650 00Yields

00 50Yields

50 800Yields

800 850Yields

850 900Yields

900 950Yields

950 050Yields

Boiling range F


g g


g g


What Defines the Crackability of the Feed?

Precursors of Gasoline and LPG: Paraffins, Cycloparaffins, Monoaromatics

S

Saturates: Paraffins + Cycloparafins

These molecules are rich in H, and they convert to gasoline with high efficiency


with high efficiency.

Precursors of LCO: Diaromatics

SSSS


Precursors of HCO, Slurry and Coke: Triaromatics and heavier

RESIN ASPHALTENES

H O N

S

S H O

H O

N

S

S


Effect of Boiling Point on Crackability

GO split into fractions •76

•78

Constant Severity• 945 °F Reaction temperature

• 5.5 Cat to Oil Ratio

•74

Wt.

%

5.5 Cat to Oil Ratio

• 32 WHSV

•70

•72

nver

sion

, WDistillation Vol % IBP-25% 25%-75% 75%-FBP

440 F 2 0 066

•68•Co

440-640 F 83 4 0640-850 F 15 81 0

850+ F 0 15 100 •64

•66

•IBP-25% •25%-75% •75%-FBP


IBP 25% 25% 75% 75% FBP•Boiling point Cuts

Impact of Feed on Yields – Examples

TABLE 1: Feed Properties For 680 1000F VGO’s

(Pilot plant data, model adjusted, from RPS Seminar)

TABLE 1: Feed Properties For 680 - 1000 F VGO s MINAS U.S. MID-

CONTINENT MIXED

VENEZUELANANS

API 31 7 25 0 22 5 19 8API 31.7 25.0 22.5 19.8Aniline Pt., F 228 199 189 176 Sulfur, W% 0.09 0.59 0.90 1.20 Nitrogen, W% 0.06 0.10 0.12 0.17gK Factor 12.54 12.05 11.86 11.67 H Content, W% 14.20 12.90 12.55 12.00

Highly Paraffinic -------------------------------- Highly Aromatic


TABLE 2: FCC Operating Results for Various FeedsTABLE 2: FCC Operating Results for Various Feeds

MINAS U.S. MID-CONTINENT

MIXEDVENEZUELAN

ANS

Reactor T, F 980 980 980 980

(Pilot plant data, model adjusted, from RPS Seminar)

Feed T, F 500 500 500 500Regen. T, F 1327 1332 1351 1378Cat/Oil, W/W 6.1 6.0 5.6 5.2

C i V% 85 6 78 2 75 5 70 0Conversion, V% 85.6 78.2 75.5 70.0C2 Minus, W% 2.8 3.0 3.1 3.3LPG, V% 33.4 28.1 26.4 23.3Gasoline, V% 65.4 61.7 59.7 55.4LCO/Bottoms V/V 1 66 1 25 1 15 1 01LCO/Bottoms, V/V 1.66 1.25 1.15 1.01Coke, W% 4.7 4.7 4.8 4.8LPG Olefinicity, V% 55.5 55.7 56.0 56.8

LCO API 22.8 17.0 15.5 14.7Bottoms API 9.4 2.2 0.2 -1.2Gasoline RON 88.5 90.0 90.4 90.8Gasoline MON 78.6 79.6 79.7 80.0

P d t V l $/bbl 30 15 29 62 29 24 28 59


Product Value, $/bbl 30.15 29.62 29.24 28.59

Effects of Coker Gas Oil

Effect of Coker Gas Oil on Combined Feed APIUnit X

25~1 API drop for 0 to 20% CGO

23

24~1 API drop for 0 to 20% CGO.

Expect 1.3 vol% lower Conversion

21

22

eed

API

20

21Fe

18

19

0% 5% 10% 15% 20% 25%


0% 5% 10% 15% 20% 25%

% Coker Gas Oil in Feed

Effects of Coker Gas Oil

Effect of Coker Gas Oil on ConversionUnit X

80%Rx Temp = 980°F to 990°F

76%

78%

, vol

%

Feed Temp = 400°F - 450°F

Actual Conversion Loss

4 l%

72%

74%

Con

vers

ion = 4 vol%

70%

72%

Adj

uste

d C

66%

68%

0% 5% 10% 15% 20% 25%


0% 5% 10% 15% 20% 25%

% Coker Gas Oil in Feed

Resid Cracking Study(ACE Pil t l t d t )

Delta Coke vs. Atm Bottoms in Feed0.55

(ACE Pilot plant data)

0.50

e

0.40

0.45

elta

Cok

e

0.35

D

0.300 2 4 6 8 10 12 14 16 18

Atm Bottoms in Feed, vol%


Long term effects are expected to be more severe as e-cat metals increase.

Resid Cracking Study(ACE Pilot plant data)

Resid Feed Study73

(ACE Pilot plant data)

71

72

wt%

)

Approximately 0.2 wt% conversion loss for every 1 vol% ATB in feed.

y = -0.2139x + 71.877R2 = 0.977770

71

vers

ion

(w

68

69

Con

v

Data interpolation at 4 wt% coke67

0 2 4 6 8 10 12 14 16 18Atm Bottoms in Feed, vol%

Data interpolation at 4 wt% coke



Resid Cracking Study

( C )(ACE Pilot plant data)Gasoline Yield vs. Atm Bottoms in Feed

50

49(wt%

)

49

ne Y

ield

(

48

Gas

oli

Data interpolation at 4 wt% coke

470 2 4 6 8 10 12 14 16 18

Atm Bottoms in Feed, vol%



Severe Response to Added NitrogenExample with 3x rule of thumb response

75%

Example with 3x rule of thumb response -1000 PPM N increase results in about 10% Conversion Loss

65%

70%

Vol%

55%

60%

Con

vers

ion,

V

45%

50%C

40%1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400

Nitrogen by Antek, ppm

Note: Nitrogen cannot be seen on an ecat report!


Note: Nitrogen cannot be seen on an ecat report!

Hydrotreated Total Feed

Effect on Conversion and Gasoline

76.5

wt%

75.0

75.5

76.0

onve

rsio

n, w

74.50.25 0.3 0.35 0.4

Co

51.5

52.0

d, w

t%

50.5

51.0

asol

ine

Yiel

d

50.00.25 0.3 0.35 0.4

Feed S, wt%

Ga

Increasing Hydrotreating Severity


Increasing Hydrotreating Severity

Atributos Requeridos del Catalizador por Tipo de CargaFactor KFactor K

Carga Residual> Selectividad a Coque

Azufre

> Tolerancia a Metales

> Capacidad de craqueo de fondos

Carga VGO> Retención de la Actividad

> Selectividad a Coque

> Tolerancia a Metales> Tolerancia a Metales

> Balanceada Transferencia de Hidrógeno

Carga HidrotratadaCarga Hidrotratada> Máxima Actividad

> Capacidad de craqueo de fondos

O ti S l ti id d C> Optima Selectividad a Coque

Impacto de Composición Química de las Cargas en el proceso de FCCImpacto de Composición Química de las Cargas en el proceso de FCC

ParafinasVGO y Cargas Hidrotratadas

Calidad: >API,<S,<RCM,<N,<Ni+V,< IR,<IC,>H2 Craqueabilidad: Rendimientos y conversión:

Cicloparafinas

VGO y Cargas Hidrotratadas

Rendimientos y conversión: Gasolina �, Octano: Mejor balance de calor Actividad del catalizador:

SATURADOSMonoaromáticos

VGOHVGO

Diaromáticos

HVGO

H O

RESINAS

H O

RESINAS

Calidad: < API, >S,>RCM,>N,>Ni+V,> IR,>IC<H2

Triaromáticos+

Tetraaromáticos+ Cargas con Residuos

N

S

N

ASFALTENOS

N

S

N

ASFALTENOS

S H O

H O

S H O

H O

RESIDUOS

, , , , , , Craqueabilidad: Rendimientos y conversión: Gasolina , Octano: Coque Instantáneo y contaminante:

August 9, 2011 Uriel Navarro Uribe, Ph. D. 104

S

S

S

S

q y Selectividad del catalizador: Diseño de matrices con selectividad a coque y gas


FCC CATALYSTY

O OOPTIMIZATIONMAT Activity E- CATCatalyst Daily addition rate

PTR Min Inventory 80% New CatalystStable condition Cat Addition Rate And MAT.

Worldwide Leader in Materials Science

History Innovation Today

History of materials innovation for a broad scope of applications

Combining expertise in materials, formulation and

Materials and new technologies leading toa broad scope of applications

Grace Davison pioneered the use of silica gel for military, industrial, and consumer applications

Silica gel first used for World War I

materials, formulation and process chemistry with applications knowledge and customer partnership to develop high value, enabling products

technologies leading to new industry segments, value-added applications, and performance-enhancing attributes

Approximately 1/3 of 2010 Silica / Alumina used in the

production of the world’s first fluid cracking catalyst for gasoline

Silica / Alumina used in world’s first heterogeneous catalysts to

Disciplined stage-gate process Open Innovation Design for Six Sigma Adjacent space focus

Approximately 1/3 of 2010 sales is derived from products that were created in the last five years

Over 350 active patents

August 9, 2011 Company Confidential 106

make polyethylene polymers

Grace Davison Refining Technologies

Mission: To supply state-of-the art products and superior technical service in order to solve our customers’ problems and enhance their profitability.

Critical Elements

• Robust R&D program with innovative scientists and engineers and a disciplined stage-gate new product development process Worldwide Segment Share

• Seasoned technical service professionals with a broad range of industry experience and expertise

• Flexible and productive manufacturing assets able to

Worldwide Segment Share

37%12%

12%

manufacturing assets able to produce a wide-range of products with the highest quality

Experience

• 60+ Years Experience in Producing FCC Catalysts 20%

19%

12%

FCC Catalysts• 30+ Years Experience in Alumina

Manufacture• 35+ Years Experience in Zeolite

Manufacture

0%

Davison Competitor 1 Competitor 2Competitor 3 Others


PRISM – Product Innovation and Strategic Marketing

PRISMIdea Business Development Test Commercia-

Evaluation Planning Development Marketing lization

MeritReview

FeasibilityReview

ReadinessReview

CompletenessReview

Wrap-upReview

• Stategate process used for product development

• Implemented in FCC in 1999/2000

• Successful introduction of products


An Emphasis on New Product Development

Grace Davison Operations, R&D/TCS Sites

4 2

4

Global headquartersGlobal headquarters

Key offices

Regional headquarters

34 Grace Davison manufacturing sites

20 R&D / Technical Service sites / Sales offices

Davison Manufacturing Sites:

Aiken, SC East Chicago, IN Norderstedt, GermanyBangkok, Thailand Edison, NJ Porvoo, FinlandBogota Columbia Epernon France Santiago Mexico

Global Headquarters

Columbia, MD

Regional Headquarters

R&D & Technical Service Sites:

Atsugi, Japan Norderstedt, GermanyCanlubang, Philippines Hesperia, CACarnforth UK Johor Bahru MalaysiaBogota, Columbia Epernon, France Santiago, Mexico

Cape Town, South Africa Hailfingen, Germany Sorocaba, BrazilCarnforth, UK Hernani, Spain St. Neots, EnglandChattanooga, TN Hesperia, CA Stenungsund, SwedenChicago, 51st, IL Kuantan, Malaysia Surat, IndiaChicago, 71st, IL Lake Charles, LA Valleyfield, QuebecCikarang, Indonesia Lima, Peru Valencia, Venezuela

Regional Headquarters

São Paulo, BrazilShanghai, ChinaWorms, Germany

Other Key Offices:

Carnforth, UK Johor Bahru, MalaysiaChennai, India Kuantan, MalaysiaChicago 71st, IL Poznan, PolandColumbia, MD Santiago, MexicoCurtis Bay, MD Shangai, ChinaDeerfield, IL Shunde, ChinaEdison, NJ Sorocaba, Brazil


Curtis Bay, MD Lokeren, Belgium Worms, GermanyDeerfield, IL Manila, PhilippinesDüren, Germany Minhang, China

Dubai, UAECambridge, MA

Epernon, France Worms, Germany

RT Sites

Refining Technologies Fundamental Strengths


Portafolio de Catalizadores FCC 2009

CCIMPACTIMPACT®®

Mínimo Coque & GasMínimo Coque & Gas

PINNACLEPINNACLE™™PINNACLEPINNACLEMínimo Coque & GasMínimo Coque & Gas

MIDASMIDAS®®

Máx. Reducción Máx. Reducción de Fondosde Fondos

GENESISGENESIS™™

Todos los tipos deTodos los tipos decargacarga

Formulación NovedosaFormulación NovedosaADVANTAADVANTA™™

Alta olefinicidad de Alta olefinicidad de ProductosProductos

AURORAAURORA®®

de Fondosde FondosTodos los tiposTodos los tipos

de cargade carga

Formulación NovedosaFormulación NovedosaFlexibilidadFlexibilidad

Bajo Coque y GasBajo Coque y GasTodos los tipos de cargaTodos los tipos de carga

SPECTRASPECTRA®®

Gasolina + Olefinas Ligeras

Gasolina + Diesel

Nuevos Lanzamientos de Catalizadores para el 2010

GENESIS®

Novedosa formulación flexible para cargas

Residuales

IMPACTIMPACT®® / / PINNACLEPINNACLE®®

Mínimo Coque y GasMínimo Coque y GasRESIDRESID--MXMX

Máxima Tolerancia a Máxima Tolerancia a MetalesMetales

MIDASMIDAS®®--300300Máxima producción Máxima producción

de destiladosde destilados

APAP--PMCPMCMáximo propilenoMáximo propileno

ALCYONALCYON®®

Ultra alta actividadUltra alta actividad

GENESIS®-LXFlexibilidad en la

formulación para cargas VGO

ASTERAASTERA®®

Desempeño versatilDesempeño versatilMIDASMIDAS®®--100/100/20002000

Máxima reducción de fondosMáxima reducción de fondos

Davison Low/No Rare Earth FCC Catalyst Solutions

RESID-MXGENESIS®

Ultimate formulationflexibility for resid feeds

IMPACT™Minimum Coke & Gas

MIDAS®

Max Bottoms Reduction

Max Metals ToleranceGENESIS®-XT Next generation -flexibility for medium to high metal feeds

ResidUltra™Next generation metals trap

Max Bottoms Reduction

REBEL®

Z-21 Technology for bottoms reduction

REDUCER™Low RE Technology for resid feeds

REMEDY™

RESULT™Next generation low to moderate metals

REACTOR™

ALCYON M™High activity high MSA

bottoms reduction

GENESIS®-LX

REMEDY™Low RE Technology for VGO/HT feeds

ALCYON™

REACTOR™Z-22 Technology for higher olefins

Hi h Z lit A ti it L Z lit A ti it

g y gUltimate formulationflexibility for VGO/HT feeds

ALCYONUltra High Activity

Company Confidential - INTERNAL ONLY

High Zeolite Activity Low Zeolite Activity

IMPACT: Estabilidad a Metales

75

80

60

65

70

dad

MAT Catalizador selectivo a

coque

50

55

60

Act

ivid

Catalizador

40

45

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

convencional

Metales Totales (Ni+V) (ppm)Desactivación

CPS a 1450°F: Ni/V=0.5

IMPACT® Mostró una tolerancia a metales y estabilidad mejoradas

T d V di

Trampas de Vanadio

Trampas de Vanadio Reduce la producción de coque contaminante e hidrógeno Protege la zeolita de la desactivación

50mm RE 50mm V

“Puntos Rojos” indican donde las tierras raras atrapan el vanadioLa mayor parte del catalizdor queda libre del Vanadio

La trampa IVT-4 se usa en la tecnología IMPACT®

Sinergía del Sistema Catalítico GENESIS™

Evaluación en Davison Circulating Riser (DCR)

79

81

1112

71

73

75

77

79

rsio

n, %

p

789

10

laci

on C

/O

La real y la calculadase superponen

65

67

69

71

Con

ver

3456R

e

631 1.5 2 2.5 3 3.5 4

Coke, wt%

21 1.5 2 2.5 3 3.5 4

Coque, %p

IMPACT MIDAS GENESIS Mezcla calculada

El Sistema GENESIS es Sinergístico

www.grace.com

Alcyon™: Una nueva Estrella emergeNo sólo hacemos catalizadores FCC,

hacemos catalizadores para ustedhacemos catalizadores para usted.

Alcyon™

Caso de Estudio: Rendimientos modelados usando Planta PilotoAlcyon

(relative to base case)

ConditionsFeed rate --Cat Adds --

En planta piloto Alcyon permitio:

• Mejorar la actividad y tener un mayor delta coque

M j l ti id d Cat Adds --Feed T (F) --ROT T (F) -5.0Regen T (F) +9.0Circulation tpm 0 7

• Mejor selectividad a coque y mayor conversión

En la FCC Alcyon permitirá:

• Alcanzar objetivos de Circulation, tpm -0.7C/O Ratio -0.4

YieldsWet Gas SCFB 44

conversión incluso a una TRx reducida

• Aliviar la limitación del compresor Wet Gas, SCFB -44

Gasoline, lv% +2.0LCO, lv% --Slurry, lv% -0.3Coke wt%

compresor

• Mayor rendiiento a gasolina y menor rendimiento de fondos

Coke, wt% --

Conversion, lv% +0.3

La alta actividad de Alcyon™ alivia la limitación del compresor yLa alta actividad de Alcyon™ alivia la limitación del compresor y proporciona la misma conversión a menor Temperatura del Riser

Desde su lanzamiento en 2003 Grace Davison ha tenido más de 140 aplicaciones del

MIDAS-2000 Desde su lanzamiento en 2003, Grace Davison ha tenido más de 140 aplicaciones del

catalizador MIDAS alrededor del mundo

Dado el exito de las tecnologías MIDAS y GENESIS, se han invertido significativos esfuerzos de R&D para mejorar las capacidades para producir MIDAS technology en todas las plantas.

Desempeño similar a la serie MIDAS-100p

Ventas MIDAS®Ventas MIDAS

row

thSa

les

Gr

2004 2005 2006 2007 2008 2009 2010

El catalizador MIDAS® ha sido ampliamente aceptado por los Refinadores

RE-Free Innovations Save Cost and Maintain Performance

Reduce Re2O3 by 90% Maintain

activity and catalyst additions

-30%additions Daily cost

decreases by 30%

Portafolio de Aditivos de Grace Davison

Olefinas y Octano

CombustiblesLimpios

La tecnología basada en ZSM 5 Reduce el azufre en la gasolina FCCLa tecnología basada en ZSM-5 Aumenta el rendimiento a Olefinas ligeras (C3=)

Incrementa el octano de la Gasolina

Reduce el azufre en la gasolina FCC

OlefinsMax®

SuRCA®

Neptune™D-PriSM®

GSR®-5

OlefinsMax®

OlefinsUltra®

OlefinsUltra® HZ

Ambiental Flexibilidad

Actividad

Reduce Emisiones en el Gas de chimenea

SOx NOx CO Fluidización

Restauran la salud del inventario

Super DESOX® XNOx®

DENOX®CP®-5CP-P®

ACTIVA™ FLOWMOTION™

G D i I t d j l i diti ZSM 5 FCC 1984

Tecnologías de Aditivos para Olefinas y Octano

Grace Davison Introdujo el primer aditivo ZSM-5 para FCC en 1984.

Estructura 3-DZSM-5

OlefinsMax®• Más ampliamente usado - Usado en más de 150 unidades a nivel mundialp• Ha producido hasta 9 % de Propileno

OlefinsUltra®• La máxima actividad disponible en aditivos comerciales• Única tecnología de matriz que provee máxima actividad por unidad de cristal ZSM-5g q p p• Excelente resistencia a la atrición

OlefinsUltra® HZ• Próxima Generación de ZSM-5 con incluso mayor actividad del cristal• Incluye tecnología de ajuste de sitios ácidosy g j

FCC Operation:

37 000

39,000

41,000

43,000

Unidad FCC II Refineria de Salamanca, Gto.Carga Fesca •Feed Rate: 28/ 25/38 MBDO

27,000

29,000

31,000

33,000

35,000

37,000

Carg

a Fe

sca,

BPD

25,000

,

EVALUACIÒN INDUSTRIAL DEL CATALIZADOR GEMINI HP-414 UNIDAD FCCII REF "ING ANTONIO M AMOR"

GRAF CO8REP ENE/2011

9.6

11.6

13.6

UNIDAD FCCII, REF. "ING. ANTONIO M. AMOR"

CONS. DE CAT. Ton/d•Cat. Addition 2/3/4/Tons/day

1 6

3.6

5.6

7.6

Ton/

d

123

1.601-jun-10 01-jul-10 31-jul-10 30-ago-10 29-sep-10 29-oct-10 28-nov-10 28-dic-10 27-ene-11

FECHA

ANALISYS STRATEGYSTRATEGY ANALYSIS

FCC CATALYST

•2011 - 20122008- 2010

FCC CATALYST BID PROCESS

CATALYST

2011

CATALYST PERFORMANCEADDITIVES E=CATRE . PLANTA PILOTO

2012- 2013

FCC CATALYST BID PROCESS PP

RE OPTIMIZATION- STRATEGY

RE on Catalysts

• Based in a detailed analysis weBased in a detailed analysis wetook the desition to reduce RE on zeolite and RE used as V Trap.

Cadereyta I Salamanca Salina Cruz

Q4´10, wt % 3.5 3.5 3.5

Q1´11, wt % 1.2 2.5 2.4

Delta, wt % 2.3 1.0 1.2

65 % Reduction in Cadereyta´s Catalyst and around 30 %Reduction in Salamanca aand Salina´s Catalysts.

Precios de la “RE”: Oxido de Lantano “La Oxide”.

Estimated Export Price Breakdown for La OxideEstimated Export Price Breakdown for La OxideData Source: Asian Metals (www.asianmetals.com)

El perfil del precio cotizado ( exportación) ha cambiado significativamente acorde a la reducción de cuotas.

126GRACE Confidential

La mayor demanda en China también ha influido en el precio cotizado.

Fresh Catalyst Properties, Additions and ECAT Activity

Catalyst BASE Low Rare Earth

REMEDY™ catalyst

Re2O3, Wt.% 2.6 0.7 0.2Re2O3, Wt.% 2.6 0.7 0.2Zeolite SA, m2/gm 220 260 250Total SA, m2/gm 290 330 320

Catalyst Additions, tpd

5 10 5

ECAT Activity 74 74 74

New FCC technology delivers required activity without rare earth

onve

rsio

n

Gas

Yie

ld

PG Y

ield

ctan

e

lefin

Con

tent

rom

atic

Con

tent

CO

Aro

mat

ic

Con

tent

oke

Yie

ld

egen

erat

or T

emp

atal

yst/O

il

atal

yst E

ntra

inm

ent

yclo

ne E

ffici

ency

eq’d

Stri

ppin

g St

eam

Rat

e

Affected Variable

Adjusted Variable

Gasoline

onve

rsio

n

Gas

Yie

ld

PG Y

ield

ctan

e

lefin

Con

tent

rom

atic

Con

tent

CO

Aro

mat

ic

Con

tent

oke

Yie

ld

egen

erat

or T

emp

atal

yst/O

il

atal

yst E

ntra

inm

ent

yclo

ne E

ffici

ency

eq’d

Stri

ppin

g St

eam

Rat

e

Affected Variable

Adjusted Variable

GasolineGasoline


Co

G LP O O Ar

LC C Re

Ca

C Cy

ReVariable


Co

G LP O O Ar

LC C Re

Ca

C Cy

ReVariable





ntGasoline ntGasolineGasoline


Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

nt

Aro

mat

ic C

onte

nt

LCO

Aro

mat

ic

Con

tent

Cok

e Y

ield

Reg

ener

ator

Tem

p

Cat

alys

t/Oil

Cat

alys

t Ent

rain

me n

Cyc

lone

Effi

cien

cy

Req

’dSt

ripp

ing

Stea

m R

ate

A ffected Va riable

Adjusted Variable

Gasoline


Con

vers

ion

Gas

Yie

ld

LPG

Yie

ld

Oct

ane

Ole

fin C

onte

nt

Aro

mat

ic C

onte

nt

LCO

Aro

mat

ic

Con

tent

Cok

e Y

ield

Reg

ener

ator

Tem

p

Cat

alys

t/Oil

Cat

alys

t Ent

rain

me n

Cyc

lone

Effi

cien

cy

Req

’dSt

ripp

ing

Stea

m R

ate

A ffected Va riable

Adjusted Variable

GasolineGasoline





Why is the FCC Important to Refiners?Average Sized FCC

PRODU CT S:44,000 BPD@ $ 25/BBL

FEED:40,000 BPD@ $20 /BBL

Low Value F eeds to High Value Products =

Int roduct ion to U OP FC C T ec hno log y 3uop

FEED-PRODUCT DIFFERENTIAL = $300,000/Day

THANK YOU!

GRACIAS!GRACIAS!

BE SAFE!

130

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