Activated Carbon Injection System to

Control EAF Mercury Emission

Presenter – Aldo Giachero

May 2014
 Sources of Mercury Air Emissions
in the U.S.
What are the biggest sources of mercury air emissions in the U.S.?

According to EPA's 2008 National Emissions Inventory, coal-fired electric power

plants are the largest source of human-caused mercury air emissions in the U.S.

These power plants account for about 48% of total U.S. man-made mercury
emissions.

Other large sources are:

• Industrial boilers (about 7% of U.S. mercury emissions),
• Burning waste from the manufacture of Portland cement (about 7%),
• Electric Arc Furnaces used in steelmaking (about 8%)
• Gold mining (about 3%).

Source: http://publicaccess.supportportal.com/ics/support/KBAnswer.asp?questionID=21198&subscribe=1
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 Sources of Mercury Air Emissions
in the U.S.
Source Category 1990 Emissions 2005 Emissions 2008 Emissions
(tpy) Baseline (tpy) (tpy)
NEI for HAPs, 2005 MATS proposal 2008 NEI v2
11/14/2005 3/15/2011

Utility Coal Boilers 58.8 52.2 29.5

Industrial/Comm.
Institutional Boilers & 14.4 6.4 4.5
Process Heater

Portland Cement Non- 5.0 7.5 4.2

Hazardous Waste

Electric Arc Furnaces 7.5 7.0 4.7

2.5
Gold Mining 4.4 1.7

Source: http://www.epa.gov/ttnchie1/net/2008neiv2/2008_neiv2_tsd_draft.pdf
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 Mercury Air Emissions from
Electric Arc Furnaces
The Electric Arc Furnace (EAF) steelmaking plants are internationally recognized
as a significant source of mercury emissions.

In the EAF steelmaking different grades of scrap metal are recycled: this
material is contaminated by the presence of chemical substances and thus
various root sources of emissions are plausible.

The most common source of mercury comes from scrap obtained by old
motor vehicles containing mercury switches.

The scrap quality is the most influencing factor for mercury emission from EAF
facilities, but also the raw materials, as fluorspar, should be considered as a
source.

Source: http://publicaccess.supportportal.com/ics/support/KBAnswer.asp?questionID=21198&subscribe=1
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 Mercury Air Emissions from
Electric Arc Furnaces

Fluorspar (CaF2)
contains over 1 ppm of
mercury.

Other raw materials

contain up to 0.2 ppm
of mercury, as per a
more recent
investigation by
Mo i Rana in 2004.

Source: Mercury Emissions from Steelmaking: A Review - D. Roseborough and B. Lindblad, 2008
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 Mercury Air Emissions from
Electric Arc Furnaces
Mercury in the EAF Flue-Gasses

Mercury can be present in three forms:

• elemental Hg (Hg⁰);
• particulate bound Hg (HgP);
• reactive (divalent) gaseous mercury (Hg²+), such as HgCl2.

Due to the relatively low chlorine and sulfur content in the EAF flue gas, the mercury
content in steelmaking emissions have historically been believed to be comprised of
approximately 80 % Hg0, 5 % HgP and 15 % Hg2+.

The predominant form of the mercury to be controlled at the bag filter inlet is the
elemental form, Hg0, which is difficult to capture because of its higher volatility and
chemical inertness.
Source: D. Roseborough, et al.; Mercury Emissions from Steelmaking: A Review, Jernkontorets Forskning D825, May 30, 2008

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 Mercury Air Emissions from
Electric Arc Furnaces
The following table provides an overview of the specific emission factors that
can be used as reference for the emission floor assessment in USA and Europe:

SOURCE EMISSION FACTOR NOTES

EPA: AP42 – 2009 0.000110 [lb/ton] 55 [mg/tls]

0.000004 [lb/ton] 2 [mg/tls] Minimum value

IPPC: EUR 25521 EN 2013
0.000400 [lb/ton] 200 [mg/tls] Maximum value

Existing Sources: Avg. of top

SMA: Environment & Energy Issues 0.000130 [lb/ton] 65 [mg/tls]
12% of sources with data
Impacting U.S. EAF Steelmaking
Sector 2012
(Based on data from 29 Facilities) New Sources: Best
0.000025 [lb/ton] 13 [mg/tls]
performance in category

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 U.S. National Air Toxics Standards
for EAF
US National Air Toxics Standards for EAF Steelmaking Facilities

Mercury:
The USA EPA Maximum Achievable Control Technology (MACT) standards for mercury
are based on pollution prevention, i.e. to comply with one of the following options for
each scrap provider:

1. Prepare, submit for approval, and implement a detailed site-specific plan for the removal of
mercury switches from motor vehicle scrap;
2. Certify participation in and purchase motor vehicle scrap only from scrap providers who
participate in an EPA-approved program for the removal of mercury switches (for example
NVMSRP: National Vehicle Mercury Switch Recovery Program, with the goal to collect 80 to 90
percent of available mercury switches by 2017);
3. Certify that the only materials from motor vehicles in the scrap are those recovered for their
specialty alloy content and that the scrap is not reasonably expected to contain mercury
switches; or
4. Certify that the scrap does not contain motor vehicle scrap.
Source: http://www.epa.gov/ttn/atw/area/eafb.pdf 8
 U.S. National Air Toxics Standards
for EAF

US National Air Toxics Standards for EAF Steelmaking Facilities

Contaminants in scrap other than Mercury

Comply with one of the following options:

1. Prepare, submit for approval, and implement a pollution prevention plan for scrap selection
and inspection to minimize the amount of chlorinated plastics, free organic liquids, and lead
(except for the production of leaded steel).
2. Do not charge scrap that contains scrap from motor vehicle bodies, engine blocks, oil filters, oily
turnings, machine shop borings, transformers or capacitors containing polychlorinated
biphenyls, lead-containing components (except for the production of leaded steel), chlorinated
plastics, or free organic liquids.

Source: http://www.epa.gov/ttn/atw/area/eafb.pdf
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 U.S. National Air Toxics Standards
for EAF
US National Air Toxics Standards for EAF Steelmaking Facilities

Particulate matter (PM): Comply with one of the following options

• Install, operate, and maintain a capture system that collects emissions from each EAF and AOD
vessel.
• Except for small stainless or specialty steel facilities, meet a PM limit of 0.0052 gr/dscf for each
EAF and AOD vessel.
• For small (less than 150,000 tons per year) stainless or specialty steel facilities, meet a PM
emission limit of 0.8 pounds per ton of steel produced.

Opacity:
• Maintain the opacity of emissions from the melt shop that are due to the operation of any EAF
or AOD vessel below 6 percent.

Source: http://www.epa.gov/ttn/atw/area/eafb.pdf
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 European Air Toxics Standards for
EAF

European Best Available Techniques for EAF Steelmaking Facilities

Mercury
• BAT for the electric arc furnace (EAF) process is to prevent mercury emissions by
avoiding, as much as possible, raw materials and auxiliaries which contain mercury.
• The BAT-associated emission level for mercury is < 0.05 mg/Nm³.

Particulate matter
• The BAT-associated emission level for dust is < 5 mg/Nm³ (0.0020 gr/dscf).

Dioxin (PCDD-PCDF)
• The BAT-associated emission level for Polychlorinated Dibenzodioxins/Furans
(PCDD/F) is <0.1 ng I-TEQ/Nm³.

Source: IPPC: BAT for Iron and Steel Production - 2012

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 Compliance with the Rules

As awareness increases and BATs become available, future revision of the rules can
lead to more stringent mercury emission limits and continuous emission monitoring
requirements.
Different approaches and different technical solutions are adopted to prevent or to
control the mercury emissions from EAF in Europe and USA.

In some cases more stringent local rules pushed the operator to find additional
control solutions.
COMPLIANCE WITH
POLLUTION PREVENTION
EPA NATIONAL RULE & EU BAT
APPROACH
EMISSION LIMIT

POLLUTION PREVENTION COMPLIANCE WITH USA/EU

+ MORE RESTRICTIVE
APCD LOCAL/FUTURE EMISSIONLIMITS
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 EU ACI Systems for
Mercury/Dioxin Control

In some European EAF Facilities emission control devices are installed to ensure the
compliance with the imposed mercury concentration at the stack.

The following are cases of European EAF plants in which AC is used as sorbent material
for capturing mercury and other pollutants present in the EAF flue gasses:

• two EAFs based in Italy, in which the ACI system was installed with the scope of
controlling polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated
dibenzofurans (PCDF) emission, with consequent and significant reduction on
mercury emission;

• one EAF based in France, provided with the ACI because of a very stringent
mercury emission limit imposed by the local authorities;

• one EAF based in Norway, where a fixed-carbon bed system is installed for mercury
removal.
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 EU ACI Systems: Mercury Emission
Performance
EAF PLANT A - 100 t B - 140 t C - 100 t D - 90 t
LOCATION Italy Italy France Norway
Hg CONTROL
ACI ACI ACI AC Fixed Beds
DEVICE
PAC INJECTED 20÷25 [kg/h] 10 [kg/h] 10 [kg/h] 60,000 [kg] (**)
FLOW-RATE 570,000 [Nm³/h] 1,400,000 [Nm³/h] 1,000,000 [Nm³/h] 215,000 [Nm³/h]

Hg EMISSION LIMIT 0.05 [mg/Nm³] 0.05 [mg/Nm³] 0.005 [mg/Nm³] 16 [kg/year]

REFERENCE STEEL
100 [t/h] 145 [t/h] 104 [t/h] 110 [t/h]
PRODUCTION
0.006÷0.026 0.0016÷0.0062
0.814 [kg/month]
0.0016 [mg/Nm³] (*) [mg/Nm³] [mg/Nm³]
(2012)
Hg PERFORMED (2013) (2013)
EMISSION IN THE 0.91 [g/h] (*) 18 [g/h] 4.3 [g/h] 1.79 [g/h]
YEARS 2012-2013
9.1 [mg/tls] (*) 124 [mg/tls] 41 [mg/tls] 16.3 [mg/tls]
0.000018 [lb/ton] (*) 0.000234 [lb/ton] 0.000082 [lb/ton] 0.000033 [lb/ton]
(*) Performed in the year 2010.
(**) Referred to the quantity of activated carbon contained in the fixed beds. 14
 EU ACI Systems: Mercury Emission
Performance
• In the case of plants A and B in Italy, the system was primarily installed for the PCDD-F
control, with the scope to obtain concentration at the stack lower than 0.1 ngITEQ/Nm³.
Although these systems are not focused on the mercury control, a significant reduction of
the Hg emission is reached in full compliance with the imposed limits.

• In the case of plants C in France, the more stringent local imposed emission limit pushed
the company to install an ACI system for the Hg control. Adjusting the PAC granulometry
and concentration in the off-gas they are maintaining the compliance with the limit.

• The Plants B and C are performing Hg emission levels in compliance with the imposed
limits with a very low PAC consumption: the performance can be further improved, if
required by future regulations, increasing and adjusting the injection rate.

• In plant D, Norway, a different solution with activated carbon fixed beds was adopted: this
solution is effectively working, however, because of the sizeable dimensions of the system,
and considering additional pressure loss, it is not suitable for high fume flow-rates (i.e. in
the case that EAF primary and secondary emissions are both conveyed to the same
dedusting unit).
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Hg & PCDD/F Emission Control:
Study Case A

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 Hg & PCDD/F Emission Control:
Study Case A
Powdered Activated Carbon (PAC) Injection System to Control EAF’s
dioxins and Mercury Emissions: Case of North Italy based EAF – Plant A
DIOXFREE is a Powdered Activated Carbon (PAC) injection
system suitable to operate efficiently during all the EAF plant
process phases.

Mercury, PCDDs/Fs, PAH and other pollutants are adsorbed on

PAC surface efficiently if:
1- The sorbent dosage is regulated according to the fume
variable conditions
2- The PAC is homogeneously distributed
3- The PAC is properly selected

The removal of Hg from a gas stream occurs both through

physisorption(1) and chemisorption mechanisms.
Fume Treatment Technologies
The PAC physical and chemical properties plays an important
role on the overall adsorption efficiency.

(1) Physisorption, also called physical adsorption, is a process in which the electronic structure of the atom 17
or molecule is barely perturbed upon adsorption
 Hg & PCDD/F Emission Control:
Study Case A

Electric Arc Furnace: 140 t/h

Tap to Tap: 40 min (Avg.)
2 FILTERING UNITS
Fume Treatment Plant: (Primary & Secondary fume + 2 LF)
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 Hg & PCDD/F Emission Control:
Study Case A

Installation
570000 m3/h
(PRIMARY FUME):
PAC: Surface ratio > 700 m2/g
Mean PAC
20 µm
Granulometry:
PAC concentration in
20 ÷ 25 mg/Nm3
fume:

SELECTABLE 3 WAYS DOSAGE

1 - Fixed PAC conc. in fumes
2 - Variable PAC conc. According to
the fume temperature
3 - Fixed PAC Flowrate

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 Hg & PCDD/F Emission Control:
Study Case A
CFD ANALYSIS
For each plant a Computational Fluid Dynamics (CFD) model is developed in order to improve the PAC
distribution in the fume flowing to the bag filter sections: adsorbent particles are tracked using the
Discrete Particle Modelling (DPM) method.

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 Hg & PCDD/F Emission Control:
Study Case A
The PAC storage is performed by
means of a silo complete with hopper,
discharge and dosing systems.

The PAC is pneumatically conveyed

into the fume duct. A suitable
continuous weighing and feeding
system has been adopted to optimize
PAC dosage according to the different
process parameters. INJECTION
SYSTEM

The system can be easily monitored CONTROL

remotely via PLC to check in real time ROOM

all process variations and possible

unexpected system arrests.

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 Hg & PCDD/F Emission Control:
Study Case A

WEIGHING
SYSTEM

BLOWER

Fume Treatment Technologies

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 Hg & PCDD/F Emission Control:
Study Case A

SAFETY ISSUES: explosion hazard

EU
• ATEX 1999/92/EC (1999). Directive on the minimum requirements for improving the
safety and health protection of workers potentially at risk from explosive atmospheres.
• ATEX 94/9/EC (1994). Directive on the approximation of the laws of the member states
concerning equipment and protective systems intended for use in potentially explosive
atmospheres.

USA
• NFPA 654. Standard for the Prevention of Fire and Dust Explosions from the
Manufacturing, Processing, and Handling of Combustible Particulate Solids.

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 Hg & PCDD/F Emission Control:
Study Case A
SAFETY DESIGN
The system has been designed in compliance with the EU directives ATEX 1999/92/EC and 94/9/EC,
concerning explosion protection measures to guarantee the highest possible level of safety in areas
where combustible dusts or gases are or may be present.

PAC St1
Dust Explosion Class (Kst up to 200 bar m/s)

In accordance with Directive

1999/92/EC, the classification of
areas where explosive atmosphere
may occur has been carried out in
order to select the appropriate
equipment to use in such zones.

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 Hg & PCDD/F Emission Control:
Study Case A
Mercury Emissions
• The concentration value measured in the year 2010, 0.0016 mg/Nm³ (0.000018 lb/ton),
is the maximum value registered from 2009 to 2013;
• All the other values are ranging from 0.0003 to 0.0008 mg/Nm³ (0.000006 ÷ 0.000016
lb/ton).

The Hg emission rate of this plant is significantly lower when compared to the other plants
considered in this study. This is due also to the different quality of the charged scrap.

The plant was installed with the primary

scope of PCDD-F control, in order to
maintain their emission at the stack
under 0,1 ngITEQ/Nm³.

The injection system settings and PAC

features can be easily adapted to obtain
Mercury abatement efficiency higher
than 90%.
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 Hg & PCDD/F Emission Control:
Study Case A
Other Pollutants Emissions
PRE POST
POLLUTANT EMISSION LIMIT INSTALLATION INSTALLATION
YEAR YEAR
PCDD/F [ngITEQ/Nm³] 0.5 >0.5 <0.1
PAH (Bohorneff series) [μg/Nm³] - 3.76 0.14
PCB tot. [μg/Nm³] - 0.23 0.01

The activated carbon has the capability to

efficiently adsorb other gaseous pollutants
as PCDD-F, PCB and PAH, the emission of
which couldn’t be controlled by means of
the simple filtration.

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Heavy Metal Recovery Unit: Study
Case D

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 Heavy Metal Recovery Unit: Study
Case D

Activated Carbon System For Heavy Metal Recovery: AC Fixed Bed

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Heavy Metal Recovery Unit: Study
Case D

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 Heavy Metal Recovery Unit: Study
Case D
Technical Data

o Airflow: 215000 Nm³/h

o Pollutants recovery: Mercury (app. 150 kg/a)
Dioxins (app. 15 g/a)
Chlorinated Carbons (app.7.6 kg/a)
o Activated Carbon Filter: 6 adsorbers, type APF-H 3200 (in AISI 304)
o Activated Carbon: 60000 kg
o CO-Monitoring
o Nitrogen-Flush
o High purification efficiency: over 98 %
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 Heavy Metal Recovery Unit: Study
Case D

Performed Emissions

MEASURED EMISSIONS
PRE POST
EMISSION
POLLUTANT LIMIT INSTALLATION INSTALLATION
YEAR YEAR
Hg 16 kg/year 4654 g/month 9 kg/year
Dust [mg/Nm3] 15 (2008) 2148 (2008) 0.705 (2009)
4.5 (2009)

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 Heavy Metal Recovery Unit: Study
Case D

2012 Mercury Emissions

18

16

14
Hg (kg/month)
12
Hg cumulative
10

0
ry ry ch ril ay ne ly st be
r er be
r
be
r
nua rua ar Ap M Ju Ju ugu m t ob m m
b M e c ve ce
Ja Fe
A pt O
Se No De

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 CONCLUSIONS

• ACI technology is able to comply with the mercury emission limit that cannot be
met by means of pollution prevention practices.

• The activated carbon has the capability to efficiently adsorb other gaseous
pollutants as PCDD-F, PCB and PAH, the emission of which couldn’t be controlled
by means of the simple filtration.

• The activated carbon beds technology is performing very good results, however
this is to be considered as an individual case, installed for a smaller dedusting
system treating only the primary off-gasses of a 90t EAF. The carbon bed system
installation would be more complicated for existing plants or new higher-capacity
plants, in terms of flue gas logistics and dimensions.

• Significant ACI system features are the adaptability to all the dedusting system
configurations and the installation possible without the need of dedusting system
modifications.
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AKNOWLEDGEMENTS

THANK YOU FOR YOUR ATTENTION

Aldo Giachero

TTF S.r.l. – Tecnologie per l’Ambiente

Via Degli Artigiani, 58G
16162 - Genova, Bolzaneto – Italy
Office Phone: +39 010 2518836
E-mail: a.giachero@ttf.ge.it

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