mercury sorbents that allow continued use of fly ash in concrete€¦ · state regulations on...

Mercury Sorbents that Allow Continued Use of Fly

Ash in Concrete

Confidential - Albemarle Corporation © 2012

Ash in Concrete

Workshop of the UNECE Task Force on Heavy Metals –

Berlin, 12 th – 13th April 2012

Dr. Florian KohlEMEA Public Affairs Advisor

1) Albemarle Corporation2) Legislation

USAEU

3) Mercury Control Technologies4) Examples

Outline


4) ExamplesMidwest CrawfordPPL Corette Montana

5) Summary

• A world leader in specialty chemicals• > 4,000 employees• Headquartered in Baton Rouge,

Louisiana• 3 business segments

– Catalysts– Fine Chemicals– Polymer Solutions

• Customers in more than 100 countries• Responsible Care company

Net Sales

0

1

2

3

$ B

illio

n

Albemarle Corporation


20102005 2006 2007 2008 2009

• Responsible Care company• Net sales 2010: 2.3 billion $

Fine Chemicals 25%

Polymer Soluti ons 35%

Catalysts 40% Americas 47%

Europe + MEA 35%

Asia-Pacific 18%

0

Legislation USA

Regulation on mercury emissions

U.S. Federal law on coal-fired power plants new emission limit values as of December 2011

• 1,2 lbs/Tbtu (pounds per Trillion British Thermal Units) for bituminous and sub -bituminous coal


Units) for bituminous and sub -bituminous coal - equals approx. 1,5 µg/Nm 3

• 4,0 lbs/Tbtu for Lignite (5% of U.S. coal)- equals approx. 5,0 µg/Nm3

• 0,025 lbs/Tbtu for new power plants power plants have 3 years time for implementation

State Regulations on Utility BoilersState Regulations on Utility BoilersState Regulations on Utility BoilersState Regulations on Utility Boilers lb/TBtu(equiv) Compliance Emission Limit Or % Reduction Arizona 0.87 31-Dec-13 0.0087 pounds/gigawatt-hour 90 Colorado 1.74 1-Jul-14 0.0174 pounds/gigawatt-hour 80 Connecticut 0.60 1-Jul-08 0.60 pounds/trillion BTUs 90 Delaware 0.60 1-Jan-13 0.60 pounds/trillion BTUs 90 Illinois 0.80 1-Jul-09 0.0080 pounds/gigawatt-hour 90 Maryland 0.80 1-Jan-13 Percent reduction only 90 Massachusetts 0.25 1-Oct-12 0.0025 pounds/gigawatt-hour 95

Legislation USA


Massachusetts 0.25 1-Oct-12 0.0025 pounds/gigawatt-hour 95 Minnesota 0.80 2011/4 Percent reduction only 90 Montana 0.90 1-Jan-10 0.90 pounds/trillion BTUs - New Hampshire 1.60 1-Jul-13 Percent reduction only 80 New Jersey 0.66 15-Dec-07 3 milligrams/megawatt-hour 90 New York 0.60 1-Jan-15 0.60 pounds/trillion BTUs - Oregon 0.60 1-Jul-12 0.60 pounds/trillion BTUs 90 Utah 0.65 31-Dec-12 0.65 pounds/trillion BTUs 90 Wisconsin 0.80 1-Jan-15 0.0080 pounds/gigawatt-hour 90 Average 0.82 Apr-12 89

Plus Georgia & New Mexico have individual plant requirements. North Carolina requires multi�pollutant control.

Note that 0.82 lb Hg/TBtu = ~ 0.82 µg/Nm3 Hg. Compare with 30 & 50 µg/Nm3 European standards.

[Figure 5]

Legislation USA


President Obama addresses mercury: http://www.whitehouse.gov/blog/2011/12/21/protecting-american-families-and-environment-mercury-pollution

EU regulations• Large Combustion Plants Directive2001/80/EC � No Hg ceiling• IPPC Directive (Integrated Pollution Prevention and Control)96/61/EC ��2008/1/EC codified version �� No Hg ceiling• Waste incineration directive2000/76/EC�� Hg �0.05 mg/m³

Legislation EU


2000/76/EC�� Hg �0.05 mg/m³

Industrial Emissions Directive (IED)�Aims to revise and recast 7 separate instruments into a single act, including the 3 directives mentioned above �No Hg ceiling for coal-fired power plants but: Central element is the implementation of BAT: “Best Available Technique”�Requirement that ELVs in individual permit installations shall not exceed BAT-AELs

Germany is planning to introduce new ELV as of 2016: 10 µg / Nm3

�Brominated Powdered Activated Carbon (Br -PAC) provided a great

Mercury Control


Carbon (Br -PAC) provided a great leap forward in effective mercury

capture

� Albemarle invented brominated powdered activated ca rbon (B-PAC)

�First and only user of gas-phase bromination (chemically reacted bromine, bonded to the PAC) instead of salt-impregnation (physically applied br omine, could be washed off), which also allows maximum bromine content.

�Bromine oxidizes Hg °°°° to Hg² + and reacts with it to HgBr2, which is easy to remov e from the gases in the combustion stack by adsorption ont o solids.

�Brominated activated carbon is 10 times more effici ent than plain activated carbon (PAC)

Brominated Activated Sorbent Injection


(PAC)

�Concrete-Friendly TM PAC for preservation of fly ash

�H-PACTM for utility and industrial plants with high tempera ture flue gas environments up to 700°°°°F (400°°°°C), such as hot-side Electrostatic Precipitators (E SP)

�Only PAC mercury sorbents with demonstrated positiv e effects on ESP performance (increased ESP efficiency)

�Process for mercury reduction in cement kilns witho ut having to add a baghouse.

Flue gas flow chart

Brominated

AC

Hg+2Hg+2

Hg0


CaBr

NaBr

Hg0

Hg+2Hg+2

Detroit Edison St. Clair Plant - Total Hg Removal Thirty Day Average = 94%

70%

80%

90%

100%

Tota

l Mer

cury

Rem

oval

The Milestone of U.S. Utility Mercury Control History: 94% removal with subbituminous coal (2004)

First experiences with ACI


0%

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Tota

l Mer

cury

Rem

oval

B-PAC Injection Rate = 3 lb/MMacfB-PAC Injection Rate = 3 lb/MMacf

The use of fly ash by the concrete industry

The use of the fly ash

•9.7 mio. short tons of utility fly ash was used to replace cement in U.S. concrete in 2009.

•Utilities are paid for cement-quality fly ash and avoid disposal expenses


fly ash and avoid disposal expenses

•Activated carbon in fly ash absorbs Air Entraining Agent (AEA). This reduces the quality of concrete.

•If the fly ash cannot be sold for use in concrete the indirect mercury control cost will increase 2-5 times

� Environmental benefits: reduced greenhouse gas emissions, land disposal requirements, utilization of virgin resources, and e nergy to convert the natural products into Portland cement.

� Economic benefits: reduced costs associated with disposal, increased revenue from the sale of fly ash, and savings from using fly ash in place of other, more costly materials.

Benefits of marketing the fly ash


� Performance benefits: greater resistance to chemical attack, increased strength, and improved workability: high fly ash-co ntent concrete can be used for high performance, long-life pavements that are designed to last 50 years – twice the lifetime of conventional paveme nts .

http://www.uswag.org/c2p2factsheet.pdf

Coal Type Subbituminous

Unit Boiler 234 MWeTangential

Coal Type Subbituminous

Unit Boiler 234 MWeTangentia l

Particulate Control Cold Side ESP

ESP Stream Size 117 MWex 2

Midwest Generation Crawford PAC ™ Trial


154 C (full load)

Treated Gas Flow 460,000 acfm

ESP Temperature o

Hg Average 0.08 ppm

Coal S & Cl 0.3% & 80 ppm

Fly Ash Sales Yes

Goal: Reduce Hg emissions by >70% and keep fly ash properties

Hg content in coal: 80ppb (dry)

30-Day Hg Rem oval & In jection Rate81% Average Hg Rem oval at 4 .6 lb /M M acf

60

70

80

90

100

Hg

Rem

oval

%

10

12

14

16

Inj.

Rat

e, lb

/MM

acf

C-PACTM Results with Subbituminous Coal


0

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20

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50

60

8/16

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Hg

Rem

oval

%

0

2

4

6

8

Inj.

Rat

e, lb

/MM

acf

Hg Rem oval Inj Rate

C-PAC C-PAC

C-PAC Foam Index Results @ 4.6 lb/Mmacf (~72 mg/Nm³)

Foam Indexes o f C raw ford F ly Ash w ith C -PAC

60

80

100

Foa

m In

dex

(dro

ps o

f AE

A)

(1-w

t% V

inso

l)

Fron t H oppers (85%?)

B ack H oppers (15%?)

D ark--La farge

L ight--STC

D is tribu tion

Low -Q uality C oncrete


0

20

40

16Aug

19Aug

22Aug

25Aug

28Aug

31Aug

3 Sep 6 Sep 9 S ep 12Sep

15Sep

18S ep

Foa

m In

dex

(dro

ps o

f AE

A)

(1-w

t% V

inso

l)

B aseline

Long-term

D is tribu tion

Prem ium C oncrete

Air Content and Slump

5

6

7

8

Air

(%)

& S

lum

p ("

)

60

80

100

Add

ed A

EA

(m

l/100

kg

cem

ent)Air Slump AEA


1

2

3

4

No Ash Baseline Long-term

Air

(%)

& S

lum

p ("

)

0

20

40

Add

ed A

EA

(m

l/100

kg

cem

ent)

With a little more AEA, the C-PAC air volume is ide ntical to ash control

Setting Times the Same as Without C-PAC

100

1000

10000

100000

Pen

etra

tion

Res

ista

nce

(PS

I)

Initial Set 500 PSI

Final Set 4000 PSI


Headwaters data

1

10

100

100 1000

Time (min)

Pen

etra

tion

Res

ista

nce

(PS

I)

Ash

C-PAC

Still High Compressive Strength

Headwaters data

0

2000

4000

6000

8000

UC

S (

psi)

3 day 7 day 28 day 91 day


0

No Ash Ash C-PAC

0

2000

4000

6000

8000

No Ash Ash C-PAC

UC

S (

psi)

7 day 14 day 28 day 90 day

Albemarle data

PPL Montana Corette Station

• ~163 MW, PC Boiler

• PRB Coal

• Cold-side ESP

• Hg Reg. = 0.9 lb/Tbtu (1/2010)

PPL Montana Corette


• Hg Reg. = 0.9 lb/Tbtu (1/2010)

Objective:

1. Demonstrate that C-PAC™ is able to achieve strict Hg

Field trial PPL Montana Corette plant

PPL Montana Corette


is able to achieve strict Hg ELV

2. Keep properties and ensure marketing of fly ash (amount of C-PAC™ 1.5%)

Inj. Pt.

>800oF

+15”W.C.

PPL Montana Corette


32 Lance, Albemarle Injection Array

Hoses for Compressed Air Only

Hot-Side C-PAC™ Injection into an ESP (PPL Montana plant)

4,000

5,000

6,000

Hg

Out

(ng

/Nm

3)

Appendix K TrapsOhio Lumex CEM

PSA CEM Concrete-Friendly C-PAC

PPL Montana Corette

PAC Injection before the APH

Coal Specs: Hg ~0.08 ppm, 0.3% sulfur, 30% moisture, less than 5%


The permanent unit uses even less sorbent for these reductions & the fly ash is being sold as cement for concrete

0

1,000

2,000

3,000

9/28 12 PM 9/28 6 PM 9/29 12 AM 9/29 6 AM 9/29 12 PM 9/29 6 PM 9/30 12 AM 9/30 6 AM 9/30 12 PM

Hg

Out

(ng

/Nm

3)

3 lb/MMacf 5 lb/MMacf

85% Removal 95% Removal moisture, less than 5% ash

(48 mg/m 3) (80 mg/m3 )

Commercial Sorbent

ProductionAlbemarle increased capacity & is working on further increases

� BB--PAC™PAC™�� HH--PAC ™ PAC ™ high-temperature�� CC--PAC™PAC™ concrete-friendly™

Our Plant


� ACI Injection Systems & Equipment� Full-Scale� M-PACTTM

� Mobile Demo Unit

Load-out at Ohio sorbent production plant

Selection of tailor made activated carbons, according to specific requirements of the plant

Selection of activated carbons

Renewable and sustainable carbons


anthracite

Wood chipsSaw dustCoconut shells

activated carbons based on coal

hard coal

� C-PAC is able to achieve high-level mercury reductions while retaining the capability of fly ash sales for concrete.

� Compared to ash – containing control concrete, concrete with C-PACTM –

fly ash was shown to exhibit the same air content, slump, and setting time with only a relatively higher dosage of AEA.

� The higher standard deviations of foam index values of fly ashes with C-

Conclusions


� The higher standard deviations of foam index values of fly ashes with C-PACTM were no higher than those without.

� C-PACTM mercury sorbent does not appear to affect air stability with mixing and produces concretes at least as strong as fly–ash–containing concrete without it.

� Albemarle is selling C-PACTM commercially with excellent mercury removal results and the fly ash is being sold.

Acknowledgement

Daryl LipscombDaryl LipscombDaryl LipscombDaryl Lipscomb

Ron Landreth Ron Landreth Ron Landreth Ron Landreth

Yinzhi Zhang Yinzhi Zhang Yinzhi Zhang Yinzhi Zhang

Emma Zhou Emma Zhou Emma Zhou Emma Zhou


Emma Zhou Emma Zhou Emma Zhou Emma Zhou

Wolfgang HardtkeWolfgang HardtkeWolfgang HardtkeWolfgang Hardtke

Contact details

Dr. Florian Kohl

EMEA Public Affairs Advisor

[email protected]


[email protected]

+32 10 48 17 56

+32 470 470 827

mercury sorbents that allow continued use of fly ash in concrete€¦ · state regulations on...

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