Portland Cement NESHAP Emissions Testing / Monitoring

Erick Mirabella

emirabella@montrose-env.com

October 1, 2014

General Overview

Acronyms, Definitions, Omissions

Quick review of PC MACT Regulation

Pollutants and Limitations

Source Test Preparation

Engineering & Compliance Tests

Procedures and Methodologies

Opacity Monitoring

Process Data

Questions

Acronyms

NESHAP – National Emissions Standards for Hazardous Air Pollutants

MACT – Maximum Achievable Control Technology

CISWI - Commercial & Industrial Solid Waste Incinerator

NHSM – Non-Hazardous Secondary Materials

CPMS – Continuous Parametric Monitoring System

CEMS – Continuous Emissions Monitoring System

RATA – Relative Accuracy Test Audit

HAP – Hazardous Air Pollutants

Definitions Operating day - any 24-hour period beginning

at 12:00 A.M. during which the kiln operates for any length of time

Open clinker storage pile – any non-enclosed pile left on the ground for more than 3 days

Startup – the time when a kiln first starts firing fuel until it begins producing clinker (feed is introduced into the kiln for 120 minutes or when the feed rate exceeds 60% of capacity)

Shutdown - the cessation of kiln operation that begins when feed to the kiln is halted (when continuous kiln rotation ceases)

Definitions (continued) New source – any source where construction /

reconstruction commenced after May 6, 2009

Malfunction – a condition that is infrequent, sudden, or not reasonably preventable (cannot be caused by poor maintenance or careless operation)

Kiln - a device (including any associated preheater or precalciner devices, inline raw mills, inline coal mills or alkali bypasses) that produces clinker by heating limestone and other materials for subsequent production of Portland cement

Omissions

This presentation does not specifically detail the following areas of the NESHAP: o Specific test locations

Preheater or precalciner devices Inline raw mills & coal mills Clinker coolers Alkali bypasses Commingled sources Open clinker storage piles

o Related regulations & rules CISWI (40 CFR 60, Subparts CCCC & DDDD) Boiler MACT (40 CFR 63, Subpart DDDDD) NSPS (40 CFR Part 60, Subpart F)

Review

NESHAPS - stationary standards covering 187 hazardous air pollutants (40 CFR 63)

Requires use of Maximum Achievable Control Technology (MACT)

Applies to "major sources" that emit or have the potential to emit 10 ton/yr of any single HAP or 25 ton/yr of multiple HAPs.

Minimum stringency requirements are referred to as “floor” standards based on the average emissions from the best performing 12% of existing sources

Chronology

Original rule – June 14, 1999

New rule issued – September 9, 2010

PCA vs. EPA – December 9, 2011

Proposed amendments - July 18, 2012

Final rule effective - February 12, 2013

Implementation (compliance) for existing sources - September 9, 2015

Plants may seek a 1-year extension through the relevant authority, under General Provisions, Section 63.6 (4)(i)(A)

Changes to NESHAP Recent amendments

o Compliance date extension o Revised MACT floor (select limitations) o Reduced testing requirements and change

in monitoring requirements o Sets work practices for clinker piles and

startup / shutdown o Adds other affected sources units such as

clinker coolers & raw material dryers o Clarifies NHSM rule

23 cement units have now been re-classified as CISWI units

Pollution – Affecting our health …and our sensibilities

Pollutants of Concern

Total Hydrocarbons (THC)

Organic Hazardous Air Pollutants (oHAP)

Particulate Matter (PM)

Hydrochloric Acid (HCl)

Mercury (Hg)

Dioxins & Furans (PCDD/PCDF or D/F)

Total PM and PM10/2.5 - condensible analysis (local permit)

Various surrogates such as SO2

Emissions Limitations

Pollutant Existing Source

Standards New Source Standards

Mercury 55 lb/MM tons clinker a 21 lb/MM tons clinker a

PM 0.07 lb/ton clinker b 0.07 lb/ton clinker b

THC 24 ppmvd @ 7% O2 a, c 24 ppmvd @ 7% O2

a, c

HCl 3 ppmvd @ 7% O2 a 3 ppmvd @ 7% O2 a

Organic HAP (alternative to THC)

12 ppmvd @ 7% O2 d 12 ppmvd @ 7% O2

d

PCDD/PCDF 0.2 ng/dscm @ 7% O2 (TEQ) e 0.2 ng/dscm @ 7% O2 (TEQ) e

a Standards based on a 30 day rolling average.

b Standards based on 3-run test average. c Measured as propane d If the source opts to comply with the THC limit, this standard does not apply. e If the average inlet temperature to the first PM control device during the D/F performance test is 400 °F or less, the limit is changed to 0.4 ng/dscm @ 7% O2 (TEQ)

Preparing for a Source Test Requirements?

Review test schedule & unit conditions (operators must be involved)

Plan for standby (should a contingency day be part of scope?)

No surprise engineering tests

Pre-establish T&M rates

Ensure safety orientation / instructor is pre-scheduled

Plant liaison must be available

Preparation (continued)

Work permits in place

Plant analyzers must be calibrated

Uninterrupted/dedicated circuits available (who is responsible?)

Elevators (proposal probably based on them working, T&M if they’re not)

Ports clean, caps/flanges loosened

Scaffolding / man-lift in place

Communication!!!

Engineering Tests Why are they important?

Compliance dress rehearsal BEFORE the compliance/performance test

Determine effectiveness of new controls

Allows for adjustment

Compares emissions to the new limits

Uncovers unforeseen obstacles

Stratification testing important

Multiple engineering tests may be required

Compliance / RATA Tests

Know the scope of work!

Should you worry? (generally not if engineering tests were performed)

What can go wrong? (everything/nothing)

Timely maintenance and good work practices very important

Qualified contractor with method experience (complicated methods)

Calibrate plant CEMS and ensure gas calibrations are current

Annual RATAs

RATAs for Part 75 must be performed by accredited firm

Nine to twelve RM test runs conducted for direct comparison with plant CEMS o NOx and SO2 RATA (PS 2) o THC RATA (PS 8A) o Flow RATA (PS 6) o HCl RATA (PS-15 or PS-18) o Hg RATA (PS-12A or PS-12B)

RATAs may also be required by 40 CFR 60 and operating permit

Hydrogen Chloride (HCl) Reference method - EPA 321 (FTIR)

3.0 ppmvd @ 7% O2 limit (30-day rolling average following performance testing)

Performance testing every 30 months, RATA every year (when applicable)

Testing on mill on and off conditions

Continuous monitoring required for new and existing kilns (major & minor sources)

HCl alternatives available for sources utilizing scrubbers

HCl RATA

If the facility has an inline raw mill, a RATA test under PS-15 or PS-18 must be conducted with the raw mill on

Span for HCl CEMS is two times the emission standard

Must have a second span for expected higher emissions during “mill off” operation

EPA protocol gases are not yet available for low-level HCl

HCl Alternatives Alternative compliance method for

units that utilize wet scrubbers, dry scrubbers and tray towers o Establish site specific operating

parameters during performance test o Continuously monitor established

operating parameters o Continuous SO2 monitoring possible

Performance testing required every 30 months for resetting all parameters

HCl Alternatives (continued)

Wet scrubbers o Continuously measure and record pressure

drop across the scrubber, liquid flow rate, and pH in ≤ 15-minute intervals

Dry scrubbers (sorbent injection) o Continuously measure and record sorbent

injection rate in ≤ 15-minute intervals

Both scrubber types o Sulfur dioxide (SO2) may be used as an

operating parameter o Annual SO2 RATA requirement

Wet HCl Test Method (old) EPA Method 26A (schematic)

HCl by FTIR (current)

Fourier Transform Infrared Spectroscopy

Hot/wet analyzer with real-time data collection (continuous monitoring)

Can simultaneously measure multiple gases from a single sample stream

Sub-ppm resolution possible

Sample collection – Hot temperatures are critical!

Can replace several CEMS analyzers

Inside an HCl by FTIR

Interferometer

I/O Module

Gas Cell

Temperature Control

Power Brick

Pump

Power Supply

O2 Sensor

Purge Flow Meter

Network Switch

CAI 600 SC Series - Picture curtesy of California Analytical Instruments

Half Time! (break)

Total Hydrocarbons (THC)

Reference method - EPA Method 25A

24 ppmvd @ 7% O2 limit (as propane) based on 30-day rolling average

Initial compliance based on first 30 kiln operating days after rule implementation

Annual testing required on mill & bypass, RATA every year (PS-8A)

Tests at both mill on and off conditions

Flame ionization detection (FID) with continuous monitoring (THC CEMS)

Organic HAP* Alternative Meet oHAP standard by monitoring THC

EPA Methods 18 and/or 320 (FTIR), plus simultaneous EPA 25A tests (FID)

12 ppmvd @ 7% O2 limit (organic HAP)

Triplicate test runs (≥60 minutes) at both mill on and off conditions

Testing required every 30 months for resetting THC monitoring parameter

* Formaldehyde, benzene, toluene, styrene, m-xylene, p-xylene, o-xylene, acetaldehyde, and naphthalene

oHAP (continued) Test run durations can be extended to

adequately capture THC variability over time

Compliance shown as average of 3 test runs performed at both mill on and off conditions based on ratio of time at each operating condition

THC will then be considered a surrogate to oHAP and it must be monitored continuously

oHAP Scaling When oHAP is measured in compliance

at over 75% of the limit: o The site-specific THC parameter will be set

according to average THC measured during the test runs or 75% of standard, whichever is greater

When oHAP is measured at 75% or less of the limit: o Scaling factor for best performers o THC operating parameter is then set

to max 75% of HAP limit (ratio up)

oHAP Scaling Example

HAP test measurement is 6 ppm (value < 9 ppm or 75% of 12-ppm HAP limit)

Plant THC CEMS measures 30 ppm at the same time (concurrent test runs)

Facility can now ratio THC operating parameter up to corresponding HAP limit o 9 ppm * 30 ppm = 6 ppm (X) = 270 ppm o Solve for “X” (270 ppm / 6 ppm) = 45 ppm

45 ppm THC is now the new facility operating limit for oHAP

Particulate Matter (PM) Reference Methods - EPA 5 or 5i (both

measure front-half (filterable) PM only

0.07 lb/ton clinker (existing sources) 0.02 lb/ton clinker (new sources)

Annual compliance based on average of three 60-minute isokinetic test runs

Testing during mill on or off conditions (one dust concentration condition only)

Permit may require PM10/2.5 and/or condensibles (EPA 201A/202)

PM CPMS Continuous “parametric” monitoring

(CPMS) system now required

CPMS uses same PM CEMS hardware, but output measured in milliamps (mA) – antiquated!

Testing every 12 months required to determine and reset CPMS operating limit (based on either mill on or off condition)

30-day rolling average established by identifying average CPMS response based on highest 1-hr PM test

PM Scaling Example PM source test results are 0.03 lb/ton

(value is below 0.0525 lb/ton or 75% of the 0.07-lb/ton limit)

PM CPMS measures 6 mA with a zero instrument air reading of 4 mA the same time

Facility can scale mA operating parameter up to the corresponding reading o 4 + (0.0525 / (0.03 / (6-4))) = 7.5 mA

o 7.5 mA is new facility operating limit for PM

Particulate Matter EPA Method 5 (schematic)

Mercury (Hg)

Reference method - EPA 30B (paired sorbent traps) or EPA 29 (wet-isokinetic)

55 lb/MM ton clinker (existing sources) 21 lb/MM ton clinker (new sources)

Limits based on 30-day rolling average following initial performance testing

Testing required annually until Hg levels are below MDL for 2 consecutive years (moved to every 30 months after that)

Testing during mill on condition only

Hg (continued)

Hg CEMS - CVAFS or sorbent trap-based system (must include flow rate monitor)

Hg protocol gases not yet available, but Hg generators are available now

Hg typically higher during mill-off conditions due to reduced adsorption capacity of raw mill particles in the mill

Efficient PM controls can remove some particle-bound Hg, but most Hg is emitted in vapor form

Hg RATA

Annual RATA – mill on condition only

Hg CEMS required for: o New and existing kilns o Major sources

Two CEMS options: • Continuous mercury CEMS – PS 12A • Sorbent trap CEMS – PS 12B

If the facility has an inline raw mill, RATA testing under PS12A, PS12B, or Procedure 5 must be conducted with the raw mill on

Hg RATA (continued) Span for Mercury CEMS is two times the

emission standard

Must have a second span for expected higher emissions with “mill off” operation.

A RATA is not required for “mill off” operation

Speciation of Hg Emissions

45%

40%

10% 5%

Raw Materials / Fuel Hg Contribution

Limestone Ash Coal Other

6%

36% 58%

Raw Mill On

Particlebound

Oxidized

Elemental

6%

78%

16%

Raw Mill Off

Mercury Analysis On-site vs. Off-site

On-site Hg analysis o Same-day turnaround for RATA determination o Higher DLs could mean longer test runs o Thermal analysis destroys sample (a bad

analysis means a re-test)

Off-site Hg analysis o 1 or 2-day turnaround (best case) o Must ship samples (time & expense) o Lower DLs could mean shorter test runs o Better QA/QC, especially for speciation

Hg Testing Train (old) EPA 101A (schematic)

Hg Sorbent Train (new) EPA 30B Hg (schematic)

Stack Wall Note: FAMS speciation train is optional.

Heated Probe Assembly

Teflon tubing to control boxTeflon tubing to control box

Teflon tubing to control box

Control Box

RotameterTeflon impinger

with desiccant Exhaust

Dry Gas MeterPump

FAMS

TOTAL Hg

TOTAL Hg

TOTALIZER

Mercury Separation Speciation trap (schematic)

Dioxin/Furan (PCDD/PCDF)

Reference Method - EPA 23 (isokinetic)

0.20 ng/dscm @ 7% O2 emissions limit TEQ (APCD above 400 °F)

0.40 ng/dscm @ 7% O2 emissions limit TEQ (APCD 400 °F and below)

Testing required every 30 months

Triplicate test runs required on both mill on and mill off conditions

Can be combined with EPA Method 5 PM sampling train

PCDD/PCDF (continued)

With careful planning/approval, results can be used to update California AB2588 emissions inventory

Concentrations generally based on chlorine, organic precursor (from raw feed), residence time at temperature

Note: Lower APCD temps do not always lower PCDD/PCDF emissions since the concentrations of chlorinated VOC still play a role

PCDD/PCDF Sampling Train EPA Method 23 (schematic)

Opacity Monitoring

Requirement removed for kilns and clinker coolers at major sources after Sept. 9, 2015

10% Opacity limit for raw material areas, finished product storage bins, conveying system transfer points, bagging systems, bulk loading/unloading systems, raw and finish mills, and raw materials dryers

The Rule allows for demonstration of continuous compliance with either a COMS or Method 22 observations

Opacity (continued)

If Visible Emissions (VE) are observed during any EPA Method 22 performance test, a 30-minute Method 9 must be completed, beginning within 1 hour of the observance of the VE (63.150 (iν))

Any totally enclosed conveying system transfer point, regardless of the location of the transfer, is NOT required to conduct a Method 22 (63.150 (ν))

Process Data

APCD temperatures

Various feed rates

COMS, CMS & CPMS data

CEMS data including criteria pollutants (if necessary), Hg, THC and HCl

Other possibilities – SO2, scrubber solution pH, pressure drop across scrubber, flow rates, sorbent injection rates, etc.

No Summary This has gone on long enough!

Questions ???

Montrose Environmental Group Erick Mirabella emirabella@montrose-env.com