Api mpms 19 4 2012 (american petroleum institute)

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 involveca

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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

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`,,```,,,,````-`-`,,`,,`,`,,` -Manual of Petroleum Measurement Standards Chapter 19.4

Evaporative Loss Reference Information and Speciation Methodology

Measurement Coordination

THIRD EDITION, OCTOBER 2012

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iii Copyright American Petroleum Institute

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`,,```,,,,````-`-`,,`,,`,`,,` -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, andChapter 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 involvecalculation of the vapor space temperature in order to determine vapor density, whereas this step is notinvolved 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 mannerfor both fixed- and floating-roof tanks)

2) Reconciliation of nomenclature Chapters 19.1 and 19.2 previously had different nomenclature for the samevariables 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 tableswere 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 designationsNew 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 temperaturesconcluded that a more sophisticated model for estimating storage tank temperatures has relatively little impact onestimated emissions, and thus the methodology now presented in Chapters 19.1 and 19.2 is the same aspreviously 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 6 Fuel Oil The default properties for No 6 Fuel Oil have been revised, resulting in a significant increase in theestimated true vapor pressure The former default properties are now presented as being suitable for vacuumresidual oil A new default speciation profile has also been added for No 6 Fuel Oil The study on which thesechanges are based has been added as Annex G

4) Maxwell-Bonnell correlations The annex presenting the Maxwell-Bonnell correlations has been edited with theconclusion that the separate correlations for predicting the normal boiling point from distillation data are notreliable

v Copyright American Petroleum Institute

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`,,```,,,,````-`-`,,`,,`,`,,` -vi Copyright American Petroleum Institute

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1 Scope 1

2 Normative References 1

3 Symbols 2

4 Variables 2

4.1 Meteorological Data 2

4.2 Stock True Vapor Pressure P V 27

4.3 Component Saturated Vapor Pressure 29

4.4 Stock Liquid Molecular Weight M L 29

4.5 Stock Vapor Molecular Weight M V 30

4.6 Component Molecular Weight M i 30

4.7 Concentrations for Selected Compounds in Petroleum Liquids 36

4.8 Tank Solar Absorptance α 38

5 Speciation Methods 39

5.1 Speciation Based on Liquid Profiles 39

5.2 Speciation Based on Vapor Profiles 41

6 Speciation Example 42

7 Speciation Theory 45

7.1 Introduction 45

7.2 Raoult’s Law 46

7.3 Precision, Accuracy, and Variability of Methods 47

7.4 Common Mistakes 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

P i o vii Copyright American Petroleum Institute

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Tables

1 Meteorological Data for Selected U.S Locations 3

2 Typical Properties of Selected Petroleum Liquids 28

3 Properties of Selected Petrochemicals 30

4 Concentrations (weight percent) of Selected Components in Selected Petroleum Liquids 37

5 Concentrations (weight percent) of Selected Components in No 6 Fuel Oil 37

6 Concentrations of PAHs in Selected Petroleum Liquids 38

7 Solar Absorptance α for Selected Tank Surfaces 39

8 Vapor Profile for Simulated Gasoline 42

9 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 6 Fuel Oil – True Vapor Pressure (psia) versus Temperature (°F) 85

G.2 No 6 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 6 Fuel Oil Liquid Phase Speciation Profile 87

G.5 No 6 Fuel Oil Liquid Phase Speciation Profile – Metals 88

G.6 No 6 Fuel Oil Liquid Phase Speciation Profile 89

G.7 Key to Sample IDs 90

G.8 No 6 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: T B – T A (°F) 104

I.2 Difference Between Equilibrium Bulk Temperature T BE and Ambient Temperature T A (°F) 120

I.3 Difference Between Liquid Surface Temperature and Ambient Temperature (°F) 126

I.4 Liquid Surface Temperature T L (°F) 126

I.5 Effect on Emissions for Fixed Roof Tanks – Vapor Pressure P V (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

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MPMS Ch 19.1 for fixed-roof tanks, API MPMS Ch 19.2 for floating-roof tanks, API MPMS Ch 19.5 for

marine vessels, and other methods used for total hydrocarbon emission estimates This process is referred

to as speciation

Speciation of emissions from hydrocarbon mixtures accounts for the higher evaporation rate of the more volatile components, resulting in a different composition of the mixture in the vapor phase than in the liquid phase The methodology presented in this standard assumes that there is sufficient liquid present such that the chemical composition at the liquid surface may be considered to not change as a result of the evaporative loss

This standard also contains reference information used for estimating emissions in accordance with API

MPMS Ch 19.1, API MPMS Ch.19.2, and API MPMS Ch.19.5

The methodology in this standard applies to:

a) liquids with vapor pressure that has reached equilibrium with ambient conditions at a true vapor pressure less than the ambient atmospheric pressure (i.e not boiling);

b) liquids for which the vapor pressure is known or for which sufficient data are available to determine the vapor pressure;

c) liquid mixtures where Raoult’s Law can be used to describe the vapor phase equilibria

This methodology does not apply to:

a) emissions that result from leaks from piping components (e.g valves, flanges, pumps, connectors etc.); b) liquid mixtures where Raoult’s Law cannot be used to describe the vapor phase equilibria (e.g mixtures

in which hydrocarbons are dissolved in water, or mixtures of hydrocarbons with alcohols)

2 Normative References

The following referenced documents are indispensable for the application of this document For dated references, only the edition cited applies For undated references, the latest edition of the referenced document (including any amendments) applies

API Manual of Petroleum Measurement Standards (MPMS) Chapter 19.1, Evaporative Loss from Fixed-Roof

Tanks, 4th Edition, 2012

Edition, September 2009

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`,,```,,,,````-`-`,,`,,`,`,,` -3 Symbols

NOTE 1 “19.1” and “19.2” refers to API MPMS Ch 19.1 and API MPMS Ch.19.2 respectively

NOTE 2 Symbols used in Annex I are listed in Section I.1

4 Variables

4.1 Meteorological Data

Meteorological data may be used to determine vapor space, liquid bulk, and liquid surface temperatures for storage tanks and can be obtained from local weather records or from historical averages given in Table 1 Data for this table are 30-year averages for the years 1961 through 1990, and are available at

http://rredc.nrel.gov/solar/old_data/nsrdb/redbook/sum2/state.html

API MPMS Ch 19.1 provides methods for determining tank temperatures for fixed-roof tanks API MPMS

Ch 19.2 provides methods for determining tank temperatures for floating-roof tanks Annex I of this standard documents these methods

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`,,```,,,,````-`-`,,`,,`,`,,` -Table 1—Meteorological Data for Selected U.S Locations Location Symbol Units Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Annual

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`,,```,,,,````-`-`,,`,,`,`,,` -Location Symbol Units Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Annual

Cold Bay, AK T MIN °F 24.1 22.8 25.0 28.6 34.9 40.8 46.0 47.1 43.2 34.9 29.8 26.6 33.6

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Las Vegas, NV T MIN °F 33.6 38.8 43.9 50.7 60.3 69.4 76.3 74.1 66.2 54.3 42.6 34.0 53.8

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Sioux Falls, SD T MIN °F 3.4 9.7 22.6 34.9 45.9 56.1 62.2 59.4 48.7 36.0 22.6 8.6 34.2

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Corpus Christi, TX T MIN °F 45.3 48.0 55.2 63.1 69.4 73.4 74.8 75.0 72.3 63.9 55.6 48.4 62.1

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Green Bay, WI T MIN °F 5.7 9.5 21.4 34.0 43.7 53.4 58.8 56.8 48.7 38.5 26.8 12.6 34.2

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`,,```,,,,````-`-`,,`,,`,`,,` -4.2 Stock True Vapor Pressure P V

For storage of pure chemicals, the stock true vapor pressure can be calculated using Antoine’s equation, as set

forth in 4.3

For selected petroleum liquids, such as gasoline, jet fuels, and No 2 fuel oil (diesel), the stock true vapor

For other volatile refined petroleum stocks and crude oils, values for the vapor pressure constants A and B may

be calculated as described below, and then the stock true vapor pressure calculated from Equation 5 using the

constants A and B thus determined

a) For refined petroleum stocks: The vapor pressure constants A and B are calculated from Equation (1) and

Equation (2), based on the stock RVP (1 psi to 20 psi) and the slope of the ASTM D86 distillation curve, S,

at 10 volume percent evaporated (°F/vol %) In the absence of ASTM D86 distillation data on refined

petroleum stocks, approximate values of the distillation slope S from Table 2 may be used

b) For crude oils: The vapor pressure constants A and B are calculated from Equation (3) and Equation (4)

based on the RVP (2 psi to 15 psi):

−

) 7 459 (T LA

B A

Alternately, if the stock’s normal boiling point and API gravity are reliably known, the true vapor pressure can

be determined using the Maxwell-Bonnell correlation described in Annex D

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`,,```,,,,````-`-`,,`,,`,`,,` -Table 2—Typical Properties of Selected Petroleum Liquids

Petroleum Liquid

Mixture

Vapor Molecular Weight a

Liquid Molecular Weight b

Condensed Vapor Density (at 60 °F) c (see Note 1)

Liquid Density a (see Note 2)

ASTM D86 Distillation Slope d

Vapor Pressure Equation Constants e

True Vapor Pressure (at 60 °F) (see Note 3)

lb/lb-mole lb/lb-mole lb/gal lb/gal ºF/vol % dimensionless ºR psia

Midcontinent Crude Oil 50 207 4.5 7.1 – Equation 3 Equation 4 –

NOTE 1 Condensed vapor density is not used to estimate or speciate emissions, but is used to convert pounds of emissions to equivalent gallons This may have application to inventory reconciliation, but is typically not needed for reporting emissions For

multicomponent petroleum liquids, the condensed vapor density, W VC , is less than the stock liquid density, W L If the condensed vapor density is unknown, it may be estimated from the following equationc (which was developed primarily for gasoline stocks):

W VC = 0.08 M V

NOTE 2 Liquid density is not used to speciate emissions, but it is a required property for estimating working (clingage) loss from a floating-roof tank

NOTE 3 True vapor pressure is calculated from Equation 5.

a U.S EPA Report AP-42, Fifth Edition, November 2006 [15], Table 7.1-2

b Liquid molecular weights from “Memorandum from Patrick B Murphy, Radian/RTP to James F Durham, EPA/CPB Concerning Petroleum Refinery Liquid HAP and Properties Data, August 10, 1993,” as adopted in versions 3.1 and 4.0 of EPA’s TANKS software

c API MPMS Ch 19.1, 3rd Edition [3] , 19.1.2.2.2.13

d API 2518 June 1962[47], Figure 1

e For motor gasolines, see API 2519, 3 rd Edition, Figure 4;

for crude oil, see API 2519, 3rd Edition, Figure 5;

for Jet Naphtha, Jet Kerosene, and No 2 Fuel Oil, see Barnett and Hibbard[39];

for No 6 Fuel Oil, see Annex G

f Properties given for Vacuum Residual Oil are those given for Residual Fuel Oil No 6 in API MPMS Ch 19.4, 2nd Edition[41], Table 2.

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`,,```,,,,````-`-`,,`,,`,`,,` -4.3 Component Saturated Vapor Pressure P i o

B A

LA 32)5/9(

log019337

B A

LA 32 ) 5 / 9 (

10019337

where

P i o = the vapor pressure, at temperature T LA , of component i (psia),

T LA = the stock liquid surface temperature (°F), and

A, B, C = Antoine constants The Antoine constants A, B, and C for selected petrochemicals are given in

Table 3 Antoine’s equation is discussed further in Annex B

The units conversion term, 0.019337, has units of (psia/mmHg)

If Antoine constants for a particular component are not available, the vapor pressure may be found from

particular temperature T that is not listed, the following relationship should be used:

1 2 1

P1 = vapor pressure at temperature T1, and

P2 = vapor pressure at temperature T2

This is the equation of the line through the points (1/T1, logP1) and (1/T2, log P2) on a plot of log P versus 1/T This

two-point linear interpolation equation draws upon the Clausius–Clapeyron equation (a simpler version of the

Antoine equation) and provides a method whereby the equation of the line between two adjacent data points is

used to relate pressure and temperature between these points Use of this equation to extrapolate a value for

P i o at a temperature outside of the range bounded by T1 and T2 may result in loss of accuracy

4.4 Stock Liquid Molecular Weight M L

and can be determined by the following methods

a) Table 2 gives typical stock liquid molecular weights for selected petroleum liquids

b) When the weight fractions are known for all the components of a stock liquid, the stock liquid molecular

weight can be calculated as:

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`,,```,,,,````-`-`,,`,,`,`,,` -where

c) Two analytical methods are available: gel permeation chromatography (GPC) using a refractive index

(RI) detector, and gas chromatography (GC) using a flame ionization detector (FID) More information on

these methods can be found in reference [14]

4.5 Stock Vapor Molecular Weight M V

The stock vapor molecular weight is the average molecular weight of the stock vapor on a weight basis The

stock vapor molecular weight may be determined the following methods

a) Table 2 gives typical stock vapor molecular weights for selected petroleum liquids

b) When the mole fractions are known for all the components of a stock vapor, the stock vapor molecular

weight can be calculated as:

where

c) Vapor samples may be analyzed

4.6 Component Molecular Weight M i

Molecular weights for selected petrochemicals are given in Table 3

Table 3—Properties of Selected Petrochemicals a

Chemical

Name

CAS Registry

No Molecular Weight

Liquid Density b (lb/gal)

True Vapor Pressure i

at 60 °F (psia)

Antoine’s Equation c

Normal Boiling Point (°F)

Constants Temperature Range d

{2-propenoic acid} 00079-10-7 72.06 8.77 1.344 5.652 648.6 154.68 68 158 282 Acrylonitrile

{2-propenenitrile} 00107-13-1 53.06 6.73 1.383 6.942 1,255.9 231.30 –60 172 172 Allyl alcohol 00107-18-6 58.08 7.13 0.326 11.658 4,510.2 416.80 70 207 206 Allyl chloridee

Tiêu đề	Evaporative Loss Reference Information And Speciation Methodology
Trường học	American Petroleum Institute
Chuyên ngành	Petroleum Measurement Standards
Thể loại	manual
Năm xuất bản	2012
Thành phố	Washington

Định dạng
Số trang	148
Dung lượng	2,13 MB

Api mpms 19 4 2012 (american petroleum institute)

Speciation Based on Vapor Profiles

Raoult’s Law Versus Other Equations of State