Module 2 VOCs

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Published on November 8, 2007

Author: Sevastian

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Volatile Organic Compounds (VOCs) :  Volatile Organic Compounds (VOCs) VOC - Origins and Effects:  VOC - Origins and Effects VOCs are organic substances which are volatile and are photochemically reactive includes a long list of individual substances, many of which are CEPA 99 toxic the definitions of VOC vary effects precursor to ground level ozone precursor to secondary fine particulate human health impacts nuisance effects, such as odours NOx VOC O3 ( SMOG ) Definition of VOC - NERM / NPRI :  Definition of VOC - NERM / NPRI Definition based on list of excluded substances refers to Order Adding Toxic Substances to Schedule 1 to the Canadian Environmental Protection Act, 1999, published in the Canada Gazette, Part II (July 3, 2003). “Volatile Organic Compounds that participate in atmospheric photochemical reactions, excluding…” methane, ethane, list of 44 substances or classes of substances, excluded on the basis of their negligible photochemical reactivity list appears in Gazette Notice, Appendix of CCPA Guideline, Appendix 3 of Supplementary Guide to Reporting Criteria Air Contaminants (CACs) to the NPRI 2003 NERM uses the NPRI definition Definition of VOC - OMOE:  Definition of VOC - OMOE “Any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions and has a vapour pressure of 0.01 kPa or greater at 25°C” OMOE has a list of substances excluded from the definition of VOC OMOE also has a list of over 600 included substances, but does not call this an all inclusive list Still More on the Definition of VOCs:  Still More on the Definition of VOCs VOC is distinct from the following: total hydrocarbons (THC), non-methane hydrocarbon (NMHC), and total organic compounds (TOC) caution: some of the estimation methods result in estimates of the above - they are not necessarily equivalent to VOC Key Issues:  Key Issues reporting thresholds NERM/NPRI, OMOE Reg. 127, Alberta ATH - alternate thresholds – NPRI Parts 2 & 3 major stack criteria for VOCs – NPRI Part 4 Reporting of stack parameters required for NPRI if stacks  50m and emissions meet reporting thresholds speciation of VOCs – NPRI Part 5 data reconciliation between reported total VOCs and reportable individual compounds VOC and Species Reporting:  VOC and Species Reporting From CCPA Guideline, Table 2-1 VOC Speciation - NPRI Part 5 Substances:  VOC Speciation - NPRI Part 5 Substances Additional speciation requirements for VOC to NPRI beginning with 2003 reporting year Applies to the substances listed in Schedule 1, Part 5 of the January 2003 Gazette notice 34 individual substances 20 isomer groups 6 other groups and mixtures NPRI Part 5 Substances (cont’d):  NPRI Part 5 Substances (cont’d) required to report part 5 substances to NPRI if: facility has already triggered VOC reporting requirements (total VOC to air > 10 tonnes/yr); and quantity of Part 5 substance released to air is greater than 1 tonne per year additional major stack reporting requirement total VOC released to air from a stack (height > 50m) is greater than 5 tonnes; report the quantity of each Part 5 substance released from each stack (height > 50m) NPRI Flowchart for Part 5 Substances (draft):  NPRI Flowchart for Part 5 Substances (draft) VOC Reporting Requirements - NERM:  VOC Reporting Requirements - NERM NERM matches NPRI definition of VOC emissions reported as “total VOC” are to air only releases of individual substances which are VOCs are to ALL media NERM has an additional substance group, “VOC Mixtures” for reporting VOC mixtures and individual VOCs that are not on the pick list (all media) individual VOCs (air) + VOC mixtures (air) = total VOCs (air) Example of VOC reporting thresholds:  Example of VOC reporting thresholds A facility releases a mixture which consists of 14 tonnes of benzene and 2 tonnes of toluene, to all media the discharge to air is 75% of this amount, from a stack with a height of 55 metres above grade benzene and toluene are: both VOCs both on NPRI Part 1 and NERM substances list both on NPRI Part 5 Example of VOC reporting thresholds:  Example of VOC reporting thresholds Part 1, NPRI employee and concentration thresholds are met what does this facility report for Part 1, and to what media? 14 tonnes benzene, all media, to NERM and NPRI 2 tonnes toluene, all media to NERM, and also to NPRI if 10 tonnes MPO threshold is met Example of VOC reporting thresholds:  Example of VOC reporting thresholds Part 4, NPRI CACs what does this facility report for Part 4, and to what media? 12 tonnes total VOC to air (75% of 16 tonnes), to both NERM and NPRI Example of VOC reporting thresholds:  Example of VOC reporting thresholds Part 5, NPRI speciated VOCs what does this facility report for Part 5, and to what media? Benzene 14 tonnes, all media, to NERM 10.5 tonnes, air releases, to NPRI toluene 2 tonnes, all media, to NERM 1.5 tonnes, air releases, to NPRI Example of VOC reporting thresholds:  Example of VOC reporting thresholds what does this facility report to NPRI w.r.t. stack parameters stack height, diameter, velocity, temperature total VOCs - 12 tonnes to air (> 5 tonnes) benzene - 10.5 tonnes to air (> 1 tonne) toluene - 1.5 tonnes to air (> 1 tonne) Irreconcilable differences?:  Irreconcilable differences? Balance the individual Part 1 & Part 5 substances with total VOC and aggregate amounts for each program Check that the amounts are reasonable between programs VOC Emission Sources:  VOC Emission Sources process emissions (stacks) fugitive emissions (leaking process equipment) storage operations loading operations landfarms water effluents spills and accidental releases combustion processes others (e.g. batch operations) General Quantification Methods:  General Quantification Methods total VOC emissions can be estimated using the general methodologies described earlier: direct measurement (CEMs, PEMs, stack testing) emission factors mass balance emission models and correlations emissions of individual VOCs may be estimated by: speciating total VOCs applying the same quantification methods for total VOCs to sources which are composed 100% of a single substance VOC Emission Sources - Fugitive:  VOC Emission Sources - Fugitive Valves Flanges/connectors Pump seals Compressor seals Pressure relief valves to atmosphere Open-ended lines and sampling connections Fugitive Emissions - Info Sources:  Fugitive Emissions - Info Sources CCPA Guideline for Quantifying Emissions from Chemical Facilities, Section 4 - Fugitives CCME, “Environmental Code of Practice for the Measurement and Control of Fugitive VOC Emissions from Equipment Leaks” CMA (now American Chemistry Council) - Improving Air Quality: Guidance for Estimating Fugitive Emissions (from 1989) Fugitive Emissions - Info Sources (cont’d):  Fugitive Emissions - Info Sources (cont’d) U.S. EPA - Protocol for Equipment Leak Emission Estimates API - Fugitive Emissions from Equipment Leaks II: Calculation Procedures for Petroleum Industry Facilities NPI (Australia) - Emission Estimation Technique Manual for Fugitive Emissions Fugitive VOC Emissions:  Fugitive VOC Emissions Defining VOC service CCME Code = equipment streams with at least 10% VOC by volume CCPA members are encouraged to consider streams with less than 10% VOC by volume where these may contribute to VOC emissions Fugitive Emissions Estimation Requirements:  Fugitive Emissions Estimation Requirements Develop a count of all component (valves, flanges, etc.) actual counts from process & instrumentation diagrams model counts by predicting based on number of liquid pumps, valves (from CMA, 1989) Stream Assignment gas/vapour, light liquid, heavy liquid Fugitive VOC Estimation Methods:  Fugitive VOC Estimation Methods Select methodology is leak detection and repair (LDAR) program in place? Methods range from SOCMI average emission factors (no monitoring required) screening ranges stratified correlation method increasing accuracy and resource intensity; can result in order of magnitude difference in estimate Screening Range* Method:  Screening Range* Method Recommended as minimum method for CCPA members * formerly known as leak / no leak method Correlation Method:  Correlation Method Supported by CCPA during review of CCME Code Quantification Methods Fugitive Emissions:  Quantification Methods Fugitive Emissions Example A process unit at a chemical facility has 500 valves, 50 compressor seals and 525 connectors which are in Gas/Vapour service where the total VOC composition exceeds 10% by volume. The unit operates for 8 hours per day. Fugitive Emissions (cont’d):  Fugitive Emissions (cont’d) Fugitive Emissions - Speciation:  Fugitive Emissions - Speciation May be needed to estimate individual substance emissions from total VOC use measured data where available U.S. EPA SPECIATE program has VOC speciation profiles for certain source types or streams Fugitive Emissions - Other Considerations :  Fugitive Emissions - Other Considerations Open-ended lines that are capped or otherwise plugged or equipped with a 2nd valve exempt from CCME Code requirements BUT CCPA recommends that emissions from these components be included where data is available inaccessible components (those which cannot be monitored) CCPA recommends estimating emissions based on average measured leak rate for same components associated with the same process unit Emissions from Storage Tanks:  Emissions from Storage Tanks Information Sources: CCPA Guideline for Quantifying Emissions from Chemical Facilities, Section 5 - Storage Tanks CCME, “Environmental Guidelines for Controlling Emissions of VOCs from Aboveground Storage Tanks” U.S. EPA, AP-42 - Section 7.1 - Organic Liquid Storage Tanks NPI (Australia) - Emission Estimation Technique Manual for Fuel and Organic Liquid Storage U.S. EPA: TANKS Emission Estimation Software Emissions from Storage Tanks :  Emissions from Storage Tanks Requirements Emissions Methodology Temperature Data - storage and ambient Data on storage tank: capacity, colour, roof type, seals, fittings, Data on material stored: vapour pressure, composition, volume throughput or number of tank turnovers Vapour Recovery Systems and Other Emission Controls Emissions from Storage Tanks :  Emissions from Storage Tanks Recommended Emissions Methodology U.S. EPA AP-42 Section 7.1, Sept 1997 or latest “TANKS” software, (www.epa.gov) Temperature Data is required average tank storage temperature, if known if not: for non-heated tanks, use average ambient temperature for location data from Environment Canada weather office Emissions from Storage Tanks:  Emissions from Storage Tanks tank throughput or number of turnovers is needed use actual volume throughput if known or if number of turnovers is known, calculate: total annual = no. turnovers X total tank working throughput volume capacity volume for surge tanks assume turnover = 4 per year, if no other information available Emissions from Storage Tanks Speciation:  Emissions from Storage Tanks Speciation May be needed to estimate individual substance emissions from total VOC composition of vapour phase is different from liquid phase Raoult’s Law: Pi = (P)(xi) TANKS will do the calculation for you if you input the liquid composition U.S. EPA SPECIATE program also has VOC speciation profiles for certain source types Emissions from Storage Tanks:  Emissions from Storage Tanks Vapour Recovery and Other Emission Controls External Controls, e.g. vapour recovery, apply percent (%) control efficiency Fixed roof tanks with pressure/vacuum vents, TANKS has inputs - user can enter breather vent settings or use default values Atmospheric tanks blanketted with gas, EPA indicates that “the gas blanket will not affect emissions if the tank is operated near atmospheric pressure” Emissions from Storage Tanks Other Considerations:  Emissions from Storage Tanks Other Considerations Pressurized Tanks no appropriate correlations from U.S. EPA or Australia’s NPI recommended that members include components associated with pressurized tanks in their fugitive emissions inventory Emissions from Storage Tanks Other Considerations:  Emissions from Storage Tanks Other Considerations Inorganic Chemical storage U.S. EPA equations & TANKS developed to estimate evaporative losses from organic liquids Can be used to model losses from inorganic liquid storage tanks, if liquid has a measurable vapor pressure Emissions from Loading Operations:  Emissions from Loading Operations loading losses tank trucks rail cars marine vessel drums vapour recovery, vapour balancing or other controls Emissions from Loading Operations:  Emissions from Loading Operations Loading Losses use site-specific measurements if unavailable, refer to: EPA AP-42 (fifth edition, January 1995),Chapter 5.2, “Transportation and Marketing of Petroleum Liquids” Emissions from Loading Operations:  Emissions from Loading Operations LL = 124 * S * P * M / T where: LL = loading loss, mg VOC/litre of liquid loaded M = molecular weight of vapours, kg/kgmol P = true vapour pressure of liquid loaded, kPa (absolute) T = temperature of bulk liquid loaded, oK (oC + 273.15) S = saturation factor, an experimentally determined dimensionless constant (see Table 6-1 in CCPA Guideline, or AP-42) Emissions from Loading Operations:  Emissions from Loading Operations Saturation factor Emissions from Loading Operations:  Emissions from Loading Operations Consider site-specific situations loading of pressurized railcars tanks equipped with gas blanket Loading of drums can be approximated using tank truck calculations Vapour Recovery VOC removal or destruction as a % efficiency applied to estimated emissions Emissions from Loading Operations Speciation:  Emissions from Loading Operations Speciation May be needed to estimate individual substance emissions from total VOC use measured data, or composition of liquid product, where available U.S. EPA SPECIATE program has VOC speciation profiles for certain source types Sources and Quantification Methods - Combustion:  Sources and Quantification Methods - Combustion VOCs and individual substances from combustion sources (e.g. boilers and heaters) AP-42 emission factors available check if published factors are for TOC or VOC e.g. AP-42 Table 1.4-2 Sources and Quantification Methods - Combustion:  Sources and Quantification Methods - Combustion VOCs and individual substances from combustion sources (e.g. boilers and heaters) emission factors for specified organic compounds, trace elements and metals some are listed in AP-42 (e.g. PAHs, metals) others can be found in U.S. EPA “Locating and Estimating” series (e.g. dioxins and furans, mercury, lead, PAHs) Sources and Quantification Methods - Combustion Example:  Sources and Quantification Methods - Combustion Example Use of speciation profiles to speciate VOC emissions Profile Number 003, External Combustion Boiler – Natural Gas, from the U.S. EPA SPECIATE program, % of the TOC estimate. Sources and Quantification Methods - Combustion Example:  Sources and Quantification Methods - Combustion Example Sources and Quantification Methods - Flares:  Sources and Quantification Methods - Flares To estimate VOCs from flares the composition of the flared gas is needed a general assumption from U.S. EPA, in the absence of site-specific information, is that 0.5 wt% of hydrocarbons are not “combusted” this is based on a 98% destruction efficiency Sources and Quantification Methods - Other Sources of VOCs and Reportable Substances:  Sources and Quantification Methods - Other Sources of VOCs and Reportable Substances Wastewater Spills Landfarm, landtreatment Underground injection Batch Processes Covered in “Quantification of Other Sources” (Afternoon Session) CEPA 1999 Toxic Designation:  CEPA 1999 Toxic Designation Section 64 of CEPA 1999 substance enters/may enter the environment in a quantity/concentration or under conditions that: have or may have an immediate or long-term harmful effect on the environment or its biological diversity; constitute or may constitute a danger to the environment on which life depends; or constitute or may constitute a danger in Canada to human life or health. NPRI VOC Speciation:  NPRI VOC Speciation Remaining VOCs, not required to be reported as individual substances under Part 1 or Part 5 Identify reactivity of the remaining VOCs, in aggregate, as high medium low unknown This requirement was repealed in Amendment published in the Canada Gazette Part I, Jan. 17, 2004

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