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

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

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

Contribution to Total Emissions as a % Typical Materials & Fuel – Mercury Content Contribution to Total Emissions as a %

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 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. 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

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.

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

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 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

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 ).

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 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 > 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

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

Performance Standard-12B QA/QC Criteria ABLE 12B - 1 Q A /QC C RITERIA FOR S ORBENT RAP M ONITORING YSTEM O PERATION 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 ?4% of average sampling rate After monitoring Invalidate the data from the paired traps or, if certain conditions are met, report adjusted data a 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 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 traps or, if certain condition ns are met, Paired sorbent trap agreement ?10% Relative Deviation (RD) if the average concentration is > 1.0 ?g/m 3 ?20% RD if the average concentration is ? 1.0 ?g/m Either invalidate the data from the paired traps or report the results from the trap with the higher Hg concentration. Performance Standard-12B QA/QC Criteria

Performance Standard-12B QA/QC Criteria Cont.

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 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 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.

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? 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

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

your partner for mercury measurement success OHIO LUMEX COMPANY your partner for mercury measurement success Thank You for Attending Shawn Wood shawn.wood@ohiolumex.com Phone: 330-405-0837 Fax: 330-405-0847 Cell: 919-931-3084