New Antifoam Reduces Silicone Carryover

Bruce Wright
Senior Technical Engineer

Galveston, TX

May 3-6, 2011

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Agenda
Delayed coker foam control Silicone decomposition New coker antifoam Case histories

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Delayed Coker Foaming

Operation of the delayed coker drum makes it an ideal

place for foam to form

Gas (steam and hydrocarbon) flowing through hot, viscous, and polar liquid Cracking of molecules creating additional polarity Pressure P not too high hi h so that h the h gases can b be pulled ll d off ff the h drum and sent to the main fractionator

Excessive or uncontrolled foaming causes foam-over

from the drum into the main fractionator

Will carry coke fines into the main fractionator and up the tower fouling the trays, downcomers, and lines Will force the unit to shut down
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Antifoams for Delayed Cokers

Polydimethylsiloxanes (PDMS) are currently the most

cost-effective coker foam control agents available

PDMS: Reduces foaming while filling drum Minimizes foam-over potential in coke drum Allows smaller outages; more coke production Silicon poisons downstream HDS catalyst Mechanical entrainment Distillation of small silicone molecules Higher MW PDMS = increased stability / slower

decomposition
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Coker Antifoam Technology

Hydrocarbon to Fractionator

Typical Antifoam Injection Locations

Antifoam injection
Sensor Sensor
Hydrocarbon Vapor

Antifoam injection

Furnace Coker Feed Line

Foam

Headed Drum

Coke

Unheaded Drum

Coke Removal

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Factors Affecting Antifoam Performance

Dilution of antifoam in carrier stream Type of diluent can make a difference Inject so antifoam is spread on foam front Injection should be opposite overhead vapor line Less foaming with higher drum temperatures Thermal decomposition rate of PDMS

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How Does Silicon End Up in Liquid Products?

Entrainment controlled by: Injection away from OH Use carrier to blow antifoam to foam front High boiling carrier to minimize flashing Decomposition rate controlled by: Drum temperature PDMS molecular weight
Vapor Antifoam Injection

Hot Gas

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Poly-DimethylSiloxane (PDMS)
CH CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 3 O Si Si Si Si Si Si Si Si Si Si O O O O O O O O O O CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 Si

Relatively thermally stable Effectively reduces foam in oil based systems

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Poly-DimethylSiloxane (PDMS)

CH3 (CH3)3SiO-(SiO)n-Si-(CH3)3 CH3

Very strong; protects adjacent Si-C linkage Most susceptible to degradation; forms active site

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Thermal Degradation of Silicone

PDMS begins to decompose at 350C (662F) Higher temperature = faster decomposition Forms cyclic methysiloxane trimers and larger Defoaming ability is reduced Breakdown products go overhead and contaminate

cracked products leads to HDS poisoning

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PDMS Degradation Mechanism

Bends back & reacts at each end Cleaves Degradation products include: Hexamethylcyclotrisiloxane Octamethylcyclotetrasiloxane, etc. Volatile species; B.P. ~ 350F (~177C) Seven or less monomers volatile at coker temperatures
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Cyclic Trimer Breakdown Products

CH3 H3C Si Si CH 3 O H3C Si O O CH3

CH3

H3C H3C

Si O

O Si

CH3 Si CH3 O CH3

H3C

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Decomposition Products of Silicone Oil Product Cyclic Trimer C li T Cyclic Tetramer t Cyclic Pentamer Cyclic Hexamer B.P. C 134 175 8 175.8 210 245
o

B.P. F 273 348 410 473

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Higher Viscosity Silicone

Higher viscosity = larger molecule Larger molecule takes longer to degrade
Defoams longer Lower dosage required Less Si in products Less catalyst contamination

Even ultra-high viscosity silicone oil will

thermally decompose

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MW of Stressed Silicone
PDMS Stressed for 5 Hours at 375C (700F)

Silicone MW Viscosity(cSt) Initial

MW Stressed

% Reduction

60,000 100,000

95,348 105,204

82,646 98,802

13.3% 6.1%

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Higher MW Results in Less Si to Coke Drum

Coker Antifoam Case Example Moving to High Viscosity Antifoam (600 Mcst)
1.80

1.60

1.40

Plant switched from 60Mcst to 600Mcst Antifoam resulting in less usage and lower silicon addition

Antifoam (lb Si/Mbbl Resid)

1.20

1.00

0.80

0.60

0.40

0.20

0.00
Oct-99 Mar-00 Nov-99 Oct-00 Jul-00 May-00 Nov-00 Dec-99 Jan-00 Apr-00 Aug-99 Feb-99 Jun-99 May-99 Aug-00 Sep-00 Dec-00 Feb-00 Sep-99 Mar-99 Jan-99 Jun-00 Apr-99 Jul-99

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Silicon Reduction in Products

60,000 cSt ppm Si 34 7.9 7.3 600,000 cSt ppm Si 12.3 3.2 2.7 ppm Si reduction 21.7 4.7 4.6 %Si reduction 63% 59% 63%

Naphtha LCGO HCGO

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How Can We Overcome Si Poisoning?

Find a cost-effective non-silicon antifoam /

defoaming agent Identify alternate structures of siloxane antifoams Trap silicon compounds in the cracked gases

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Introducing Baker Petrolite FOAMSTOP 5000 Low Catalyst Impact (LCI) Antifoam
Limit to higher molecular weight PDMS
High viscosity difficult to handle Higher molecular weight costs more

New type of antifoam developed

Alternate structure PDMS Effective at lower dosages Significantly lower rate of thermal decomposition Prevents foam build-up Patents granted
Baker Petrolite FOAMSTOP is a trademark of Baker Hughes Incorporated
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Field Trial #1
Coker makes fuel grade coke Base case 600,000 cSt silicone antifoam Measured foam knock down Re-foam after drum switch Plant wanted to reduce Si contamination of coker

products

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Field Trial #1
Sample 600,000 cSt (ppm Si) 3.29 FOAMSTOP 5000 LCI (ppm Si) 1.29 % Reduction

Coker Naphtha Coker Kerosene

62.5%

4.41

1.92

56.5%

All samples taken at the same timing before drum switch

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Field Trial #1
Results with Baker Petrolite FOAMSTOP LCI

antifoam
Knocked down foam better Prevented re-foam after switch better Could allow reduced outages Reduced silicon contamination of products by over 50%

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Field Trial #2

Anode grade coke production Si in product poisoning catalyst Excessive defoamer usage Used U d 600 600,000 000 cSt St silicone ili antifoam tif f for f four years

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Field Trial #2
PPM Silicon In Cracked Products
Coker Product 600,000 cSt FOAMSTOP 5000 LCI 35 9 35.9 10.3 2.2 Drum 2 Naphtha LCGO HCGO
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% Reduction

Drum 1 Naphtha LCGO HCGO 58.0 58 0 38.8 5.5 38 73 60

33.8 28.7 1.8

8.2 3.2 0.9

75 88 50

Samples taken one hour before drum switch

Field Trial #2
Baker Petrolite FOAMSTOP 5000 LCI antifoam

reduced Si in product
More efficient to add antifoam early
Foam easier to prevent than knock down Use less antifoam

Kept foam down after drum switch New material easy to handle

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Summary
Baker Petrolite FOAMSTOP 5000 low catalyst

impact antifoam is more stable than traditional coker antifoams Controls foam better More M persistent i i in the h coke k d drum Reduces silicon contamination of coker products which slows deactivation rates of downstream hydrotreater catalysts Improves refinery profitability by minimizing costs of HDS catalyst replacement
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Closing
Thank you for your attention! Contact information: bruce.wright@bakerhughes.com

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