Mats Rule

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Understanding Mercury Compliance in the NESHAP or
Cement Mact
Ohio Lumex takes a close look at what's really in
the NESHAP Rule ( Cement Mact ) for the Portland
Cement MFG Industry pertaining to MERCURY with an
overview of requirements using Sorbent Trap
Sampling for compliance
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Important Dates for NESHAP or Cement Mact
Cement Mact Announcement EPA Finalizes
Amendments to Air Toxics Standards for Portland
Cement Manufacturing December 20, 2012 In
response to a federal court decision, petitions
for reconsideration and technical information
received after final rules were issued in 2010,
the U.S. Environmental Protection Agency (EPA)
finalized amendments to the agencys air toxics
rule for Portland cement manufacturing. The
amended rule will maintain dramatic reductions of
mercury, acid gases, particulate matter and total
hydrocarbons from existing cement kilns across
the country, while ensuring that emissions from
new kilns remain low. Final rule published for
release on Feb 12, 2013 Website
http//www.epa.gov/ttnatw01/pcem/pcempg.htmlIMP
  New Compliance Date Sept. 9th 2015   Todays
final amendments apply to two air emissions rules
for the Portland cement industry air toxics
standards and new source performance standards.
The final air toxics rule retains emission limits
for mercury, acid gases and total hydrocarbons
from the 2010 rules, along with retaining
requirements that kilns continuously monitor
compliance with limits for mercury, total
hydrocarbons and particulate matter
(PM). NESHAP National Emission Standards for
Hazardous Air Pollutants ( Portland Cement MFG )
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Final Emissions Limits for Portland Cement
MFG.   Pollutant
Limits for Existing Source Final Limits
for New Source   Mercury
55 pounds per million
tons of 21 pounds per million tons of
(major and area sources) Clinker,
averaged over 30 Days Clinker, averaged
over 30 Days NOTE Standards for Fugitive
Emissions from open clinker storage piles These
Clinker Piles ( sources ) under this rule would
be controlled by work practices which minimize
emissions by various means ( Enclosing piles,
spraying piles and shielding piles from wind )
The EPA estimates that this rule will affect
about 100 Portland Cement facilities located in
the US Puerto Rico about 86 Mfg plants and 14
facilities will be affected for clinker piles /
storage work practices.
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Typical Cement Plant with Rotary Kilns
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Typical Cement Plant Process
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Examples of 4 main raw materials used for
Portland Cement Manufacture
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Looking at Raw Materials to make Cement Clinker
Limestone
Shale
Clay
Iron Ore
Cement Clinker
Cement clinkers are formed by the heat processing
of cement elements in a kiln. Limestone, Shale,
Clay or Ash and iron ore in specific proportions
are heated in a rotating kiln
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Cement Raw Material Breakdown
The most common materials in cement are
Limestone 70 80 Shale or Clay 10 -
20 Sand 2 - 5 Iron Ore Source 1 -
2 Limestone, Shale Clay are sedimentary
materials and are typically low in metals
including mercury. NOTE The exception comes
when these materials are associated with
volcanics. Conclusion Recommend sending raw
material samples to Ohio Lumex lab to analyze for
mercury concentration so you have a better
understanding of the source of mercury in your
cement MFG process.
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Sources of Mercury in Cement
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Typical Materials Fuel Mercury Content
Contribution to Total Emissions as a
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Cement is Made in a 2 Step Process
Step1 First clinker is produced from raw
materials
The raw materials are delivered in bulk to the
raw mill, crushed and homogenized into a mixture
which is fed into a rotary kiln. This is an
enormous rotating pipe of 60 to 90 m long and up
to 6 m in diameter. This huge kiln is heated by a
2000C flame inside of it. The kiln is slightly
inclined to allow for the materials to slowly
reach the other end, where it is quickly cooled
to 100-200C. Four basic oxides in the correct
proportions make cement clinker calcium oxide
(65), silicon oxide (20), alumina oxide (10)
and iron oxide (5). These elements mixed
homogeneously (called raw meal or slurry) will
combine when heated by the flame at a temperature
of approximately 1450C.
Step 2 Cement is then produced from cement
clinker
Then the 2nd step is handled in a cement grinding
mill, which may be located in a different place
to the clinker plant. Gypsum (calcium sulphates)
and possibly additional materials (such as blast
furnace slag, coal fly ash ) or inert materials
(limestone) are added to the clinker. All the
materials are ground leading to a fine and
homogenous powder. The process is complete then
the cement is stored in silos before being
dispatched either in bulk or bagged.
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Cement Plant HG Species During Raw Mill On Off
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Mercury During - Raw Mill On Off Operation
Raw Mill On Kiln exhaust gases sent to raw mill,
which have a relatively high temperature and low
humidity, can be utilized for the drying of raw
materials in the raw mill when the raw mill is in
operation. Raw Mill Off During raw mill off,
the kiln exhaust gases are directly sent to the
baghouse or ESP and then to the stack. NOTE
Mercury emissions are typically higher in kiln
operations with the raw mill-off due to the
missing adsorption capacity of the freshly ground
particles in the raw mill. So some secondary
measures, such as the activated carbon injection,
may further contribute to the reduction of
mercury emissions, but will impose some technical
solutions if the filter dust is recycled back
into the kiln or into the cement mill. Some
Conclusions High particulate removal
efficiencies can be achieved with electrostatic
precipitators and bag filters. The reduction of
dust emissions is very important in terms of
reducing heavy metal emissions. Fractions of many
metals leave the kiln with the emitted dust
particles. Nevertheless, contrary to common
opinion, the upgrading of Particulate Removal
equipment does not provide an effective solution
to the capture of mercury since it is mainly
emitted in vapor form from the cement kiln stack.
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NESHAP Rule Startup / Shutdown Work Practice
Standard
Cement Plant Definitions Startup means startup
begins when the kilns induced fan is turned on
and fuel combustion is occurring in the main
burner of the kiln. Startup ends when feed has
been continuous to the kiln for at least 120
minutes or kiln feed rate exceeds 60 of
design. Shutdown means Shutdown begins when
continuous feed to the kiln is halted and ends
when continuous kiln rotation ceases. Kiln
Operating Day Means a 24 hour period that begins
at midnight during which the kiln operates for
any time. New Source Means any source that
commenced construction or reconstruction after
May 6, 2009
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NESHAP Rule Startup / Shutdown Work Practice
Standard

• Kiln Startup
• During startup the kiln must initially use any
  one or combination of the following clean fuels (
  Natural Gas, Propane, Distillate Oil, Syn-Gas or
  Ultra Low Sulfur Diesel ) until the kiln reaches
  1200F then primary fuel can commence
• All APC ( air pollution control ) devices must
  be operating prior to combusting any fuel
• Also you must keep records as specified in
  63.1355 during periods of startup shutdown
  including ( Date/time, duration, quantity of feed
  fuel used during startup )
• Requiring startup shutdown procedures to be
  included in the facilities operation
  maintenance plan.

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Looking at Mercury Monitoring in the NESHAP
Requirements 40CFR Part 60 63

• Can use HG Cems or Sorbent Trap Sampling system
  for HG monitoring requirements in accordance with
  PS-12A for Cems PS-12B for STS.
• Each pair of sorbent traps can be used to sample
  stack gas for a minimum of 1 day and a maximum of
  7 operating days ( except during RATA ).
• You must also develop an emissions monitoring
  plan in accordance with the regulation.
• No monitoring during startup and shut down
  instead adopted a work practice standard, but
• all plant air pollution control devices
  must be running during startup shutdown.
• Must measure record weight production of
  clinker in tons on an hourly basis with an
• accuracy of /- 5.
• Stack Flow rates must be corrected for moisture
  when using to calculate HG emissions
• NOTE CMS can be HG Cems or Sorbent Trap System

Terms STS Sorbent Trap Sampling System
CMS Continuous Monitoring System
PS-12B Performance Standard 12B
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NESHAP Compliance 40CFR Part 60 63 Cont.

• Must convert HG analytical data ( ug/scm ) to
  reporting format of lbs/MMton clinker over 30 day
  average.
• The STS requires the use of a Certified stack gas
  flow monitor to establish sampling flow rate/
  stack flow rate ratio and hourly data logging
  verifying percent proportional sample to stack
  flow rate.
• A rata of STS is required for initial
  certification and conducted annually there after
  for compliance.
• You must demonstrate compliance by operating a
  CMS or STS using data from the first 30 operating
  days after the compliance date of this rule (
  Sept. 9th, 2015 ).

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NESHAP Compliance 40CFR Part 60 63 Cont.

• Commingled Exhaust Requirements Kiln Coal mill
  exhaust are combined into 1 stack
• Note If the coal mill and kiln exhaust are not
  combined you must monitor at each exhaust
  location
• If you measure mercury at coal mill separately
  from kiln exhaust they must be added together
  when calculating 30 day average ( lbs / MMton of
  Clinker )
• The Plant shall demonstrate compliance and
  develop a site specific monitoring plan.
• You cannot use data recorded during monitoring
  system malfunctions, repairs of monitoring
• system malfunctions, or required monitoring
  system quality assurance or control activities in
• calculations used to report emissions.
• A monitoring system malfunction is any sudden,
  infrequent, not reasonably preventable failure of
• the monitoring system to provide valid data.

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NESHAP Sorbent Trap Sampling System Rata criteria
When performing a RATA on a STS operate sorbent
sampling system should be done in accordance to
QA requirements in Procedure 5 of Appendix F of
Part 60. The Rata must be conducted during
normal kiln operation and Raw Mill is
ON. Sorbent Trap Sampling System RATA Criteria
Section 2 breakthrough depends on stack gas Hg
concentration. The allowable section 2
breakthrough is 10 of Section 1 mass if HG
is gt 1 µg/m3 20 of Section 1 mass if HG is gt
0.5 and 1 µg/m3 50 of Section 1 mass if HG
is gt 0.1 and 0.5 µg/m3 There is no
breakthrough criterion if HG is lt 0.1 µg/m3
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Sorbent Traps for Compliance in accordance with
PS-12B

• Compliance with HG emissions standard based on
  first 30 operating days after the compliance date
  of this rule.
• Calculate the 30 kiln operating day emissions
  rate value using the assigned hourly Hg emissions
  concentrations and the respective flow and
  production rate values collected during the 30
  kiln operating day monitoring period.
• If you operate an integrated sorbent trap
  monitoring system conforming to PS-12B
• you may use a monitoring period at least 24
  hours but no longer than 168 hours
• in length. You should use a monitoring
  period that is a multiple of 24 hours except
• during a RATA as allowed in PS-12B.
• Review the QA/QC requirements in PS-12B Table
  12B-1 for Sampling Analysis

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Performance Standard-12B QA/QC Criteria
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Performance Standard-12B QA/QC Criteria Cont.
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NESHAP HG Emissions Reporting Overview

• For units that continuously monitor mercury
  emissions
• CEMS or Hg sorbent trap monitoring system, within
  60 days after the reporting periods, you must
  submit reports to the EPAs WebFIRE database.
• Each reporting period, the reports must include
  all of the calculated 30-operating day
• rolling average values derived from the CEMS
  or Hg sorbent trap monitoring systems.
• Reporting a failure to meet a standard due to a
  malfunction. For each failure to meet a
• standard or emissions limit caused by a
  malfunction at an affected source, you must
• report the failure in the semi-annual
  compliance report required by 40CFR 63.1354(b)(9)
• Reports must contain ( Date, time, duration, and
  the cause of each event including
• unknown causes) also number of events in the
  reporting period.
• Must report monitoring malfunctions, the date,
  time and duration also list the affected
• source or equipment. Provide estimate of the
  volume of pollutant emitted over the standard
• and a description of method used to estimate
  the emissions.

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NESHAP HG Emissions Reporting Overview Cont.

• Reports must also include a description of
  actions taken by an owner or operator during a
  malfunction at affected source to minimize
  emissions in accordance with 40CFR63.1348(d)
  including actions taken to correct a malfunction
• Monitoring system failures that are caused in
  part by poor maintenance or careless operation
  are not malfunctions. You may not use data
  recorded during monitoring
• system malfunctions, repairs associated with
  monitoring system malfunctions, or required
• monitoring system quality assurance or
  control activities in calculations used to report
• emissions or operating levels.
• 40CFR63.1344 Affirmative Defense for Violation of
  Emission Standards During Malfunction
• In response to an action to enforce the standards
  set forth in 63.1343(b) and (c) and 63.1345
  and you may assert an affirmative defense to a
  claim for civil penalties for violations of such
  standards that are caused by malfunction. The
  owner or operator seeking to assert an
  affirmative defense shall submit a written report
  to the Administrator with all necessary
  supporting documentation.

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Key Advantages of Sorbent Trap Monitoring System

• Simple to Install, Implement and Operate
• Typically 1 Day To Install, 1-3 Days To Certify (
  RATA )
• Highly Accurate/Precise Method for Analysis
  NIST Traceable SRM
• Multi-section sorbent tube with very low
  detection levels 1 3 ng
• Relatively Inexpensive Very Reliable compared
  to CEMs
• Generally less than 25 of the 1st Year Cost Of
  Hg CEMs
• Sorbent has a 10 Year Track Record
• Applied Widely To Coal-Utility Industry and is
  the EPA Reference Method for RATA ( Method 30B )
• Sample captured directly in stack no Hg
  transport issues
• Little or no stack or facility engineering costs
• No calibration gas costs (or daily, weekly
  calibrations only quarterly audit)
• Traps are small, non-hazardous, require no
  special storage or handling, have no expiration
  and are very simple to analyze or ship to lab (
  On-Site Analysis Can be Done Quickly )

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Keys to Success using STS

• Look at the Data!
• Ongoing Data Review
• Have a Go-To Person who will take
  accountability for the success of your Mercury
  Monitoring
• Open Dialogue with Ohio Lumex
• We try to Catch it before you dobut, if you do
  the analysis, then stay in touch.
• Sampling Trends
• Low Flow (250cc/min 400cc/min)
• Temp set to about 250 - 350 F
• Use Probe Shield if wet FGD or High Particulate

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Sorbent Trap Technology is ready NOW for
MACT-Level measurements
Ability to measure levels below 0.2 µg/dscm.
Consistently better than 10 relative accuracy
at all concentrations. NIST traceable.
Sorbent Trap monitoring is the current gold
standard for Low-Level mercury measurements.
RATA fail-proof (It is the EPA Reference Method
after all meeting your annual RATA
requirements is almost a foregone
conclusion. Low maintenance. Predictable
operating costs.
Hg CEMS Issues Sensitivity ? Reliability ?
QA/QC ?
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Questions to the Cement Plants ?

• 1 Which measurement technology will you choose
  Sorbent Trap Sampling or HG Cems ?
• 2 Are you ready to implement mercury
  measurement compliance in the NESHAP?
• Who will you turn to for expert advice regarding
  Sorbent Traps, Sampling Analysis?
• Do you know what your mercury concentrations are
  in all of your sources ?
• Do you have the personnel ready and trained to
  implement your monitoring plan

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Questions and Answers

• Any Question on NESHAP Compliance?
• Any Questions on Sorbent Trap Sampling?
• Any Questions Regarding Traps or Data?

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OHIO LUMEX COMPANY
your partner for mercury measurement success
Thank You for Attending
Shawn Wood shawn.wood_at_ohiolumex.com Phone
330-405-0837 Fax [phone] Cell 919-931-3084