1. Mercury Abatement in the US
Cement Industry
John Kline
John Kline Consulting

2. Cement Processing in US
82 Clinker Plants
Source: EPA Web Site 128 Operating Kilns

3. Mercury Emissions in US by Source
(metric tons per year)
Source Air Water Soil
Mercury from cement production 2.31 0 1.16
Mercury from large combustion plants 43.46 0.17 33.06
TOTAL EMISSIONS (tpy) 109.2 46 2658.2
Cement as % of Total 2.1% 0% 0.04%
Large Combustors as % of Total 39.8% 0.4% 1.2%
Source: The US Mercury Emission Inventory for the Arctic Council Action Plan,
Karen Rackley and Anne Pope, 1999 National Emissions Inventory for HAPs (NEI)
and 2001 Toxic Release Inventory (TRI).

6. Cement Kiln Regulations
Cement Plants
that burn
Hazardous Commercial and Industrial
Waste Solid Waste Incinerators
(CISWI)
Hazardous All Cement
Waste Plants / Kilns 82 Clinker Plants
Combustors (NESHAP) 128 Operating Kilns
(HWC)
Cement Plants
that burn Non-
Hazardous
Waste

7. Summary of Standards
Pollutant Existing Sources New Sources EPA expected
Emissions
Reductions
Mercury 55 lb/million tons clinker 21 lbs/million tons clinker 93%
THC 24 ppmvd 24 ppmvd 82%
O-HAP 12 ppmvd 12 ppmvd
PM 0.07 lb/ton clinker 0.02 lb/ton clinker 91%
HCL 3 ppmvd 3 ppmvd 96%
Bold indicates a change

8. Monitoring Standards
Original Rule Final Rule
• Particulate CEM • Particulate
Parametric Testing
• Mercury CEM • Mercury CEM
• THC CEM • THC CEM
• HCl CEM

9. Timing
• Original Compliance Date – Sept, 2013
• Revised Compliance Date – Sept, 2015
• Possibility of one year extension
– Need to demonstrate significant effort, and
– External forces at play

10. Mercury in Power Plants
• One source – Fuel
• Multiple Outlets – Bottom ash, slag, flyash,
FGD solids, FGD liquids, stack
• One pass with no recycle
• Relatively stable gas composition and
temperatures
• What goes in – comes out !

11. Mercury in Power Plants
Output
Input
And Slag
Outputs
Source - Tutorial: Mercury Chemistry in Boilers and Mercury Control Technology (Part 1), C. Senior, April 17-21, 2005
30th International Technical Conference on Coal Utilization & Fuel Systems, Clearwater, Florida

12. Distribution of mercury concentrations in solid fuels from ICR, Part 2 data for fourth quarter, 1999. Source: Inherent Mercury Controls within
the Portland Cement Kiln System—Model of Mercury Behavior within the Manufacturing System, C. Senior, C. Montgomery, A. Sarofim,
Portland Cement Association

13. Mercury in Power Plants
Mercury in Cement Plants
• One source – Fuel => multiple fuel and raw
material sources
• Multiple Outlets – Bottom ash, slag, flyash ash,
FGD solids, FGD liquids, stack => outlets stack and
dust
• One pass with no recycle => multiple potential
recycle loops
• Relatively stable gas composition and
temperatures => large swings in gas temperature
and composition (with in-line mills)

14. Typical Levels of Mercury in the Cement Industry
Mercury concentration in PPB
•Limestone 10 to 100, can be up to 1000 or more
•Coal: 20 to 200 (also Cl = 800/2000ppm)
•PRB: 40 to 100 (also Cl = 7/35ppm)
•Coke: 10 to 20
•Other fuels: <50
•AF generally low – except HWF: up to 6000 (not
in EPA) and SSW (up to 200)
Flyash – 37 Plants
•Bottom ash and fly ash: 200 to 400 Bottom Ash – 21 Plants

15. Looking Deeper at Raw Materials
The most common ingredients of cement are:
– Limestone (75% - 80%),
– Shale and/or clay (15% - 20%),
– Sand (2% – 5%),
– And Iron Source (1% - 2%)
Limestone, Shale and Clay are sedimentary
materials and therefore typically low in metals
including mercury
The exception comes when these materials are
associated with volcanics

16. Variations in Raw Materials
Monthly mass balance Hg contributions by raw material (Linero, Read, and Derosa, 2008)

17. Mercury Cycle in a Modern Cement Plant with In-Line Raw Mill
Kiln Feed
330 oC
Stack
1000 oC
90 oC Fuels From Kiln
& Precalciner
BH Catch Coal Mill
Raw Mill Feed
Source: "Fate and transport of mercury in Portland cement manufacturing facilities", J.K. Sikkema. Theses and Dissertations. Paper 11907. http://lib.dr.iastate.edu/etd/11907

18. The Hg cycle / with in-line raw mill:
can be 10 to 50 times the inputs
Source: “MERCURY IN THE CEMENT INDUSTRY”, Roberto RENZONI ,Christophe ULLRICH, Sandra BELBOOM,
Albert GERMAIN, Universite de Liege, Independently commissioned by CEMBUREAU – CSI

19. Spot Balance in Preheater Kiln
with Raw Mill Running
Spot Balance
Kiln
18-Jun-12 Filter Inlet Exit Gas Calculated
Feed In grams/hr Balance 18.8 PB 75.2 Ox.
369.1 PB Bypass grams/hr CEM Signal 174.4 Ox. 98.7 El.
83.9 Ox. % Capture 98.7 El. Fiter Capture 173.9 Total
30.0 El. 291.9 Total 57% Ox. Only Exit Gas Measured
113.9 Total 76.4 Ox.
100.3 El.
176.7 Total
Cylcone Out
18.8 PB
Fuel In Raw Mill Feed 90.5 Ox.
21.2 PB 293.4 PB 68.7 El.
178.0 Total
Raw Mill
Duct Capture
287.4 Ox. 53% Ox. Raw Mill Out CKD
102.8 El. 554.1 Total 118.0 PB
390.3 Total To Raw Mill
192.0 Ox.
68.7 El.
260.8 Total Raw Mill Product
376.1 PB Coke 0.13 PB Coal Mill
Coal 0.23 PB Exit Gas Calculated
0.16 El.
Exit Gas Measured
0.27 El.
To Coal Mill Coal Mill Product
11.5 Ox. 15.8 PB
4.1 El.
15.6 Total

20. Mercury Balance
Mercury Inputs
From Kiln Feed 54.0%
From Fuel (As-Fried) 3.1%
From Raw Fuel 0.1%
From Raw Mill Feed 42.9%
Mercury Outputs
In Raw Mill Product 55.0% All CKD
In CKD 17.3% Removed
Oxidized in Kiln Stack 11.0%
Elemental in Kiln Stack 14.4%
In Fine Coke 2.3%
in Coke Mill Stack 0.0%

21. The Hg cycle / with in-line raw mill:
can be 10 to 50 times the inputs
Source: “MERCURY IN THE CEMENT INDUSTRY”, Roberto RENZONI ,Christophe ULLRICH, Sandra BELBOOM,
Albert GERMAIN, Universite de Liege, Independently commissioned by CEMBUREAU – CSI

22. Mercury Emissions Raw Mill Off + Raw Mill On Scale
Change
Schreiber & Kellett 2009

23. Influencing
Factors
Temperature
Cl Available
O Available
SO3 Available
Source: "Fate and transport of mercury in Portland cement manufacturing facilities", J.K. Sikkema. Theses and Dissertations. Paper 11907. http://lib.dr.iastate.edu/etd/11907

24. Mercury Emissions Averages All Cement Kilns Surveyed
Good
Generalization but
each case is specific
Schreiber & Kellett 2009

25. Largest Emitters (2010 Data)
2000
1800
1600
1400
1200
1000
800
600
400
200
0
Lehigh Tehachapi AG Durkee Lehigh Cupertino

26. Pounds per Million Tons of Clinker (2010 TRI + GHG Data)
100
150
200
250
300
350
400
450
500
50
0
Larger Emitters

27. Pounds per Million Tons of Clinker (2010 TRI + GHG Data)
100
120
0
20
40
60
80
Smaller Emitters

28. Conclusions
• The mercury emission limit remains at 55 pounds
per million tons of clinker
• Compliance has been pushed to September 2015,
with the possibility of a one year extension
• More than half of the cement plants will have to
reduce emissions to meet the new limit
• Roughly a third will have to install some form of
control
• Many plants can qualify as CISWI installations
which may not be coherent with NESHAP