EIIP Vol. II: Chapter 16 Methods for Estimating Air ...

1 Volume II: Chapter 16. Methods for Estimating Air Emissions from Chemical Manufacturing Facilities August 2007. Final Prepared for Emission Inventory Improvement Program Prepared by Mitchell Scientific, Inc. Westfield, NJ. RTI International Research Triangle Park, NC. Disclaimer As the Environmental Protection Agency has indicated in Emission Inventory Improvement Program (EIIP) documents, the choice of Methods to be used to estimate emissions depends on how the estimates will be used and the degree of accuracy required. Methods using site-specific data are preferred over other Methods . These documents are non-binding guidance and not rules. EPA, the States, and others retain the discretion to employ or to require other approaches that meet the requirements of the applicable statutory or regulatory requirements in individual circumstances.

2 EIIP Volume II ii Chapter 16 Chemical Manufacturing Table of Contents Table of Contents Introduction .. Source Category Description .. Process Description .. Emission Sources .. Process Operations .. Material Charging Emissions .. Emissions from Process Emissions from Process Depressurization .. Emissions from Gas Evolution Processes .. Emissions from Gas Sweep and Purge Operations .. Surface Evaporation .. Miscellaneous Operations .. Solvent Reclamation .. Cleaning .. Wastewater Storage Equipment Process Design and Operating Factors Influencing Emissions .. VOC Control Systems .. PM/PM10 Control Systems .. Basic Air Emission Vessel Charging to an Empty Charging to a Partially Filled Vessel with Miscible Contents.

3 Subsurface Above Surface Addition of Immiscible Liquids .. Purge/Gas Sweep Purge or Gas Sweep Empty Vessel Purge or Gas Sweep Partially Filled Vessel .. Vacuum Gas Evolution .. Heating .. Evaporation Models .. Evaporation from an Open Top Vessel or a Emission Model for Liquid Material Emission Model for Wastewater Using Sampling and Test Data to Validate Emission Correlating Standard Emission Models to Test Results .. EIIP Volume II iii Chapter 16 Chemical Manufacturing Table of Contents Emission Calculations Using Material Balance .. Emission Calculations Using Emission Factors .. Single Stage Vent Devices: Condensers, Vacuum Pumps, and Vacuum Steam General Calculation Considerations.

4 Material Balance Considerations for the Vent Device .. Equilibrium Relationships Between the Exit Liquid and vapor Streams .. Checking to See If Condensation Takes Place in the Vent Device .. General Calculation Approach for Solving Single Stage Vent Device Partial Total Vent Condensers .. Liquid Ring Vacuum Pumps .. Vacuum Steam Jets .. Condensers with One Condensable Component .. Partial Vent Condensers with Single-Phase Condensate .. Option 1 Modified Rachford-Rice Method .. Option 2 Partial Pressure Correction Method .. Option 3 Material Balance Correction Method .. Non-ideal Liquid .. Vent Condenser with Two Phase Liquid-Ring Vacuum Pump .. Vacuum Steam Jets.

5 Basic Process Operations .. Emission Calculations from Solvent Reclamation Emissions from Charging the Distillation Vessel with Cold Solvent for Heating the Solvent for Receiving the Solvent from Distillation .. Drumming the Purified Solvent Emissions from the Overall Toluene Recovery Process .. Filtration Centrifuge Operations .. Vacuum Dryer Information Needed to Model a Vacuum Tray Drying Operation .. Placing the material to be dried into the vacuum oven .. Depressurization Heating Step .. Distillation Physical Property Basic Physical Properties Unit Conversations .. Basic Physical Property Relationships .. EIIP Volume II iv Chapter 16 Chemical Manufacturing Table of Contents Ideal Gas Dalton's Law.

6 Mole Fraction in a Pure Component vapor Clapeyron vapor Pressure Equation .. Antoine Other vapor -Pressure Equation Forms .. Component vapor Pressure over Equilibrium Conditions (Ideal) and Raoult's Law .. Using Raoult's Law to determine molar Non-Ideal Equilibrium Conditions and Activity References .. EIIP Volume II v Chapter 16 Chemical Manufacturing Table of Contents Table of Illustrations 3-1 Charging a pure solvent to an empty vessel.. 3-2 Charging a solvent mixture to an empty vessel.. 3-3 Charging a mixture to a partially filled vessel (subsurface addition).. 3-4 Charging a mixture to a partially filled vessel (above surface addition).. 3-5 Charging a mixture to a partially filled vessel (immiscable liquids).

7 3-6 Purging an empty vessel or reactor containing solvent 3-7 Gas sweep with a vessel containing with a single volatile 3-8 Gas sweep with a vessel containing with a volatile solvent 3-9 Vacuum operation with vessel 3-10 Vacuum operation without vessel 3-11 Reaction involving a gas evolution of one 3-12 Reaction involving gas evolution of two 3-13 Reaction involving multicomponent gas evolution and nitrogen purge.. 3-14 Vessel depressurization involving one volatile 3-16 Heatup losses from a vessel containing a single volatile component.. 3-17 Heatup losses from a vessel containing a volatile 3-18 Heatup losses from a vessel with a volatile mixture and nitrogen 3-19 Evaporation from a vessel with an open 3-20 Evaporation losses from a 3-21 Using emission measurements to represent production operations.

8 3-22 Using material balance to estimate emissions from 4-1 Condenser with solvent vapor heptane and 4-2 Condenser with toluene solvent vapor and nitrogen at vacuum conditions .. 4-3 Condenser with toluene vapor and nitrogen at atmospheric pressure .. 4-4 Rachford-Rice Method .. 4-5 Modified Rachford-Rice Method for Vent 4-6 Partial Pressure Correction Method for Vent Condenser .. 4-7 Material Balance Correction Method for Vent 4-8 Vent condenser with azeotrope, material balance correction method.. 4-9 Vent condenser with two phase condensate .. 4-10 Liquid-Ring Vacuum Pump with multi-component process stream.. 4-11 Vacuum steam jet material balance correction method.

9 5-1 Estimating emissions from a batch distillation 6-1 Calculating the moles of gas from volume, temperature, and 6-2 Calculating molar quantities for gas mixtures.. 6-3 Calculating mole fractions for liqiud 6-4 Estimating Clapeyron vapor pressure model coefficients.. 6-5 Calculating pure component vapor pressures from the Antoine 6-6 Calculating vapor pressures using the AIChE DIPPR database model.. 6-7 Estimating component vapor pressures using Raloult's 6-8 Estimating liquid composition based on vapor pressure 6-9 Determining the molar composition of a liquid from vapor pressure data.. 6-10 Estimating activity coefficients from solution 6-11 Estimating activity coefficients from azeotropic mixtures.

10 6-12 Calculating vapor compositions using activity coefficients.. EIIP Volume II vi Chapter 16 Chemical Manufacturing Table of Contents List of Figures Figure Page 3-1 Saturation Level (S) Plotted as a Function of Exit Vent Gas Flow 3-2 Toluene Emission Rate Plotted as a Function of Exit Gas Sweep Rate and Saturation Level.. 4-1 Diagrams of single stage vent 4-2 Generalized Rachford-Rice 4-3 Rachford-Rice Plot showing solution at V/F = 4-4 Rachford-Rice Plot showing solution at V/F = 4-5 Activity coefficients calculated for ethyl acetate and ethanol from the van Laar equation for the complete composition range.. 4-6 Component vapor pressures calculated for ethyl acetate and ethanol based on liquid composition, activity coefficients, and pure component vapor pressures.