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

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 agency’s 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.html#IMP

 New Compliance Date: Sept. 9th 2015 Today’s 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 )

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.

Typical Cement Plant with Rotary Kilns

Typical Cement Plant Process

Examples of 4 main raw materials used for Portland Cement Manufacture

Limestone Shale

Cement Clinker

Clay Iron Ore

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

Looking at Raw Materials to make Cement Clinker

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.

Sources of Mercury in Cement

44.02

42.16

10.26

3.56

Limestone Coal Ash Coal Other

Typical Materials & Fuel – Mercury Content

Contribution to Total Emissions as a %

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 2000°C 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 100-200°C. 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 1450°C.

Cement is Made in a 2 Step Process

Step1: First clinker is produced from raw materials

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.

Cement Plant HG Species During Raw Mill On & Off

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.

Mercury During - Raw Mill On & Off Operation

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

NESHAP Rule Startup / Shutdown Work Practice Standard

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.

Looking at Mercury Monitoring in theNESHAP 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

•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 ).

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.

NESHAP Compliance 40CFR Part 60 & 63 Cont.

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 > 1 µg/m3

≤ 20% of Section 1 mass if HG is > 0.5 and ≤ 1 µg/m3

≤ 50% of Section 1 mass if HG is > 0.1 and ≤ 0.5 µg/m3

There is no breakthrough criterion if HG is < 0.1 µg/m3

NESHAP Sorbent Trap Sampling System Rata criteria

• 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

Sorbent Traps for Compliance in accordance with PS-12B

Performance Standard-12B QA/QC Criteria

TABLE 12B-1

QA/QC CRITERIA FOR SORBENT TRAP MONITORING SYSTEM OPERATION AND CERTIFICATION

QA/QC test or specification Acceptance criteria Frequency Consequences if not met

Pre-monitoring leak check ?4% of target sampling rate Prior to monitoring Monitoring must not commence until the leak check is passed.

Post-monitoring leak check ?4% of average sampling rate After monitoring Invalidate the data from the paired traps or, if certain conditions are met, report adjusted dataa from a single trap (see Section 12.7.1.3).

Ratio of stack gas flow rate to sample flow rate

Hourly ratio may not deviate from the reference ratio by more than ±25%.

Every hour throughout monitoring period

Invalidate the data from the paired traps or, if certain conditions are met, report adjusted data from a single trap (see Section 12.7.1.3).

Sorbent trap section 2 breakthrough

?5% of Section 1 Hg mass Every sample Invalidate the data from the paired traps or, if certain conditionns are met,

report adjusted data from a single trap (see Section 12.7.1.3).

Paired sorbent trap agreement ?10% Relative Deviation (RD) if the average concentration is > 1.0 ?g/m3 ?20% RD if the average

concentration is ? 1.0 ?g/m3

Every sample Either invalidate the data from the paired traps or report the results from the trap with the higher Hg concentration.

TABLE 12B-1 Cont.

QA/QC test or specification Acceptance criteria Frequency Consequences if not met

Spike Recovery Study Average recovery between 85% and 115% for each of the 3 spike concentration levels

Prior to analyzing field samples and prior to use of new sorbent media

Field samples must not be analyzed until the percent recovery criteria has been met.

Multipoint analyzer calibration Each analyzer reading within ±10% of true value and r2≥0.99

On the day of analysis, before analyzing any samples

Recalibrate until successful

Analysis of independent calibration standard.

Within ±10% of true value Following daily calibration, prior to analyzing field samples

Recalibrate and repeat independent standard analysis until successful.

Spike recovery from section 3 of both sorbent traps

75-125% of spike amount Every sample Invalidate the data from the paired traps or, if certain conditions are met, report adjusted data from a single trap (see Section 12.7.1.3).

Relative Accuracy RA ≤20.0% of RM mean value; or if RM mean value ≤5.0 μg/scm, absolute difference between RM and sorbent trap monitoring system mean values ≤1.0 μg/scm

RA specification must be met for initial certification

Data from the system are invalid until a RA test is passed.

Gas flow meter calibration An initial calibration factor (Y) has been determined at 3 settings; for mass flow meters, initial calibration with stack gas has been performed. For subsequent calibrations, Y within ±5% of average value from the most recent 3-point calibration

At 3 settings prior to initial use and at least quarterly at one setting thereafter

Recalibrate meter at 3 settings to determine a new value of Y.

Temperature sensor calibration Absolute temperature measured by sensor within ±1.5% of a reference sensor

Prior to initial use and at least quarterly thereafter

Recalibrate; sensor may not be used until specification is met.

Barometer calibration Absolute pressure measured by instrument within ±10 mm Hg of reading with a NIST-traceable barometer

Prior to initial use and at least quarterly thereafter

Recalibrate; instrument may not be used until specification is met.

Performance Standard-12B QA/QC Criteria Cont.

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 EPA’s 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.

NESHAP HG Emissions Reporting Overview

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 MalfunctionIn 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.

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 )

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 do…but, 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

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 ?

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?

3Who will you turn to for expert advice regarding Sorbent Traps, Sampling & Analysis?

4Do you know what your mercury concentrations are in all of your sources ?

5Do you have the personnel ready and trained to implement your monitoring plan

Questions and Answers

•Any Question on NESHAP Compliance?

•Any Questions on Sorbent Trap Sampling?

•Any Questions Regarding Traps or Data?

Thank You for Attending

your partner for mercury measurement success

OHIO LUMEX COMPANY

Shawn Woodshawn.wood@ohiolumex.com

Phone: 330-405-0837Fax: 330-405-0847Cell: 919-931-3084