mercury balance in modern cement plants
TRANSCRIPT
John Kline – John Kline Consulting
Robert Schreiber Jr. – Schreiber, Yonley & Associates
April 2013
Presentation
Background
Sources of Mercury
Mercury Oxidation
Typical Emissions
Internal Cycles
Mass Balances
Conclusions
NESHAP Rules Reissued
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%
Compliance Date September 2015
Knowledge comes from coal
And Slag
Input
Outputs
Output
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
But, Cement is Very Different
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
Kiln Feed
Fuels From
Kiln &
Precalciner
Raw Mill
BH Catch
Stack
Coal
Mill
1000 oC
330 oC
90 oC
Fuel Sources
Mean Values 0.035 – 0.095
Raw Materials
0.001
0.01
0.1
1
Limestone Clay Shale Sand Flyash Bottom Ash
Mill Scale
Me
rcu
ry C
on
cen
tra
tio
ns
in
PP
M
Min
Max
Mean
And materials can vary over time
Monthly mass balance Hg contributions by raw material (Linero, Read, and Derosa, 2008)
Mercury oxidation occurs
Influencing
Factors
Temperature
Cl Available
O Available
SO3 Available
Typical Cement Kiln Emissions
Schreiber & Kellett 2009
Mercury Speciation – Long Wet
Mercury Speciation – Long Dry
Schreiber & Kellett 2009
Good
Generalization
but each case is
specific
Mercury Speciation – Summary
Schreiber & Kellett 2009
Internal Cycles
Raw mill
Can capture 90% of mercury emissions
Captured mercury tends to be oxidized
Coal mill
Captures mercury if using preheater gases
Complete internal cycle until disruption
Baghouse
Can capture a large amount of mercury
Dust removal can be effective bleed
Large internal cycles
Mercury in the Cement Industry, commissioned by Cembureau – CSI (April 2010)
Raw
Meal
BH
Dust
Scale
Change
Mercury Emissions Mill On / Off
Schreiber & Kellett 2009
Mass Balances
Periodic / Average value mass balances
Give a good overall picture
Can take into effect longer term variations in
fuels and raw materials
Spot Balances
Give a view of what is happening at the
moment
Allows identification of internal cycles
Annual Mass Balance Tons/hr PPM Hg Lbs Hg/hr
Limestone 136 1.02 0.292
Shale 20 0.01 0.037
Clay 16 0.23 0.008
Iron 5 0.00 0.000
Total Feed 174 0.90 0.3370.000
Fuel 13 0.02 0.0010.000
Total Input 0.338
Clinker 117 0.02 0.005
Hours ug Hg/DSCM Lbs Hg/hr
Mill On 6,245 241 0.094
Mill Off 1,207 2197 0.162
Stack Total 0.2560.000
Total Output 0.260
Balance 77%
Mercury Cycles
0%
100%
200%
300%
400%
500%
600%
700%
800%
900%
1000%
Raw Coal As Fired Fuel
Raw Mill Feed
Kiln Feed Preheater Exit
Raw Mill Product
CKD Stack
Plant A Mill On
Plant A Mill Off
Plant B Mill On
Plant C Mill On
Plant D Mill On
Plant E Averaged
Spot Balance Particle Gaseous
DRY TPH ppm lbs/hr Bound lbs/h lbs/hr
Inputs
Kiln Feed 122.4 3.016 0.813 0.813
Mix fuel (as fired) 6.8 2.996 0.045 0.045
Tires (as fired) 0.4 0.168 0.000 0.000
CFS (as fired) 1.4 0.586 0.002 0.002
Coarse coke 0.000 0.000
Coal fines 0.001 0.001
Raw Mill Feed Rate 121.0 2.425 0.646 0.646
Total In 0.646 0.860
Outputs
Raw Mill Product 119.6 3.145 0.828 0.828
Out of Filter in CKD 8.4 13.988 0.260 0.260
Stack Oxidized 0.166
Stack Elemental 0.217
Coke Mill Product 9.4 1.676 0.035 0.035
Coke Mill Stack 0.000
Total Out 1.123 0.383
Spot Balance
Calculated Measured
ug/DNCM ug/DNCM
Oxidized Hg+ 394 400
Elemental Hg0 517 525
Total HgT 911 925
Balance 98%
53% Oxidized captured in raw mill from kiln gas
57% Oxidized captured in Filter
98% Oxidized & elemental captured in coal mill
Spot Balance
OutputsInputs
0.0
200.0
400.0
600.0
800.0
1000.0
1200.0
1400.0
1600.0
8:00 9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00
Fuel Kiln Feed Mill Feed Mill Product CKD Stack
Raw Mill Feeder Choke
0.0
100.0
200.0
300.0
400.0
500.0
600.0
700.0
800.0
900.0
In Out In Out In Out In Out In Out In Out In Out In Out In Out In Out In Out In Out In Out
8:00 9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00
Spot Balance
Conclusions
Cement plants are more complex and
more variable than power plants
Mercury input varies according to the
raw materials and fuels used
Mercury levels vary even within a
specific raw material or fuel over time
Mercury oxidation is important to control
strategies and needs to be better
understood
Conclusions
Modern cement plants have up to 3 internal cycles
In-line raw mills
Fuel processing using preheater gases
Return dust from exhaust gas filters
Global and spot balances should be performed over several time periods to better understand the mercury cycles
Do not purchase your abatement technology until you understand your cycles