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COMMERCIAL EXPERIENCE OF METAL PASSIVATOR ADDITIVE

AND PERFORMANCE BENEFITS

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Introduction

FCC/RFCC CATALYST 1913, Thermal cracking of oils-free radical mechanism 1915, AlCl3 based cracking catalyst (Mc Afee) 1928, Houdry: solid/acid treated clay/ alumina based catalyst 1940, First synthetic silica-alumina catalyst 1948, Commercial production of microspheroidal FCC catalyst

(Davison) 1962, Zeolite cracking catalyst 1974, CO-promoter 1975, Ni passivation, 1978, Vanadium passivation 1986, ZSM-5 based octane additive

FCC HARDDWARE 1936, First fixed bed commercial cracking unit 1942, First commercial FCC unit (Standarad Oil) 1943, First commercial Thermofor catalytic cracking (TCC) 1956, First riser cracking unit (Shell Oil) 1971, Short contact riser (Kellog)

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Introduction cont….

FCC/RFCC is flexible process Loading/unloading and switch over of catalyst/

additive Addition of catalyst / additive can be varied optimally

as per the unit requirement.

Performance of catalyst depends upon Process condition Feed properties Unit constraint change Product value change Product quality requirements

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Challenges in processing of resid feeds

Resid feeds High metal content, 3-15 ppm Ni and 10-30 ppm V, in

the form naphthenates, porphyrins Higher sulphur content, 1.5-3 wt% Higher basic nitrogen, 500-1500 ppm CCR, 1-6 wt%

Other issues Statutory requirement on products and effluent Limited catalyst suppliers, short supply of key

component and rising cost

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Challenges in processing resid feeds in RFCCU

Rx

Rg490-550 OC

5 Sec

650-720OC

Hardware limitation•Regenerator metallurgy•Combustion Air•Cyclone efficiency•Wet gas compressor

Catalyst•High V tolerance•Low coke make•Higher thermal and hydrothermal•Higher attrition resistance with high zeolite content

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Vanadium deactivation mechanism

V-Porphyrins FCC catalyst

in feed (V+3, V+5) +

Reactor - reducing environment

V on catalyst surface with coke

Regenerator + O2

V2O5 (V+4, V+5)on surface Mobile (VO(OH)3, V+5) Fresh catalystOld catalyst

Particle to particle migration

RE Vanadates, zeolite destruction

+ Rare Earth in Zeolite

Steam

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FCC catalyst particles with contaminate metals

Alumina/silica alumina

RE-Y zeolite

3 micron

Binder : silica

Clay

V

Ni

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4 complete sodalite cages/UC6 half sodalite cages/UC8 one eighth sodalite cages/UC

Structure of faujasite (Y) type zeolite

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Effect of metals on SA, feed rate, CCR and coke*CCR/feed rate based on model

Coke

Only option, replace with fresh catalyst

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Options to combat Ni & V poisoning Addition of fresh catalyst

Most common method, costly for higher catalyst consumption

Feed hydrotreatment Attractive - many advantages, higher capital & operating costs Use of metal tolerant catalysts Difficult to balance between metal tolerance, activity &

selectivity and cost Chemical demetallization-DEMET

Sulfidation followed by chlorination-High cost technology

Magnetic separation-Magnacat Requires large capital, difficult to remove vanadium

Use of liquid passivators & solid additives

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Type of metal passivator / trap additive

Ni passivator (liquid emulsions)AntimonyBismuthCerium

V-Trap additive (solid/liquid)Rare earthMgO/AluminaTin

FCC AdditivesFCC Additives

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IndVi: Additive for simultaneous passivation of Ni & V

ABD: 0.78-0.91 gm/cc, AI < 4, SA: 60-70 m2/gm, APS: 85-100 micronDosage : 1-10 wt%

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Laboratory testing

Metal deactivation protocol

Blending 5 wt% additive with base catalystMetal doping (Ni-2500 & V-6852)-Mitchell methodSingle step H2 reductionHydrothermal deactivation at 788 deg.C/3hrsMeasurement of physico- chemical propertiesPerformance evaluation – ACE R+ unit

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Impact of IndVi on physical properties & Coke

Surface area, m2/gm

X-ray crysallinity

Fresh Metal doped -

Steamed

Fresh Metal doped -

Steamed

Base catalyst

263 96 23.4 5.4

Base catalyst + 5 % additive *

258 110 20.3 7.08

* Metal passivator surface area 66 m2/gm

5 wt% IndVi, reduced coke from 1 to 1.9 wt% for cat/oil ranging from 3.3 to 5.6

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Typical feed properties

Refinery HR

Density, g/cc 0.94

Sulfur, wt% 3.6

CCR, wt% 4.1

Total nitrogen, ppm 1294

Na, ppm 0.38

Fe , ppm 0.72

V , ppm 22

Ni , ppm 7

Mean average BP, C 460

Aromatics, wt% 61

Saturates, wt% 39

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Predicted plant performance yield

Reference Base case(RFCC Catalyst +

5 wt% ZSM-5 additive)

Base case + 5 wt% IndVi

Delta Yield

Yield , Wt% A B A-B

Drygas 4.77 4.53 -0.24

LPG 17.43 19.09 1.66

Gasoline 29.07 28.14 -0.93

Heavy Naphtha 9.73 10.78 1.05

Light Cycle Oil 22.61 23.35 0.74

Clarified Oil 9.28 7.11 -2.17

Coke 7.11 7.08 -0.03

-216 Conversion 68.11 69.52 1.41

Fresh feed rate M3/hr 99.16 99.16

Recycle, M3/hr 9.41 9.41

ROT, 0C 510 510

Dense bed temperature, 0CRG1/RG2

686/741 676/730 -10

CCR, MT/hr 453 474

Cat/Oil 4.94 5.17

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Predicted plant performance yield – Increasing t’put

Reference Base case(RFCC Catalyst +

5 wt% ZSM-5 additive)

Base case+ 5 wt% IndVi

Delta Yield

Yield , Wt% C D C-D

Drygas 4.26 4.02 -0.24

LPG 14.32 15.93 1.61

Gasoline 28.75 27.88 -0.87

Heavy Naphtha 9.67 10.73 1.06

Light Cycle Oil 24.05 24.8 0.75

Clarified Oil 11.96 9.77 -2.19

Coke 7 6.87 -0.03

-216 Conversion 64 65.43 1.43

Fresh feed rate M3/hr 110.16 110.16

Recycle, M3/hr 9.41 9.41

ROT, 0C 505 505

Dense bed temperature, 0CRG1/RG2

689/752 679/740

CCR, MT/hr 459 482

Cat/Oil 4.3 4.5

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Commercial production

Toll manufacturing at SCIL

Manufactured 12 MT IndVi additive for plant trial in M/s SCIL

facilities.

Physico-chemical characteristics of commercial lot match with

laboratory catalysts.

Properties Typical specifications

Surface area (m2/gm) 60-70

Na2O, wt% 0.2 max

ABD (gm/cc) 0.86-0.94

Attrition Index Less than 5

LOI Less than 5

APS, microns 85-100

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Addition rates during IndVi plant trial

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Commercial trialAttribute Unit Base Case IndVi Trial run Delta values

Total fresh feed rate m3/hr 105.6 109.3 3.7VR rate m3/hr 4.6 7.8 3.2

Feed CCR wt% 2.15 2.91 0.76

VB Naphtha + Wild Naphtha m3/hr 2.9 2.9 0

COT oC 220 217 -3ROT oC 510 510 0

Fresh Catalyst addition rate MT/day 4.0 3.8 -

ZSM-5 addition rate Kg/day 100 - -

IndVi addition rate Kg/day - 200 -

RG-1 dense bed Temperature oC 677 670 -7

RG-2 dense bed Temperature oC 726 727 +1

Yields (Cut point corrected)

Acid gas + Dry Gas wt% 4.06 4.10 +0.04

LPG wt% 12.61 12.22 -0.39

LCN (C5-150oC) wt% 34.83 31.91 -2.92

HCN(150-220oC) wt% 9.78 12.21 +2.43

LCO (220-370oC) wt% 22.31 22.85 +0.54

TCO (150-370oC) wt% 32.09 35.06 2.97

DCO (370oC+) wt% 11.35 11.82 +0.47

Coke wt% 5.06 4.89 -0.17

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Commercial trial cont..

PLANT TRIAL – RFCCU

Plant trial run of IndVi additive was conducted in RFCCU for 20 days

with 4.5% additive concentration. During the PGTR, ZSM-5 was

added to the system @ 100 kg/day along with fresh catalyst addition

rate of 4 MT/hr.

Around ~3 wt% TCO yield increased with more or less corresponding

decrease in gasoline yield. Reduction in gasoline yield and increase in

TCO yield in line with the current Refinery objective.

VR addition rate was increased by 3.2 m3/hr during the trial run due

to increased available cushion in regenerator dense bed temperature.

Even with higher VR rate, RG1 dense bed temperature was lower by 7 oC compared to base case.

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Conclusion

Ni & V are the prominent metals accumulating on catalyst which reduce

crystallinity, SA and activity and increases coke & dry gas yield.

IndVi additive developed & Commercialized by IOCL is capable of

simultaneous passivation of both vanadium and nickel.

Presence of additive in RFCC unit, helps in retaining higher surface area and

crystallinity.

Predicted plant performance yield based on laboratory data showed

reduction in bottom and increase in distillate yields.

Commercial plant trial of IndVi at HR RFCC unit showed:

Enhanced t’put containing higher VR

Enhanced TCO yield

Lower regenerator-1 dense bed temperature (by 7oC) at higher t’put,

Comparable CLO yield similar to base case

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The Authors acknowledge the contribution of followings towards successful commercial plant trial

mr g. saidulu

dr v.chidambaram

mr balaiah swam

Mr.S.p.Choudhury

dr.m.b.patel

dr.j.christopher

mr.somnath kukkade

mr. manoj kumar yadav

ms. Soma chattopadhyay

Ms sangeeta Purkaystha

Mr sujit dasgupta

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Thank You

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Backup Slides

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Effect of CCR on plant

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Effect of Metals (Ni + V), on MAT Activity

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Effect of Metals (Ni + V), on SA

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Deactivation of surface area with different metals

0

20

40

60

80

100

120

140

160

180

200

0 5000 10000 15000

Su

rfac

e ar

ea,m

2 /g

Metals, ppm

Deactivation of surface area with different metal

V

Na

Fe

Ni

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COMMERCIAL TRIAL Cont..

3131

Feed propertiesRefinery HR(actual) Jan, 09 feed, HR PR, 08

Density, g/cc

0.9391 0.921 0.866

Sulfur, wt% 3.59 2.8 0.713

CCR, wt% 4.06 2.64 1.5

Total nitrogen, ppm 1294 - 337

Na, ppm 0.38 -

Fe , ppm 0.72 -

V , ppm 21.53 34 16

Ni , ppm 6.9 3.2 6

Mean average BP, C 458 469

Aromatics, wt% 61.3 82.9

Saturates, wt% 38.7 17.1

Viscosity 104

3232

Catalyst deactivation- chemistry

1. V deposits on catalyst surface along with coke 2. V2O5 generates in oxidative environment

4 V + 5 O2 2 V2O5

3. Vanadium oxide converted in vanadic acid in presence of reducing environment (steam)

V2O5 + 3 H2O 2 VO (OH)3

La2O3 + 2H3VO4 2LaVO4 + 3H2O

Al2O3 + 2H3VO4 2AlVO4+ 3H2O

3333

Properties of Ni on RFCC catalyst

Ni exists under FCC condition as +2 or 0

valance state

Ni is 4 times more active than vanadium and it’s

activity is more predominant with higher

alumina content in catalyst

+2 state of nickel reacts to form NiAl2O4and

NiSiO3 with surface alumina and silica.

NiSiO3 is more stable, SiO2 based binders are

preferred as natural passivators for Ni

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V & Ni passivating agents

Ni Passivation Antimony, Bismuth and Cerium based emulsions are in use as additive along

with hydrocarbon feed Natural SiO2 based binder partially mitigates undesired effects Additive catalysts based on Sb, Bi have been in use as blend with base

catalyst Order of passivation-Sb > Bi > Sn > P >Al

V Passivation Tin, Antimony, Titanium, Zirconium and Rare earth based passivators are in

already use for vanadium passivation Alumina based metal trap partially passivates destructive behavior of

vanadium

3535

FCC Unit schematic