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Manual of Petroleum Measurement Standards Chapter 19.4 Evaporative Loss Reference Information and Speciation Methodology THIRD EDITION, OCTOBER 2012 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Manual of Petroleum Measurement Standards Chapter 19.4 Evaporative Loss Reference Information and Speciation Methodology `,,```,,,,````-`-`,,`,,`,`,,` - Measurement Coordination THIRD EDITION, OCTOBER 2012 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Special Notes API publications necessarily address problems of a general nature With respect to particular circumstances, local, state, and federal laws and regulations should be reviewed Neither API nor any of API's employees, subcontractors, consultants, committees, or other assignees make any warranty or representation, either express or implied, with respect to the accuracy, completeness, or usefulness of the information contained herein, or assume any liability or responsibility for any use, or the results of such use, of any information or process disclosed in this publication Neither API nor any of API's employees, subcontractors, consultants, or other assignees represent that use of this publication would not infringe upon privately owned rights API publications may be used by anyone desiring to so Every effort has been made by the Institute to assure the accuracy and reliability of the data contained in them; however, the Institute makes no representation, warranty, or guarantee in connection with this publication and hereby expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any authorities having jurisdiction with which this publication may conflict API publications are published to facilitate the broad availability of proven, sound engineering and operating practices These publications are not intended to obviate the need for applying sound engineering judgment regarding when and where these publications should be utilized The formulation and publication of API publications is not intended in any way to inhibit anyone from using any other practices Any manufacturer marking equipment or materials in conformance with the marking requirements of an API standard is solely responsible for complying with all the applicable requirements of that standard API does not represent, warrant, or guarantee that such products in fact conform to the applicable API standard `,,```,,,,````-`-`,,`,,`,`,,` - Users of this standard should not rely exclusively on the information contained in this document Sound business, scientific, engineering, and safety judgment should be used in employing the information contained herein All rights reserved No part of this work may be reproduced, translated, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher Contact the Publisher, API Publishing Services, 1220 L Street, NW, Washington, DC 20005 Copyright © 2012 American Petroleum Institute Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Foreword Nothing contained in any API publication is to be construed as granting any right, by implication or otherwise, for the manufacture, sale, or use of any method, apparatus, or product covered by letters patent Neither should anything contained in the publication be construed as insuring anyone against liability for infringement of letters patent Shall: As used in a standard, “shall” denotes a minimum requirement in order to conform to the specification Should: As used in a standard, “should” denotes a recommendation or that which is advised but not required in order to conform to the specification This document was produced under API standardization procedures that ensure appropriate notification and participation in the developmental process and is designated as an API standard Questions concerning the interpretation of the content of this publication or comments and questions concerning the procedures under which this publication was developed should be directed in writing to the Director of Standards, American Petroleum Institute, 1220 L Street, NW, Washington, DC 20005 Requests for permission to reproduce or translate all or any part of the material published herein should also be addressed to the director Generally, API standards are reviewed and revised, reaffirmed, or withdrawn at least every five years A one-time extension of up to two years may be added to this review cycle Status of the publication can be ascertained from the API Standards Department, telephone (202) 682-8000 A catalog of API publications and materials is published annually by API, 1220 L Street, NW, Washington, DC 20005 Suggested revisions are invited and should be submitted to the Standards Department, API, 1220 L Street, NW, Washington, DC 20005, standards@api.org iii `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Summary of Changes to API MPMS Chapters 19.1, 19.2 and 19.4 The third edition of API Manual of Petroleum Measurement Standards (MPMS) Chapter 19.4 was published following a revision that was carried out concurrently with revisions to Chapter 19.1, published as the fourth edition, and Chapter 19.2, published as the third edition Primary changes are: 1) Consolidation of common material in Chapter 19.4 Material that had previously been included in both Chapters 19.1 and 19.2 has been moved to Chapter 19.4 Chapter 19.4, which was previously Recommended Practice for Speciation of Evaporative Losses, now has the title Evaporative Loss Reference Information and Speciation Methodology This Chapter had already contained reference information on the properties of chemicals and typical petroleum liquids, and this information has now been removed from Chapters 19.1 and 19.2 In addition, meteorological data have been moved from Chapters 19.1 and 19.2 to Chapter 19.4 In the revised documents: a) Meteorological data are found in Chapter 19.4, b) Calculation of storage tank temperatures is found in Chapters 19.1 and 19.2 (in that fixed-roof tanks involve calculation of the vapor space temperature in order to determine vapor density, whereas this step is not involved in estimating emissions from floating-roof tanks), and c) Calculation of true vapor pressure is found in Chapter 19.4 (in that this is now calculated in the same manner for both fixed- and floating-roof tanks) 2) Reconciliation of nomenclature Chapters 19.1 and 19.2 previously had different nomenclature for the same variables These revisions adopt a common set of symbols for both chapters 3) Reorganization of the formats In addition to common material having been removed from Chapters 19.1 and 19.2, the remaining text has been edited to remove unnecessarily verbose or repetitive language The summary tables were deemed redundant, and have been deleted 4) Appendices Appendices have been redesignated as annexes 5) SI units An annex has been added to each chapter to address SI units Chapter 19.4, third edition In addition to common reference material being moved to Chapter 19.4, the following changes have been made: 1) Solar absorptance factors The former designations of Good and Poor have been replaced with the designations New and Aged, and a new category designated Average has been introduced 2) Alternative methodology for calculating storage tank temperatures An API study of storage tank temperatures concluded that a more sophisticated model for estimating storage tank temperatures has relatively little impact on estimated emissions, and thus the methodology now presented in Chapters 19.1 and 19.2 is the same as previously appeared in Chapter 19.1 (and in EPA AP-42) However, a more sophisticated model has been added as Annex I in Chapter 19.4 3) No Fuel Oil The default properties for No Fuel Oil have been revised, resulting in a significant increase in the estimated true vapor pressure The former default properties are now presented as being suitable for vacuum residual oil A new default speciation profile has also been added for No Fuel Oil The study on which these changes are based has been added as Annex G 4) Maxwell-Bonnell correlations The annex presenting the Maxwell-Bonnell correlations has been edited with the conclusion that the separate correlations for predicting the normal boiling point from distillation data are not reliable v `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - vi Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Contents Page Scope Normative References Symbols 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 Variables Meteorological Data Stock True Vapor Pressure PV 27 o Component Saturated Vapor Pressure P i 29 Stock Liquid Molecular Weight ML 29 Stock Vapor Molecular Weight MV 30 Component Molecular Weight Mi 30 Concentrations for Selected Compounds in Petroleum Liquids 36 Tank Solar Absorptance α 38 5.1 5.2 Speciation Methods 39 Speciation Based on Liquid Profiles 39 Speciation Based on Vapor Profiles 41 Speciation Example 42 7.1 7.2 7.3 7.4 Speciation Theory Introduction Raoult’s Law Precision, Accuracy, and Variability of Methods Common Mistakes 45 45 46 47 49 Annex A (informative) Validity of Raoult’s Law 51 Annex B (informative) Vapor Pressure by Antoine’s Equation 58 Annex C (informative) Comparison of Molecular Weight, Normal Boiling Point, and Blending RVP for Selected Hydrocarbons and Oxygenates 62 Annex D (informative) Vapor Pressure by Maxwell-Bonnell Correlations 66 Annex E (informative) Vapor Pressure by the HOST Test Method 69 Annex F (informative) EPA Categories of POM/PACs/PAHs 80 Annex G (informative) Properties of Heavy Fuel Oil 84 Annex H (informative) Derivations of Speciation Equations 94 Annex I (informative) Storage Tank Liquid Bulk, Liquid Surface, and Vapor Space Temperatures 100 Annex J (informative) SI Units 133 Bibliography 134 Figures C.1 Normal Boiling Point (NBP) Versus Molecular Weight 64 C.2 Pure Substance Vapor Pressure at 100°F Versus Molecular Weight 65 I.1 Heat Transfer Model 105 I.2 Insolation 106 I.3 Bulk Temperature vs Time 119 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS vii Not for Resale Contents Page Tables Meteorological Data for Selected U.S Locations Typical Properties of Selected Petroleum Liquids 28 Properties of Selected Petrochemicals 30 Concentrations (weight percent) of Selected Components in Selected Petroleum Liquids 37 Concentrations (weight percent) of Selected Components in No Fuel Oil 37 Concentrations of PAHs in Selected Petroleum Liquids 38 Solar Absorptance α for Selected Tank Surfaces 39 Vapor Profile for Simulated Gasoline 42 Speciation Example Worksheet 45 10 Speciation Example Summary 45 A.1 Summary of Results for Summer Blend Unleaded Gasoline 51 A.2 Summary of Results for Winter Blend Unleaded Gasoline 51 A.3 Compounds Selected for Speciation 52 A.4 GC Analysis Concentrations Using Average Response Factors (ARF) and Linear Regression (LR) for Liquid Phase Samples (Concentrations in μg/mL) 53 A.5 GC Analysis Concentrations Using Average Response Factors (ARF) and Linear Regression (LR) for Vapor Phase Samples (Concentrations in μg/mL) 53 A.6 Comparision of Predicted Vapor Concentrations Using the Response Factor Analytical Data 54 A.7 Comparision of Predicted Vapor Concentrations Using the Linear Regression Analytical Data 54 B.1 Variables in Antoine’s Equation 58 C.1 Molecular Weight, Normal Boiling Point, and Blending RVP for Selected Hydrocarbons and Oxygenates 63 G.1 No Fuel Oil – True Vapor Pressure (psia) versus Temperature (°F) 85 G.2 No Fuel Oil – True Vapor Pressure (psia) versus Temperature (°F) 85 G.3 Vacuum Residual Oil – True Vapor Pressure (psia) versus Temperature (°F) 86 G.4 No Fuel Oil Liquid Phase Speciation Profile 87 G.5 No Fuel Oil Liquid Phase Speciation Profile – Metals 88 G.6 No Fuel Oil Liquid Phase Speciation Profile 89 G.7 Key to Sample IDs 90 G.8 No Fuel Oil Vapor Pressure by Isoteniscope (ASTM D2879) 90 G.9 Cutter Stock Vapor Pressure by Isoteniscope (ASTM D2879) 90 G.10 Vacuum Residual Vapor Pressure by Isoteniscope (ASTM D2879) 91 G.11 Vapor Pressure by HOST Method 91 G.12 API Gravity 92 G.13 Metal Concentrations (ppmw) 92 G.14 Organic Compounds Concentrations (ppmw) 93 I.1 Difference Between Bulk and Ambient Temperatures: TB – TA (°F) 104 I.2 Difference Between Equilibrium Bulk Temperature TBE and Ambient Temperature TA (°F) 120 I.3 Difference Between Liquid Surface Temperature and Ambient Temperature (°F) 126 I.4 Liquid Surface Temperature TL (°F) 126 I.5 Effect on Emissions for Fixed Roof Tanks – Vapor Pressure PV (psia) 127 I.6 Effect on Emissions for Floating Roof Tanks: Vapor Pressure Function P* 127 I.7 Effect on Emissions for Floating Roof Tanks: Vapor Pressure Function P* % Difference 127 I.8 Effect on Emission Estimates: Good (α = 0.17) vs Average (α = 0.25) Solar Absorptance 128 I.9 Conductance c (Btu/(hr °F ft2)) 129 I.10 Fraction of Insolation Transmitted f 129 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 124 API MPMS CHAPTER 19.4    cF TA  c F −  1  + M    2c L c F  TL =       cF  + TB  c L +   1   + M      2c L c F  2c L + c F    I H cF + M     For an IFRT with an aluminum skin-and-pontoon floating roof, cSV = 1.1, 2cL = 1.5, cF = 0.5, and cI = 0.4; using H/D = β: M = cSV (2H/D + 1) + cL M = 2.2β + 1.5 IH = αI(0.5 + 0.309β)/24 IH = αI(0.021 + 0.013β) `,,```,,,,````-`-`,,`,,`,`,,` -         0.5 0.5  + αI (0.021 + 0.013β)0.5  + T 1.5 + T A  − B   1 1 ( 2.2β + 1.5)     (2.2β + 1.5) (2.2β + 1.5) + +      1.5 0.5    1.5 0.5     TL = 1.5 + 0.5 TL = TA[0.25 – 0.25/(5.87β + 4)] + TB[0.75 + 0.25/(5.87β + 4)] + αI(0.0032β + 0.0052)/(2.2β +1.5) For D = 120 ft, H = 48 ft, β = 0.4: TL = 0.211TA + 0.789TB + 0.0027αI For β = 2: TL = 0.234TA + 0.766TB + 0.0020αI An approximate expression for an IFRT with an aluminum skin-and-pontoon floating roof, independent of H/D, can be written as: TL = 0.2TA + 0.8TB + 0.002αI For an IFRT with a steel pan floating roof, cSV = 1.1, 2cL = 1.5, cF = 1.5, and cI = 0.8; assume β = 2: M = cSV (2H/D + 1) + cL M = 1.1(2(2) + 1) + 0.8 = 6.3 IH = αI(0.5 + 0.309β)/24 IH = αI(0.021 + 0.013(2)) = 0.047αI         1.5 1.5   + αI (0.047)1.5   + T B + T A 1.5 −        6.3 6.3 + +      5    5     TL = 1.5 + 1.5 Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale EVAPORATIVE LOSS REFERENCE INFORMATION AND SPECIATION METHODOLOGY 125 TL = 0.44TA + 0.56TB + 0.0037αI This matches the case for a fixed roof tank with β = 2, as expected, in that the thermal resistance of a steel pan is about the same as that for a free liquid surface For an IFRT with a steel peripheral pontoon floating roof (i.e a domed EFRT): cSV = 1.1, 2cL = 1.5, cF = 1.3, and cI = 0.7: M = cSV (2(H/D) + 1) + cI M = 2.2β + 1.8 IH = αI(0.021 + 0.013β)         1.3    + αI (0.021 + 0.013β)1.3  + TB 1.5 + T A −     (2.2β + 1.8)   (2.2β + 1.8) (2.2β + 1.8) + +      1.5 1.3    1.5 1.3     TL = 1.5 + 1.3 TL = TA[0.464 – 0.464/(3.16β + 2.58)] + TB[0 536 + 0.464/(3.16β + 2.58)] + αI(0.006β + 0.010)/(2.2β + 1.8) For D = 120 ft, H = 48 ft, β = 0.4: TL = 0.34TA + 0.66TB + 0.0046αI For β = 2: TL = 0.41TA + 0.59TB + 0.0035αI This result is similar to that for an IFRT with a steel pan floating roof, as expected, since 80 % of the area of a peripheral pontoon floating roof is assumed to consist of a single deck and thus to have the same thermal resistance as a steel pan I.4.3 Comparing Emission Estimates from AP-42 with the Well-Mixed Model Table I.3 compares the predicted liquid surface temperatures of AP-42 and the well-mixed model from I.4.2 The comparison is made for a typical tank with α = 0.2, I = 1400 Btu/ft2-day, D = 100 ft, H = 48 ft, and TA = 60 °F `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 126 API MPMS CHAPTER 19.4 Table I.3—Difference Between Liquid Surface Temperature and Ambient Temperature (°F) Tank Type TL – TA TBE TBE – TA TL 2.3 60.2 0.2 62.3 EFRT peripheral pontoon 3.0 61.9 1.9 63.0 EFRT double deck 3.8 61.4 1.4 63.8 IFRT skin-and-pontoon 1.3 60.7 0.7 61.3 Domed EFRT peripheral pontoon 1.7 60.8 0.8 61.7 FRT 1.8 60.8 0.8 61.8 AP-42: all tanks Well-Mixed Model: The effect on liquid surface temperature TL, vapor pressure PV, and vapor pressure function P* of varying values of diameter, insolation, and absorptance is shown below The base case is for solar absorptance α = 0.25, I = 1400 Btu/ft2-day, D = 100 ft, H = 48 ft, TA = 60 °F, RVP 10 gasoline, and PA = 14.7 psia In the tables below: ⎯ Diameter is varied from a small tank (20 ft diameter) to a large tank (300 ft diameter) ⎯ Insolation is varied from 800 Btu/ft2-day (Homer, AK has the least average annual insolation of sites listed in API MPMS Ch 19.1, 3rd Edition[3], at 838 Btu/ft2-day) to 2000 Btu/ft2-day (Tucson, AZ has the most average annual insolation of sites listed in API MPMS Ch 19.1, 3rd Edition[3], at 1872 Btu/ft2-day) ⎯ Absorptance is varied from α = 0.25 (the base case, which is the average of the former good and poor values for a white tank, which has the lowest absorptance of any paint color) to α = 0.71 (the average of the former good and poor values for a medium gray tank) Table I.4—Liquid Surface Temperature TL (°F) Base Casea D = 20 D = 300 63.0 63.0 63.0 61.9 64.2 69.7 EFRT (peripheral pontoon) 63.7 63.4 64.0 62.1 65.3 70.5 EFRT (double deck) 64.7 64.3 65.1 62.7 66.7 73.4 IFRT (skin-and-pontoon IFR) 61.6 61.4 61.8 60.9 62.3 64.6 Domed EFRT (peripheral pontoon) 62.2 61.7 62.4 61.2 63.1 66.2 FRT 62.2 61.8 62.5 61.3 63.2 66.4 Tank Type AP-42: all tanks I = 800 I = 2000 α = 0.71 a Base case: α = 0.25, I = 1400 Btu/ft -day, D = 100 ft, H = 48 ft, TA = 60 °F, RVP 10 gasoline, PA = 14.7 psia Emissions from fixed roof tanks are approximately proportional to the stock vapor density WV (neglecting the effect of PV on KS) Stock vapor density WV is proportional to PV The difference between the AP-42 approach and the well-mixed model on PV (and therefore on fixed roof tank emissions) is shown below For the base case, the well-mixed model emission estimate is about 1.5 % less than the AP-42 emission estimate Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - Well-Mixed Model: EVAPORATIVE LOSS REFERENCE INFORMATION AND SPECIATION METHODOLOGY 127 Table I.5—Effect on Emissions for Fixed Roof Tanks – Vapor Pressure PV (psia) Base Casea D = 20 D = 300 I = 800 I = 2000 α = 0.71 AP-42: all tanks 5.50 5.50 5.50 5.38 5.63 6.24 Well-Mixed Model: FRT 5.42 5.37 5.45 5.32 5.52 5.86 –1.5 –2.4 –0.9 –1.1 –2.0 –6.1 Tank Type % difference a Base case: α = 0.25, I = 1400 Btu/ft -day, D = 100 ft, H = 48 ft, TA = 60 °F, RVP 10 gasoline, PA = 14.7 psia Emissions from floating roof tanks consist almost entirely of standing (storage) losses for floating roof tanks storing volatile stocks such as gasoline Standing losses are directly proportional to the vapor pressure function P* The difference between the AP-42 approach and the well-mixed model on P* (and therefore on floating roof tank emissions) is shown below For the base case, the well-mixed model emission estimate is 1.7 % more than the AP-42 emission estimate for a peripheral pontoon EFRT, and 3.4 % less than AP-42 for a skin-and-pontoon IFRT Table I.6—Effect on Emissions for Floating Roof Tanks: Vapor Pressure Function P* Base casea D = 20 D = 300 I = 800 I = 2000 α = 0.71 0.117 0.117 0.117 0.113 0.120 0.137 EFRT (peripheral pontoon) 0.119 0.118 0.119 0.114 0.123 0.140 EFRT (double deck) 0.121 0.120 0.123 0.116 0.128 0.150 IFRT (skin-and-pontoon IFR) 0.113 0.112 0.113 0.111 0.115 0.121 Domed EFRT (peripheral pontoon) 0.114 0.113 0.115 0.112 0.117 0.126 Tank Type AP-42: all tanks Well-Mixed Model: Table I.7—Effect on Emissions for Floating Roof Tanks: Vapor Pressure Function P* % Difference Base Casea D = 20 D = 300 I = 800 I = 2000 α = 0.71 0.117 0.117 0.117 0.113 0.120 0.137 EFRT (peripheral pontoon) +1.7 +0.9 +1.7 +0.9 +2.5 +2.2 EFRT (double deck) +3.4 +2.6 +5.1 +2.7 +6.7 +9.5 IFRT (skin-and-pontoon IFR) –3.4 –4.3 –3.4 –1.8 –4.2 –11.7 Domed EFRT (peripheral pontoon) –2.6 –3.4 –1.7 –0.9 –2.5 –8.0 Tank Type AP-42: all tanks Well-Mixed Model: `,,```,,,,````-`-`,,`,,`,`,,` - a I.4.4 Base case: α = 0.25, I = 1400 Btu/ft2-day, D = 100 ft, H = 48 ft, TA = 60 °F, RVP 10 gasoline, PA = 14.7 psia Comparing Emission Estimates For Good and Average Absorptances The effect on liquid surface temperature TL, vapor pressure PV, and vapor pressure function P* of good (α = 0.17) vs average (α = 0.25) solar absorptance is shown below for the case of a typical white tank with I = 1400 Btu/ft2-day, D = 100 ft, H = 48 ft, TA = 60 °F, RVP 10 gasoline, and PA = 14.7 psia The value for "average" absorptance is not based on field data, but rather is taken as the average of the values for good and poor absorptance The emission estimate for α = 0.25 is 1.5 % to 3.5 % greater than the emission estimate for α = 0.17, varying by estimating method (AP-42 or the well-mixed model) and tank type Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 128 API MPMS CHAPTER 19.4 Table I.8—Effect on Emission Estimates: Good (α = 0.17) vs Average (α = 0.25) Solar Absorptance Tank Type TL PV P* Good (α = 0.17) I.5 °F psia AP-42 fixed roof tanks 61.9 5.38 AP-42 floating roof tanks 61.9 EFRT (peripheral pontoon) EFRT (double deck) TL PV P* Percent Change in Emissionsa b Average (α = 0.25) °F psia – 63.0 5.50 – +2.2 5.38 0.113 63.0 5.50 0.117 +3.5 62.5 5.45 0.115 63.7 5.57 0.119 +3.5 63.2 5.52 0.117 64.7 5.68 0.121 +3.4 IFRT (skin-and-pontoon IFR) 61.1 5.30 0.111 61.6 5.35 0.113 +1.8 Domed EFRT (peripheral pontoon) 61.5 5.34 0.112 62.2 5.41 0.114 +1.8 FRT 61.5 5.34 – 62.2 5.42 – +1.5 a For EFRTs and IFRTs, the percent change in estimated emissions is approximately the percent change in P*; for FRTs, the percent change in estimated emissions is approximately the percent change in PV b Average absorptance is taken as the average of the values for good and poor absorptance Summary Equations for vapor space temperature, liquid bulk temperature, and liquid surface temperature are summarized below for FRTs, IFRTs, and EFRTs Evaluation of Variables In the equations that follow: IH = αI(0.5 + 0.309 H/D)/24 K = 0.026αSIH For FRTs: M = cSV (2H/D + 1) + cL = 1.1 (2H/D + 1) + 0.8 = 2.2H/D + 1.9 For IFRTs: M = cSV (2H/D + 1) + cI For FRTs: J = 2cSL H + cB D + cL D = 2(4.5)H + 2D + 0.8D = 9H + 2.8D Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - Evaporative losses (emissions) from a storage tank are a function of the true vapor pressure of the liquid, which is a function of the liquid surface temperature This temperature may be estimated from meteorological and tank construction data The report in this annex provides the theoretical basis for these estimates for the scenario of the stock liquid in a tank that is neither heated nor insulated and has achieved thermal equilibrium with annual average meteorological conditions EVAPORATIVE LOSS REFERENCE INFORMATION AND SPECIATION METHODOLOGY 129 For IFRTs: J = 2cSL H + cB D + cI D Default values for c and f are given in Tables I.9 and I.10, respectively Table I.9—Conductance c (Btu/(hr °F ft2)) Boundary Resistance Conductance Default Conductance Shell and fixed roof in the vapor space 1/cSV cSV = 1.1 Shell beneath the liquid surface 1/cSL cSL = 4.5 Bottom 1/cB cB = Liquid surface top side liquid 2cL 2cL 1/[(1/2cL) + (1/2cL)] No floating roof (1/2cL) + (1/2cL) 1.5 1.5 cL = 0.8 Floating roof (1/cF) + (1/2cL) cF 2cL 1/[(1/cF) + (1/2cL)] 3(1/1.5) = 1/0.5 0.5 1.5 cI = 0.4 (1/1.5) 1.5 1.5 cI = 0.8 3(1/1.5) = 1/0.5 0.5 0.8(1.5) + 0.2(0.5) = 1.3 1.5 cI = 0.4 1.5 cI = 0.7 0.6 0.8(3.6) + 0.2(0.6) = 3.0 1.5 cE = 0.4 1.5 cE = 1.0 IFR aluminum pontoon IFR steel pan IFR double deck IFR peripheral pontoon* 1/3.6 + 2/1.5 = 1/0.6 EFR double deck a EFR peripheral pontoon a For heat flow, the areas of the floating roof act in parallel rather than in series, so the conductances are additive Assume 80 % single deck and 20 % double deck Table I.10—Fraction of Insolation Transmitted f Boundary Value Shell and roof in the vapor space 0.5 Shell beneath the liquid surface 1.0 Double deck external floating roof 0.5 Peripheral pontoon external floating roof 0.9 Assumptions 20 % of the EFR is pontoon area Vapor Space Temperature For fixed roof tanks the report in this annex provides an expression to estimate the vapor space temperature TV and daily change in vapor space temperature ΔTV needed to estimate standing losses for FRTs The vapor space temperature TV is estimated as:  αI (H s / D + 1.6)   H / D + 0.5  0.4  +  + TB  TV = T AA  s  H s / D + 0.9  170H s / D + 150  H s / D + 0.9  or, for typical values of HS /D, TV may be approximated as: TV = 0.8TAA + 0.2TB + 0.008αI `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 130 API MPMS CHAPTER 19.4 And the daily change in vapor space temperature ΔTV is:  H / D + 0.5   H / D + 1.6   + αI  s  ΔTV = (T AX − T AN ) s H / D +  s   85H s / D + 74  or, for typical values of H/D, ΔTV may be approximated as: ΔTV = 0.8(TAX – TAN) + 0.02αI Liquid Bulk Temperature When measured liquid bulk temperature data are available, they should be used to determine the liquid surface temperature When measurements are not available, and the tank can be reasonably assumed to be in equilibrium with ambient conditions, the following approaches may be used to estimate the liquid bulk temperature: a) For EFRTs: TBE = TA + αI(0.042f + 0.026 H/D)/(2cSL H/D + cB + cE) b) For IFRTs: TBE = TA + (cI D IH + KM)/(JM – cI 2D) c) For FRTs: TBE = TA + (cL D IH + KM)/(JM – cL2D) for cL = 0.8: TBE = TA + (0.8D IH + KM)/(JM – 0.6D) TB = TA + 0.0035αI [1 + 3.6(HS /D) + 3.4(HS /D) ]/[1 + 5.0(HS /D) + 4.2(HS /D)2 ] or, for typical values of HS /D, TB may be estimated as: Liquid Surface Temperature Given the liquid bulk temperature, the liquid surface temperature may be determined as follows: a) EFRTs: TL = [TA cF + 2TB cL + αIf /24]/(2cL + cF) for an EFRT with a double deck roof, with 2cL = 1.5, cF = 0.6, and f = 0.5: TL = 0.29TA + 0.71TB + 0.010αI for an EFRT with a peripheral pontoon roof, with 2cL = 1.5, cF = 3.0, and f = 0.9: TL = 0.67TA + 0.33TB + 0.008αI Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - TB = TA + 0.0028αI EVAPORATIVE LOSS REFERENCE INFORMATION AND SPECIATION METHODOLOGY 131 b) IFRTs:    cF TA  c F −  1   + M   2c L c F  TL =       cF  + TB  c L +   1    + M     2c L c F  2c L + c F    I H cF + M     For an IFRT with an aluminum skin-and-pontoon floating roof: for D = 120 ft, H = 48 ft, β = 0.4: TL = 0.21TA + 0.79TB + 0.0027αI for H/D = 2: TL = 0.23TA + 0.77TB + 0.0020αI or, for a more approximate expression independent of H/D: TL = 0.2TA + 0.8TB + 0.002αI For an IFRT with a steel peripheral pontoon floating roof (i.e., a domed EFRT), for D = 120 ft, H = 48 ft, β = 0.4: TL = 0.34TA + 0.66TB + 0.0046αI for H/D = 2: TL = 0.41TA + 0.59TB + 0.0035αI For an IFRT with a steel pan floating roof, the liquid surface temperature would be calculated as for a fixed roof tank with no floating roof c) FRTs: TL = TA (0.5 – cL /2M) + TB (0.5 + cL /2M) + IH /(2M) for cSV = 1.1, cL = 0.8: TL = TA[0.5 – 0.8/(4.4H/D + 3.8)] + TBE [0.5 + 0.8/(4.4H/D + 3.8)] + αI(0.021 + 0.013H/D)/[4.4H/D + 3.8] or, for typical values of H/D, TL = 0.4TA + 0.6TB + 0.004αI I.6 Recommendations Liquid surface temperatures can be estimated using the equations in API MPMS Ch 19.1 for all tank types (fixed roof tanks and floating roof tanks) with a reasonable level of accuracy Users may use the more precise but more complicated equations given in Section I.5 of this annex to differentiate temperatures for specific tank types and locations However, both the API MPMS Ch 19.1 equations and the equations in this annex are based on the stock liquid having reached approximate thermal equilibrium with annual average meteorological conditions Thus these equations have a loss of accuracy when applied to time periods of less than one year, particularly if the given time period has meteorological conditions that differ significantly `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 132 API MPMS CHAPTER 19.4 from the annual average Furthermore, the stock has to be idle in the tank for a number of days in order for the liquid bulk temperature to achieve approximate thermal equilibrium with atmospheric conditions There is, then, increased loss of accuracy in the calculation of liquid surface temperature when using calculated liquid bulk temperature rather than measured liquid bulk temperature `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale Annex J (informative) SI Units Guidelines to convert the inch pound units employed in this document to equivalent units of the International System of Units are given in API MPMS Ch 15[45] The unit of length is either the kilometer, designated km, or the meter, designated m The unit of mass is the kilogram, designated kg The unit of volume is the cubic meter, designated m3 The unit of time is the year, designated yr The unit of temperature is the degree Celsius, designated °C, or the Kelvin, designated K The unit of heat energy is the joule, designated J The unit of pressure is the kilopascal, designated kPa `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 133 Not for Resale [1] API Publication 2514A, Atmospheric Hydrocarbon Emissions From Marine Vessel Transfer Operations, 2nd Edition, September 1981 [2] API MPMS Chapter 19.2, Evaporative Loss from Floating-roof Tanks, 2nd Edition, September 2003 [3] API MPMS Chapter 19.1, Evaporative Loss from Fixed-Roof Tanks, 3rd Edition, March 2002 [4] NIST Standard Reference Database Number 69, March, 2003 Release (webbook.nist.gov/chemistry) [5] Dean, J A Ed., Lange's Handbook of Chemistry, Fourteenth Edition, McGraw-Hill, New York, 1992 [6] Felder, R M and Rousseau, R W., Elementary Principles of Chemical Processes, John Wiley and Sons, New York, 1978 [7] Gallant, R W., Physical Properties of Hydrocarbons, Volume 1, Gulf Publishing Company, Houston, TX, 1974 [8] Mass, J M., "Continuous Distillation: Separation of Binary Mixtures", Section 1.1 of Handbook of Separation Techniques for Chemical Engineers, P A Schweitzer, editor-in-chief, McGraw-Hill Book Company, New York, 1979 [9] Littlejohn, David, and Lucas, Donald, Test Method for Vapor Pressure of Reactive Organic Compounds in Heavy Crude Oil Using Gas Chromatography, Lawrence Berkeley National Laboratory, Berkeley, CA, May 28, 2002 [10] Null, H R., Phase Equilibrium in Process Design, Wiley-Interscience, New York, 1970 [11] Reid, R C., J M Prausnitz, and B E Poling, The Properties of Gases and Liquids, Fourth Edition, McGraw-Hill, New York, 1987 [12] Robinson, R N., Chemical Engineering Reference Manual, Fourth Edition, Professional Publications, Inc., Belmont, CA, 1987 [13] API Publication 2525, Phase I, Review of Air Toxics Emission Calculations from Storage Tanks, December 1992 (withdrawn) [14] API Publication 2525, Phase II, Air Toxic Emissions Calculation Validation Program: Analysis of Crude Oil and Refined Product Samples and Comparison of Vapor Composition to Model Predictions, December 1992 (withdrawn) [15] U.S Environmental Protection Agency, AP-42 Compilation of Air Pollutant Emission Factors, Volume I: Stationary Point and Area Sources, Fifth Edition, Section 7.1, “Organic Liquid Storage Tanks,” November 2006, www.epa.gov/ttn/chief/ap42/ch07/final/c07s01.pdf [16] Wright, D A., M N Menon, and S H Peoples, AB2588 Emission Estimation Techniques for Petroleum Refineries, Draft Final Report, prepared for Western State Petroleum Association, July 12, 1989 [17] Wu, H S., K A Pividal, and S I Sandler, “Vapor-Liquid Equilibria of Hydrocarbons and Fuel Oxygenates,” J Chem Eng Data, 1991, Vol 36, No 4, pp 418-421 [18] The Chemical Rubber Co., Handbook of Chemistry and Physics, 83rd Edition, Cleveland, OH, 20022003 [19] Soave, G., “Equilibrium Constants From a Modified Redlich-Kwong Equation of State,” Chem Eng Sci., 1972, Vol 27, No 6, p 1197 [20] Peng, D.Y and Robinson, D.B., “A Two Constant Equation of State,” I.E.C Fundamentals, 1976, Vol 15, pp 59-64 [21] ASPEN/SP Process Simulator, Simulation Sciences, Inc., Houston, TX [22] Timmermanns, J., Physio-Chemical Constants of Pure Organic Compounds, Elsevier, New York, 1950 [23] Perry’s Chemical Engineers’ Handbook, Sixth Edition, R.H Perry, D.W Green, and J.O Maloney, Editors, McGraw-Hill Book Co., Inc., New York, 1984 [24] U.S Environmental Protection Agency, TANKS program version 4.09d Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS 134 Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - Bibliography EVAPORATIVE LOSS REFERENCE INFORMATION AND SPECIATION METHODOLOGY 135 [25] API Publication 4593, Transport and Fate of non-BTEX Petroleum Chemicals in Soils and Groundwater, September 1994, Washington, DC [26] Wang, Zhendi, et al., “Using Systematic and Comparative Analytical Data to Identify the Source of an Unknown Oil on Contaminated Birds”, Journal of Chromatography (1997) p 260 [27] Guerin, M.R., Energy Sources of Polycyclic Aromatic Hydrocarbons, Oak Ridge National Laboratory, Oak Ridge, TN, Conf 770130-2, 1977 [28] Page, D.S, P.D Boehm, G.S Douglas, A.E Bence, Identification of Hydrocarbon Sources in the Benthic Sediments of Prince William Sound and the Gulf of Alaska Following the Exxon-Valdez Oil Spill, Third Symposium on Environmental Toxicology and Risk Assessment: Aquatic Plant and Terrestrial, American Society for Testing and Materials, Philadelphia, PA, 1994 [29] Pancirov, R.J and R A Brown, “Analytical Methods For Polynuclear Aromatic Hydrocarbons In Crude Oils, Heating Oils, And Marine Tissues”, Proceedings of the 1975 Conference on Prevention and Control of Oil Pollution, American Petroleum Institute, Washington, DC, 1975, p 103-113 [30] Davani, B., W Sanders, and G Jungclaus, Residual Fuel Oil As Potential Source Of Ground Water Contamination, Proceedings U.S EPA Symposium on Waste Testing and Quality Assurance, July 2427, 1989, Washington, DC, American Chemical Society, Washington, DC, 1989 [31] U.S Environmental Protection Agency Emergency Planning and Community Right-to-Know Act Section 313: Guidance for Reporting Toxic Chemicals: Polycyclic Aromatic Compounds Category, EPA 260-B-01-03, Washington, DC, August, 2001 [32] Malaiyandi, M., A Benedik, A.P Holko, and J.J Bancsi, Measurement of Potentially Hazardous Polynuclear Aromatic Hydrocarbons from Occupational Exposure During Roofing and Paving Operations, p 471-489, In: M Cooke, A.J Dennis, and G.L Fisher (Eds.), Polynuclear Aromatic Hydrocarbons: Physical and Biological Chemistry Sixth International Symposium Battelle Press, Columbus, OH, 1982 [33] U.S Environmental Protection Agency, Gasoline Distribution Industry (Stage I) Background Information for Proposed Standards, EPA-453/R-94-002a Research Triangle Park, NC January 1994 [34] Lisal, M., Smith, W.R., and Nezbeda, I., “Accurate Computer Simulation of Phase Equilibrium for Complex Fluid Mixtures Application to Binaries Involving Isobutene, Methanol, Methyl tert-Butyl Ether, and n-Butane,” J Phys Chem B 1999, 103, 10496-10505 [35] R M Stephenson and S Malanowski, Handbook of the Thermodynamics of Organic Compounds, Elsevier Science, New York, 1987 [36] Canadian Petroleum Products Institute, Code of Practice for Developing a Refinery Emission Inventory, Rev 5, December 2001 [37] Ferry, Robert L., Evaluation of the Maxwell-Bonnell Calculator for Estimating the TVP of Low Volatility Hydrocarbon Stocks, prepared by The TGB Partnership for the American Petroleum Institute, October 5, 2002 [38] Sturm, G.P., Jr and Shay, J.Y., Comprehensive Report of API Crude Oil Characterization Measurements (COCS Report), prepared by TRW Petroleum Technologies for the Technical Data Committee of the American Petroleum Institute, April 2000 [39] Barnett, H.C and Hibbard, R.R., “Properties of Aircraft Fuels,” National Advisory Committee for Aeronautics (NACA) Technical Note 3276, Washington, DC, August 1956 [40] ASTM D2879 Vapor Pressure-Temperature Relationship and Initial Decomposition Temperature of Liquids by Isoteniscope [41] API MPMS Chapter 19.4 Recommended Practice for Speciation of Evaporative Losses, 2nd Edition, September 2005 [42] U.S Department of Commerce, National Oceanic and Atmospheric Administration, Comparative Climatic Data Through 1990, National Climatic Data Center, Asheville, North Carolina, 1990 [43] API Publication 999, Technical Data Book—Petroleum Refining, 9th Revision, Washington, D.C., 1988 [44] API 4261, Alcohols and Ethers, 3rd Edition, June 2001 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale 136 API MPMS CHAPTER 19.4 [45] API MPMS Chapter 15 Guidelines for the Use of the International System of Units (SI) in the Petroleum and Allied Industries, (formerly API Publication 2564), 3rd Edition, December, 2001 [46] API Production Tank Emissions Model (E&P TANK 2.0), Publication 4697, 2000 [47] API Bulletin 2518 Evaporation Loss From Fixed-Roof Tanks, June 1962 [48] API 19.1D Documentation File for API Manual of Petroleum Measurement Standards Chapter 19.1— Evaporative Loss From Fixed Roof Tanks, 1st Edition, March 1993 (formerly API Bulletin 2518, 2nd Edition, December, 1990) [49] API Standard 650 Welded Tanks for Oil Storage, 11th edition, June, 2007 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale API Monogram® Licensing Program Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: certification@api.org Web: www.api.org/monogram ® API Quality Registrar (APIQR ) • ISO 9001 • ISO/TS 29001 • ISO 14001 • OHSAS 18001 ã API Spec Q1đ ã API Spec Q2đ • API QualityPlus® • Dual Registration Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: certification@api.org Web: www.api.org/apiqr API Training Provider Certification Program (TPCP®) Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: tpcp@api.org Web: www.api.org/tpcp API Individual Certification Programs (ICP®) Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: icp@api.org Web: www.api.org/icp Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS API Engine Oil Licensing and Certification System (EOLCS) Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: eolcs@api.org Web: www.api.org/eolcs www.api.org/quote API-U™ Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: training@api.org Web: www.api-u.org Motor Oil Matters Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: motoroilmatters@api.org Web: www.motoroilmatters.org API Data® Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Service: (+1) 202-682-8042 Email: data@api.org Web: www.APIDataNow.org API Diesel Exhaust Fluid Certification Program Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: apidef@api.org Web: www.apidef.org API Publications Phone: 1-800-854-7179 (Toll-free U.S and Canada) (+1) 303-397-7956 (Local and International) Fax: (+1) 303-397-2740 Web: www.api.org/pubs global.ihs.com API Perforator Design Registration Program Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: perfdesign@api.org Web: www.api.org/perforators API Standards Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: standards@api.org Web: www.api.org/standards API WorkSafe® Sales: 877-562-5187 (Toll-free U.S and Canada) (+1) 202-682-8041 (Local and International) Email: apiworksafe@api.org Web: www.api.org/worksafe Not for Resale `,,```,,,,````-`-`,,`,,`,`,,` - THERE’S MORE WHERE THIS CAME FROM REQUEST A QUOTATION Product No H190403 `,,```,,,,````-`-`,,`,,`,`,,` - Copyright American Petroleum Institute Provided by IHS under license with API No reproduction or networking permitted without license from IHS Not for Resale

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