BASF s Mercury Sorbent HX A Mercury MATS Compliant Technology William Hizny, Fabien Rioult PhD, Xiaolin Yang PhD

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1 BASF s Mercury Sorbent HX A Mercury MATS Compliant Technology William Hizny, Fabien Rioult PhD, Xiaolin Yang PhD EUEC 2014 February 3-5, 2014 Phoenix, AZ 1

2 Overview Mercury Sorbent HX MATS compliant mercury emissions demonstrated Review of field trials An established pattern of compliant performance Preserved fly ash properties in concrete A low carbon in the fly ash solution for mercury emissions compliance Summary 2

3 Mercury Sorbent HX is a brominated mineral sorbent enabling a low carbon solution for mercury emissions compliance Macroporous mineral selected to optimize bromine utilization in system FLY ASH FLY ASH Untreated PAC offers uninhibited access to mercury capture sites FLY ASH Activated carbon (particle) Bromine content provides sufficient mercury oxidation with minimal potential impact on balance of plant FLY ASH Bromine (surface) Kaolin (particle) 3

4 Mercury Sorbent HX Field demonstration programs Site A B C Coal Powder River Basin Powder River Basin Powder River Basin Nominal load capacity 800 MW 200 MW 300 MW Particulate collection device Coincident Dry Sorbent Injection (DSI) ESP ESP Fabric filter No Yes No DSI material n/a Sodium bicarbonate n/a Mercury sorbent injection location Upstream air preheater Upstream air preheater Upstream air preheater DSI injection location n/a Downstream air preheater Injection system design Eductor Rotary valve Rotary valve Fly ash currently sold Yes Yes Yes n/a 4

5 Mercury Sorbent HX Equipment schematic Site B Hg CEMS* / Inlet Mercury Sorbent (~700 F) Sodium Bicarbonate (~290 F) Stack SO 2 (0.61 lb/mmbtu) ESP Boiler Air Heater Stack ( 285 F) S Cl Hg PRB Coal Assay 0.34% 0.36% 5ppm 6ppm 85ppb 168ppb Hg CEMS* / Outlet Thermo Scientific Mercury CEMS* [* CEMS = Continuous Emissions Monitoring System] 5

Mercury Sorbent HX Test matrix Site B Test program 1 2 Sodium bicarbonate injection On Off Injection methodology Parametric n/a Mercury sorbent

6 Mercury Sorbent HX Test matrix Site B Test program 1 2 Sodium bicarbonate injection On Off Injection methodology Parametric n/a Mercury sorbent injection On On Injection methodology As needed for MATS Hg compliance Parametric Portable injection systems used for dry sorbent and mercury sorbent injection 6

7 Mercury Capture, % Stack Mercury Emission, lb/tbtu Mercury Sorbent HX Injection, lb/mmacf Test Program 1 Parametric SBC injection with MATS mercury compliant emissions Steady intraday mercury sorbent injection rates for MATS compliance Analysis inconclusive as to cause(s) of step change in mercury sorbent injection rate between successive days 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Dual Injection - Field Performance Site B MATS 1.2 lb/tbtu 0.8 Day 1 Day 2 (AM) ,000 2,000 3,000 4,000 Sodium Bicarbonate Injection Rate, lb/hr Hg Capture Stack Hg HX Injection

8 Mercury Capture, % Stack Mercury Emission, lb/tbtu Test Program 2 Parametric injection of Mercury Sorbent HX Parametric curve based on hourly average mercury emissions Responsiveness confirmed that Mercury Sorbent HX flowed well through an injection system nominally designed for PAC BASF Mercury Sorbent HX - Field Performance Site B 100% % % % % % % % % 1.6 MATS 1.2 lb/tbtu 10% 0.8 Day 2 (PM) 0% Sorbent Injection Concentration, lb/mmacf Hg Capture Stack Hg 8

9 Mercury Capture, % Mercury Capture, % Mercury Capture, % Stack Mercury Emission, lb/tbtu Stack Mercury Emission, lb/tbtu Stack Mercury Emission, lb/tbtu Mercury Sorbent HX demonstrated an established pattern of compliant performance 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% BASF Mercury Sorbent HX - Field Performance Site C 100% BASF Mercury Sorbent HX - Field Performance Site B % % % % % 1.6 MATS 1.2 lb/tbtu 40% % 90% 80% 0% % % Sorbent Injection 20% Concentration, lb/mmacf 60% Hg Capture 10% Stack Hg 50% MATS 1.2 lb/tbtu 0.8 Site C PRB+FF Site B PRB+ESP Site A PRB+ESP 0% 40% % Sorbent Injection Concentration, lb/mmacf Hg Capture 20% Stack Hg 10% MATS 1.2 lb/tbtu BASF Mercury Sorbent HX - Field Performance Site A % Sorbent Injection Concentration, lb/mmacf Hg Capture Stack Hg 9

ASTM C 457 metrics determine concrete compatibility of mercury sorbents in fly ash Concrete Sample Mixes Cement Source Lehigh Mitchell Type I/II Cement, lb/yd 3 450 451 Fly Ash (Source) Class C (Site

10 ASTM C 457 metrics determine concrete compatibility of mercury sorbents in fly ash Concrete Sample Mixes Cement Source Lehigh Mitchell Type I/II Cement, lb/yd Fly Ash (Source) Class C (Site A) Entrained Mercury Sorbent None BASF Mercury Sorbent HX Sorbent in Ash n/a 1%-wt Fly Ash, lb/yd Replacement, % Sand, lb/yd Stone, lb/yd Water, lb/yd AEA* BASF MasterAir AE 90 AEA* (oz/cwt) Right amount of air voids? Concrete Air Volume after 60 minutes agitation after initial mix Right size of air voids? Specific Surface Area Right spacing of air voids? Spacing Factor > 3% > 600 in 2 /in 3 < in [* AEA = Air Entraining Admixture] 10

11 FAIL FAIL FAIL PASS PASS PASS Fly ash mixed with Mercury Sorbent HX demonstrated stable entrained air properties 7.0 Concrete Air, % Specific Surface Area, in 2 /in 3 Spacing Factor, in Sample 1 Sample 2 Fly ash Fly ash only containing 1%-wt BASF Mercury Sorbent HX 300 Sample 1 Sample 2 Fly ash Fly ash only containing 1%-wt BASF Mercury Sorbent HX Sample 1 Sample 2 Fly ash Fly ash only containing 1%-wt BASF Mercury Sorbent HX After Initial Mixing After 60 Minutes Agitation Threshold Value 11

Normalized Injected Carbon Content for Equivalent Mercury Capture Mercury Sorbent HX is a low carbon in the fly ash solution for MATS Hypothetical MATS Compliant Application (PRB+ESP) 1 Mercury

12 Normalized Injected Carbon Content for Equivalent Mercury Capture Mercury Sorbent HX is a low carbon in the fly ash solution for MATS Hypothetical MATS Compliant Application (PRB+ESP) 1 Mercury Sorbent HX achieves mercury MATS compliance at an injected carbon level significantly lower than even the latest generations of PACs 0 PAC Gen1 PAC Gen2 Mercury Sorbent HX As a novel solution that balances mercury control and fly ash quality, the Mercury Sorbent HX patent has been allowed by the United States Patent and Trademark Office (12/2013) Note: Relative values based on comparative study of published technical literature for PRB coal-fired units equipped with a cold-side ESP. 12

abrasion Pneumatic transport of mercury sorbents may cause abrasion and erosion of the conveyance system over time Material Mercury Sorbent HX

13 Low carbon = Low abrasion Mercury Sorbent HX less abrasive than PAC Head with PVC coating Einlehner Abrasion Test* Stirring Staff Bronze Wire Suspension with sorbent Before Test* After Test* Key metric: weight loss of bronze wire disc per fixed number of revolutions Higher values = More abrasion Pneumatic transport of mercury sorbents may cause abrasion and erosion of the conveyance system over time Material Mercury Sorbent HX mg_loss / 100k revolutions 13.8 PAC 53.8 Mercury Sorbent HX is almost 4 times less abrasive than PAC [* Generic test photos; for illustration purposes only] 13

14 Summary Mercury Sorbent HX consistently delivers high mercury removal to achieve MATS compliant mercury emissions Demonstrated on both electrostatic precipitator and fabric filter equipped units Mercury Sorbent HX differentiates itself as a low carbon in the fly ash solution for mercury emissions compliance Preserves the salable properties of fly ash for concrete applications Petrographic analysis confirms air-void system for freeze-thaw durability Less abrasive material than PAC 14

innovative solution for mercury capture BASF works closely with the utilities in the organization of their

15 BASF, ready to supply In 1908, kaolin operations began in McIntyre, Georgia and have grown over the years to yield 4 plants and numerous mines BASF leverages its expertise in materials science to provide a unique innovative solution for mercury capture BASF works closely with the utilities in the organization of their trials Mercury Sorbent HX can be supplied in supersacks, trucks, or trains BASF Production Site, McIntyre, GA 15

16 Questions / Acknowledgment Fabien Rioult Ph.D. Business Development Mgr., Clean Air fabien.rioult@basf.com mercury@basf.com BASF would like to acknowledge the utilities that graciously extended an opportunity to demonstrate Mercury Sorbent HX. We have respected their request for anonymity. BASF also would like to acknowledge United Conveyor Corporation (UCC) for conducting some of the trials discussed in this paper. 16

BASF Mercury Sorbent HX

2013 World of Coal Ash (WOCA) Conference - April 22-25, 2013 in Lexington, KY http://www.flyash.info/ BASF Mercury Sorbent HX William Hizny 1, Fabien Rioult PhD 1, Xiaolin Yang PhD 1 1 BASF Corporation,