NBSIR 78 - 878

LIQUEFIED NATURAL GAS RESEARCH

at the

NATIONAL BUREAU OF STANDARDS

CRYOGENICS DIVISION • NBS-INSTITUTE FOR BASIC STANDARDS • BOUIDER, COLORADO

NBSIR 78 - 878

LIQUEFIED NATURAL GAS RESEARCH

at the

NATIONAL BUREAU OF STANDARDS

D.E. Diller, Editor

Cryogenics Division

Institute for Basic Standards

National Bureau of Standards

Boulder, Colorado 80302

Progress Report for the Period

1 July - 31 December 1977

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Sidney Harnnan, Under Secretary

Jordan J. Baructi, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler. Director
Prepared for

:

American Gas Association, Inc.

1515 Wilson Boulevard

Arlington, Virginia 22209

LNG Density Project Steering Committee

(in cooperation with the American Gas Association, Inc.)

Pipeline Research Committee

(American Gas Association, Inc.)

Federal Power Commission

Bureau of Natural Gas

Washington, DC 20426

U. S. Department of Commerce

Maritime Administration

Washington, DC 20235

U. S. Department of Commerce

National Bureau of Standards

Institute for Basic Standards

Boulder, Colorado 80302

U. S. Department of Commerce

National Bureau of Standards

Office of Standard Reference Data

Washington, DC 20234

U. S. Department of Commerce

National Bureau of Standards

Office of International Standards

Washington, DC 20234

LNG Sampling Measurements Supervisory Committee

LNG Custody Transfer Measurements Supervisory Committee

National Aeronautics and Space Administration

Lewis Research Center

Cleveland, Ohio 44135

American Bureau of Shipping

45 Broad Street

New York, NY 10004

ii
ABSTRACT

Twenty-nine cost centers supported by seven other agency sponsors in

addition to NBS, provide the basis for liquefied natural gas (LNG) research

at NBS. During this six-month reporting period the level of effort was over

20 man-years/year with funding expenditures of over $500,000. This

integrated progress report, to be issued in January and July, is designed to:

1) provide all sponsoring agencies with a semi-annual

report on the activities of their individual programs

;

2) inform all sponsoring agencies on related research being con- ducted at the Cryogenics Division

;

3) provide a uniform reporting procedure which should maintain

and improve communication while minimizing the time, effort

and paperwork at the cost center level.

The contents of this report will augment the quarterly progress meetings of some sponsors, but will not necessarily replace such meetings.

Distribution of this document is limited and intended primarily for the

supporting agencies. Data or other information must be considered pre - liminary, subject to change and unpublished, and therefore not for citation

in the open literature .

Key words: Cryogenics; liquefied natural gas; measurement; methane;

properties; research.
CONTENTS

Cost Center Page

REFERENCE DATA

a) THERMOPHYSICAL PROPERTIES DATA FOR PURE COM- 2750574 and 1

PONENTS AND MIXTURES OF LNG COMPONENTS 2750548

(American Gas Association, Inc.; NASA Lewis

Research Center)

b) FLUID TRANSPORT PROPERTIES 2750124 6 (NBS-Office of Standard Reference Data)

c) PROPERTIES OF CRYOGENIC FLUIDS (NBS) 2750122 8 d) PROPERTIES OF CRYOGENIC FLUID MIXTURES (NBS: 2750123, 11

(NBS-Office of Standard Reference Data; AGA) 2750129 and

2754574

e) DENSITIES OF LIQUEFIED NATURAL GAS MIXTURES (LNG 2751574 14

Density Project Steering Coininittee - AGA)

f) PROGRAM FOR REDUCING THE COST OF LNG SHIP HULL 2751430, 17

CONSTRUCTION — PHASE II SHIP STEEL IMPROVE- 275243 0 and

MENT PR0GRAI>1 (Maritime Administration) 2753430

II. MEASUREMENT SCIENCE

a) CUSTODY TRANSFER - LNG SHIPS (Maritime Adminis- 2750460, 19

tration; LNG Custody Transfer Measurements 2751575,

Supervisory Committee) 2752575 and

. . . -v - ^ 2753575

b) HEATING VALUE OF FLOWING LNG (Pipeline Research 2756579 21

Committee - AGA)

c) LNG DENSITY REFERENCE SYSTEM (American Gas Asso- 2757574 and 2 3 ciation. Inc.; National Bureau of Standards) 2750154

d) LNG SAMPLING MEASUREMENT STUDY (LNG Sampling Mea- 2750575 and 2 4 surements Supervisory Committee; Pipeline Re- 2755574

search Committee - AGA)

III. TECHNOLOGY TRANSFER

a) SURVEY OF CURRENT LITERATURE ON LNG AND METHANE 2759574 2 6 (American Gas Association, Inc.)

b) LIQUEFIED NATURAL GAS TECHNOLOGY TRANSFER (Mari- 2750403, 2 8 time Administration; American Gas Association, 2751403,

Inc.; American Bureau of Shipping; NBS-Office 2750570

of Standard Reference Data) 2754574

2758574,

2750127 and

2750461

c) OIML JOINT SECRETARIAT ON LNG MEASUREMENTS (Ameri- 2750104 31 can Gas Association, Inc.; NBS-Office of International Standards; NBS-Cryogenics Division)

d) FEDERAL POWER COMMISSION CONSULTATION 2750404 3 3

IV
1. Title. THERMOPHYSICAL PROPERTIES DATA FOR PURE COMPONENTS AND

f^iIXTURES OF LNG COMPONENTS

Principal Investigators . R. D. Goodwin, H. M. Roder, G. C. Straty,

R. Tsumura*, W. M. Haynes, and R. D. McCarty

2. Cost Center Number . 2750574, 2750548

3. Sponsor Project Identification . American Gas Association, Inc.,

Project BR-50-10. National Aeronautics and Space Administration,

Lewis Research Center, Purchase Order C-78014-C.

4. Introduction . Accurate phase equilibrium, equation of state (PVT) , and

thermodynamic properties data are needed to design and optimize gas

separation and liquefaction processes and equipment, and for mass and

heat transfer calculations. Accurate data for the pure components and

selected mixtures of hydrocarbon systems will permit developing

comprehensive accurate predictive calculation methods which take into

account the dependence of the thermophysical properties of mixtures on the composition, temperature, and density.

This project will provide comprehensive accurate thermophysical

properties data and predictive calculation methods for compressed and

liquefied hydrocarbon gases and their mixtures to support the development of LNG technology at NBS and throughout the fuel gas industry. It

will also serve as the base for a comprehensive mixtures prediction

methodology.

5. Objectives or Goals . The objectives of our work are the determination

of comprehensive accurate thermophysical properties data and predictive

calculation methods for the major pure components (methane, ethane,

propane, butanes, and nitrogen) and selected mixtures of liquefied

natural gas and hydrocarbon mixtures at temperatures between 90 K and

300 K and at pressures up to 35 MPa (5000 psi) . Our goal is to provide

a range and quality of data that will be recognized as definitive or standard for all foreseeable low temperature engineering calculations.

6. Background . Liquefied natural gas is expected to supply an increasing

percentage of the United States' future energy requirements. It is

likely that massive quantities of liquefied natural gas will be

imported during the years 1978 - 1990. Ships and importation terminals

are being built for transporting, storing, and vaporizing liquefied

natural gas for distribution. Accurate physical and thermodynamic

properties data for compressed and liquefied natural gas and hydrocarbon

mixtures are needed to support these projects. For example, accurate

compressibility and thermodynamic properties data are needed to design

and optimize liquefaction and transport processes; accurate data for the

heating value, which for liquefied natural gas mixtures depends on the

total volume, the density, and the composition, are needed to provide a basis for equitable custody transfer. Accurate mixture data prediction

methods are needed for use in automated heat transfer calculations.

Accurate thermodynamic properties data for liquefied gas mixtures must

be based on precise compressibility and calorimetric measurements;

compressibility data give the dependence of thermodynamic properties on pressure and density (at fixed temperatures); calorimetric data give

f

Consejo Nacional de Ciencia y Tecnologia (CONACYT) Mexico City. Formerly

a guest worker with the Cryogenics Division, National Bureau of Standards,

Institute for Basic Standards in Boulder, Colorado.
the dependence of thermodynamic properties on temperature (at fixed

pressures and densities). It is impossible, however, to perform

enough compressibility and calorimetric measurements directly on multicomponent mixtures to permit accurate interpolation of the data to

arbitrary compositions, temperatures and pressures. Instead, thermodynamic properties data for multicomponent mixtures must usually be

predicted (extrapolated) from a limited number of measurements on the

pure components and their binary mixtures. This project was initiated

to provide the natural gas and aerospace industries with comprehensive

accurate data for pure compressed and liquefied methane, the most

abundant component in LNG mixtures. We have published National Bureau

of Standards Technical Note 653, "Thermophysical Properties of Methane,

From 90 to 500 K at Pressures to 700 Bar," by Robert D. Goodwin (April

1974), and National Bureau of Standards Technical Note 684, "Thermophysical Properties of Ethane, From 90 to 600 K at Pressures to

700 Bar," by Robert D. Goodwin, H. M. Roder, and G. C. Straty (August

1976). These reports contain the most comprehensive and accurate tables

available for the thermophysical properties of pure gaseous and liquid

methane and ethane, and provide accurate basis for calculating

thermophysical properties data for LNG and other hydrocarbon mixtures.

Program and Results .

7.1 Ethane, Specific Heat Data — H. M. Roder

This phase of the program is complete. Two manuscripts describing

the results of the research have been published:

H. M. Roder, Measurements of the Specific Heats, Cg and C^, of Dense

Gaseous and Liquid Ethane, J. Res. Nat. Bur. Stand. (U.S.), Vol 80A,

No. 5, 739-59 (Sep-Oct 1976).

H. M. Roder, The Heats of Transition of Solid Ethane, J. Chem. Phys.

Vol 65, No. 4, 1371-3 (Aug 1976).

7.2 Ethane, Sound Velocity Data — R. Tsumura, G. C. Straty

This phase of the program is complete. The results of the research

have been reported in the following publication:

R. Tsumura, G. C. Straty, Speed of Sound in Saturated and Compressed

Fluid Ethane, Cryogenics Vol 17, No. 4, 195-200 (Apr 1977).

7.3 Ethane, Thermophysical Properties Data -- R. D. Goodwin

The manuscript, National Bureau of Standards Technical Note 684,

"Thermophysical Properties of Ethane, From 90 to 600 K at Pressures to

700 Bar," by R. D. Goodwin, H. M. Roder, and G, C. Straty (August 1976)

has been published and distributed.

7.4 Propane, Thermophysical Properties Data -- R. D. Goodwin

Available, published physical properties data, acquired through our Cryogenic Data Center, have been evaluated and formulated as required

for thermodynamic computations. These niomerous properties now have

been used to compute a complete set of provisional tables of

thermodynamic functions.

The manuscript, "Provisional Thermodynamic Functions of Propane, From

85 to 700 K at Pressures to 700 Bar," has been published as National

Bureau of Standards Internal Report, NBSIR 77-860 (July 1977).
7.5 Propane, PVTx and Dielectric Constant 2'ieasurerients — W. M. Haynes

As noted in the last semiannual progress report a new apparatus has been

developed for pressure, temperature, density, composition, and dielectric

constant measurements on liquids and liquid mixtures at temperatures

between 70 and 350 K and at pressures to 35 MPa (approximately 5000 psi)

.

The major features of the apparatus were described in detail in that

report. Several significant changes have been made to the apparatus as

a result of performance tests during the past few months. Difficulties

with the servosystem have precluded any density measurements up to the

present.

The problems with the servosystem, especially the capacitance sensor,

appear to have been resolved during the past month. Thin nylon screen

disks have been placed over the plates of the capacitance sensor. These

screens serve two purposes. They eliminate false signals to servosystemi

resulting from the m.etal-plated float, when not in suspension, electrically shorting the plates. (For example, when the float shorts the

upper capacitance plates, it gives a signal that says the float is

down.) The thickness of the nylon disks (although small! helps to

prevent the float from going from a region (close to the plates), for

IC which the sensitivity (-7-=-) is extremely large, to a relatively linear

region near the midpoint of the sensor where the sensitivity is an order of magnitude less; however, it is still sufficient to support the

magnet in the middle region. The servosystem. V7as difficult to stabilize

when the sensor had such a drastic change in sensitivity. The circuit

components depended critically on the particular experimental conditions.

Compensation circuits have been added to the servosystem to allovr for

the large reduction in electrical resistivity of the copper cell in

going from room temperature to 100 K. As mentioned earlier the servo- system is finally behaving as expected and density tests will be started

within the next week. The only part of the instrum.ent that has jiot been

tested is the microscope. This will be done once the servosystem. is

behaving reliably. It appears that with a new objective lens with a larger working distance (less power) and a new higher powered eyepiece

that changes of 0.001 mm in the position of the float can be detected.

However, the fiducial tool marks on the float are not as clear as they

were with a shorter working distance

.

Although density measurements have not been performied yet, m.any im^portant

tests of the apparatus have been carried out with the following results:

(a) the cell has been cooled to approxim.ately 80 K using the refluxir.g

action of nitrogen in the central support tube; the cooling rate was greater than 4 0 K/h above 15 0 K and approxim.ately 2 0 K/h at 100 K.

(b) the tem^peratures of the cell and guard ring have been controlled

at low temperatures (110-125 K) and near room temperature within a few

mK; nitrogen gas must be put into refliix tube for sufficient cooling to

regulate the temperature of the cell below 14 0 K; some difficulties have

been encountered in realizing a constant cooling rate under these

conditions; it would be nice if changes could be made to provide m.ore cooling to cell without adding any to guard ring and with the reflux

tube evacuated.

(c) the temperature differences between the bottom, and top of the cell

and between the cell and guard ring as determined with vapor bulb

pressure readings agreed with the differences indicated by differential

therm.ocouples at the sam.e locations.

(d) temperature gradients along the length of the cell can be routinely

reduced to an allowable level (< 2 0 mK) with the independent heaters

along the length of the cell.

3
(e) measured vapor pressures for liquid methane in cell and in vapor

bulbs at top and bottom of cell at temperatures between 110 and 12 5 K

corresponded to a difference of less than 20 mK when compared with

previous vapor pressure measurements obtained in this laboratory.

(f) cell and guard ring are essentially isolated from each other so that the temperature of either can be independently controlled.

(g) a preliminary measurement of the dielectric constant of saturated

liquid methane agreed to better than 0.005% with previous results from

this laboratory.

(h) the current in the support coil is stable and measurable to better

than 10 uA; noise level is substantially less.

(i) no problems have been encountered with heating in the water-cooled

support coil at power levels approaching 200 W.

Assorted rather significant changes to the apparatus (in addition to

those discussed earlier for the servosystem) during the past few months

include the following:

(a) a nut, bolt (fiberglass) , and spring arrangement was installed

between the cold shield and bottom of the cell to eliminate horizontal

vibrations of the cell.

(b) all coaxial cables into cell were replaced with new stock after a cold leak (below 120 K) developed in apparatus resulting from tiny

cracks in the stainless steel sheaths of these cables; apparently the

first supply of the coaxial cables came from a defective batch of

stainless steel material; the search for the source of this leak and the

replacement of the cables consumed approximately six weeks.

(c) metal bellows were placed in the fill and vent lines of the liquid

nitrogen reservoir to eliminate relative movement, as a function of

temperature, between the cell and the outer stainless can of the

cryostat; this step was necessary since the capacitance sensor and the

float inside the cell must remain in the middle of the support coil

located outside the cryostat, independent of the cell temperature.

It is believed that with all of the performance tests and changes of

the past few months that the apparatus is essentially ready for density

measurements. After preliminary checks on some pure fluids, measurements

will be started on LNG mixtures.

7.6 Calculational Methods — R. D. McCarty

Efforts to develop a predictive calculational method for the thermodynamic properties of mixtures have concentrated on the extended

corresponding states method. The rigorous mapping of the equation of

state of one fluid to the equation of state of another has been

accomplished for the methane-nitrogen system (see earlier progress

reports), but to achieve the maximum utility from the method other

systems must exhibit similar transformation functions. For example, in

the case of liquefied natural gas the methane-ethane system is very

important. Therefore some commonality between the methane-nitrogen

transformation and the methane-ethane transformation would be very

beneficial to the utility of the method. This argument is immediately

extendable to all of the components of any multicomponent system. It

is this "generality" of the extended corresponding states concept that

is currently being studied and no definite conclusions may be drawn at

this stage of the investigation.

4
7.7 Propane, Specific Heat Data — R. D. Goodwin

An apparatus used previously for hydrogen, oxygen, fluorine, methane

and ethane measurements is being used; however, the platinum resistance

thermometer has been replaced. Eighty-eight measurements on the empty

calorimeter from 80.3 K through 345.3 K have been represented by a new

fitting function with an rms deviation of 0.078 percent in the total,

empty heat capacity. Below 250 K, maximum deviations are only a few

hundredths of one percent.

Experimental data for propane specific heats have been obtained for the

saturated liquid from below the triple-point (85.5 K) to 242.8 K and to

288.8 K in two runs at densities of 12.6 and 11,3 mol/L respectively.

Additional data (Cv) for the single phase have been obtained at five

different densities, over diminishing ranges of temperature from about

350 K down to 155 K. These measurements are currently continuing.

8. Problem Areas . None.

9. Funding . July 1 - December 31, 1977.

Man-years expended

Equipment and/or Services Purchased

Total Reporting Period Cost

Balance Remaining

10. Future Plans . Objectives and Schedule: Quarter

Prepare and performance test PVT

and dielectric constant

properties apparatus for propane.

Measure, analyze and report PVT and

dielectric constant data for

hydrocarbon mixtures and LNG.

Evaluate and optimize promising

calculation methods for the

thermodynamic properties of

methane-nitrogen mixtures.

Measure, analyze and report specific

heat data for propane. >

0.6

6. 3K$

43.8K$

94.3K$

5
1. Title . FLUID TRANSPORT PROPERTIES

Principal Investigator . Howard J. M. Hanley

2. Cost Center Number . 2750124

3. Sponsor Project Identification . NBS-Office of Standard Reference Data

4. Introduction . Methods for predicting the transport properties of fluid

mixtures are unreliable and data are scarce. Prediction methods are

needed, however, to supply the necessary design data needed to increase

efficiency and reduce costs.

5. Objectives or Goals . The long range or continuing goal of the program

is to perform a systematic study of the theories and experimental measurements relating to transport properties, specifically the viscosity

and thermal conductivity coefficients, of simple mixtures over a wide

range of experimental conditions. The specific objectives of the program include: 1) the systematic correlation of the transport properties

of simple binary mixtures and the development of prediction techniques,

2) development of a mixture theory for the dilute gas region and the

dense gas and liquid regions, 3) extension of the theory and prediction

techniques to multicomponent systems, and 4) suggested guidelines for

future areas of experimental work.

6. Background . A continuing program has successfully expanded the stateof-the-art of transport phenomena for pure fluids. Information for pure

fluids is required as a prerequisite for mixture studies. The theory

of transport phenomena has been developed and applied to produce practical

numerical tables of the viscosity, thermal conductivity and diffusion

(3) coefficients of simple fluids: Ar , Kr , Xe , N^, 0„ , F_, He, H„, CH.,

(4) ^ z ^ ^ 4

It has been shown that a successful mixture program can emerge from

combining the results for pure fluids with mixture equation of state

studies. The equation of state work is being carried out by other

investigators in this laboratory.

7. Program and Results . A procedure to predict the transport properties of

mixtures has been developed via corresponding states. (-'-"2) '^he method

has been shown to be satisfactory. Current studies include investigating the effects of internal degrees of freedom on the thermal

conductivity coefficient and the behavior of the transport coefficients

near a critical point. (2) Tables of transport properties for propane

have been prepared and submitted for publication . )

8. Problem Areas . The lack of suitable experimental mixture transport

properties data for comparison purposes is the main problem. Also

equation of state (PVT) data for mixtures are needed.

9. Funding . July 1 - December 31, 1977.

Allocation 63.0K$/yr.

Labor 0 . 5 MY 32.9K$

Other Costs 2 . 7K$

Total 3 5. 6K$

10. Future Plans . The transport properties of ethylene will be investigated.

The corresponding states predictive procedure for mixtures will be more

fully developed and expanded in line with the concurrent equation of

state studies.

6
References

1. H. J. M. Hanley, Prediction of the Viscosity and Thermal Conductivity

Coefficients of Mixtures, Cryogenics, Vol 16, No. 11, 643-51 (Nov 1975);

H. J. M. Hanley, Prediction of the Thermal Conductivity of Fluid

Mixtures, Proceedings 7th ASME Conf . on Thermophysical properties;

H. J. M. Hanley in "Phase Equilibria and Fluid Properties in the

Chemical Industry," ACS Symp. Series No. 6 0 (19 77).

2. H. J. M. Hanley, Transport Coefficients in the One-Fluid Approximation:

Behavior in the Critical Region, J. Res. Nat. Bur. Stand. (U.S.) 82 , 18 (1977).

3. H. J. M. Hanley, W. M. Haynes and R. D. McCarty, The Viscosity and

Thermal Conductivity Coefficients for Dense Gaseous and Liquid Methane,

J. Phys. Chem. Ref. Data, Vol 6, No. 2, 597-609 (1977).

4. H. J. M. Hanley, K. E. Gubbins and S. Murad, A Correlation of the

Existing Viscosity and Thermal Conductivity Coefficients of Gaseous and

Liquid Ethane, J. Phys. Chem. Ref. Data, Vol 6, No. 4, 1167 (1977).

5. H. J. M. Hanley, P. M. Holland, K. E. Gubbins and J. M, Haile, J. Phys.

Chem. Ref. Data (in preparation).

7
1. Title . PROPERTIES OF CRYOGENIC FLUIDS

Principal Investigators . G. C. Straty, H. M. Roder, L. A. Weber, B. J.

!"!" Ackerson, and D. E. Diller

2. Cost Center Nvimber . 2750122

3. Sponsor Project Identification . NBS

4. Introduction . Accurate thermophysical properties data and predictive

calculation methods for cryogenic fluids are needed to support advanced

cryogenic technology projects. For example, liquefied natural gas is

expected to supply an increasing percentage of the United States'

energy requirements through 1990. Liquefaction plants, ships and

receiving terminals are being constructed to transport and store natural

gas in the liquid state (LNG) . Accurate thermophysical properties data

for LNG are needed to design low temperature processes and equipment.

Accurate data will benefit the energy industries and the consumer by

providing for safe and efficient operations and reduced costs.

5. Objectives or Goals . The objectives of this project are to provide

comprehensive accurate thermodynamic, electromagnetic and transport

properties data and calculation methods for technically important

compressed and liquefied gases (helium, hydrogen, oxygen, nitrogen,

methane, ethane, etc.) at low temperatures. Precise compressibility,

calorimetric and other physical property measurements will be performed

to fill gaps and reconcile inconsistencies. Definitive interpolation

functions, computer programs and tables will be prepared for engineering

calculations. The immediate goals of this work are to obtain accurate

sound velocity and thermal diffusivity data for compressed and liquefied

gases by using laser light scattering spectroscopy techniques. Sound

velocity data are useful for testing the consistency of volumetric,

calorimetric and thermodynamic properties data, and are potentially

useful for density gauging applications. Thermal diffusivity data are required for performing thermodynamic and heat transfer calculations.

6. Background . When light is incident on a perfectly homogeneous fluid,

the reradiated (scattered) light field sums to zero in all but the exact

forward direction. For a "real" fluid, however, fluctuations, arising

through various mechanisms, destroy the perfect homogeneity and result

in the scattering of light in other directions as well. For example,

thermally activated density fluctuations (phonons) , propagating with

the characteristic velocity of sound, give rise to scattered light which

is Doppler shifted in frequency from the incident light frequency and

whose spectrum contains information on the sound velocity and attenuation. Local non-propagating temperature fluctuations, which decay

diffusively, give rise to scattered light in a narrow frequency band

about the incident light frequency and whose spectrum contains

information on the lifetime of the fluctuations (thermal diffusivity)

.

Since the frequency shifts are generally very small, it was not until

the advent of the lasers with their extremely well defined frequency,

that practical experiments using these phenomena were possible.

The application of laser light scattering techniques to obtaining

thermophysical properties data was initiated to complement and check

other measurement methods and to solve measurement problems inherent

in more conventional methods. For example, laser light scattering

techniques permit measurements of sound velocities for fluids under

conditions for which sound absorption is too large to perform ultrasonic

measurements; laser light scattering techniques permit measurements of

thermal dif f usiyities under conditions for which convection interferes

with measurements of thermal conduction. The feasibility of light

scattering experiments to obtain data on binary diffusion coefficients

has also been demonstrated.

8
7. Program and Results . An apparatus has been assembled for laser light

scattering spectroscopy measurements on compressed and liquefied gases

(76-300 K, 35 MPa) . The apparatus consists of a high pressure optical

cell, a cryostat refrigerated by means of liquid nitrogen, an argon ion

laser and low-level light detection equipment.

The light scattered from fluctuations in the fluid can be analyzed with

either digital autocorrelation techniques for the examination of the

very narrow lines associated with scattering from temperature

fluctuations (Rayleigh scattering) or with a scanned Fabry Perot

interferometer for the measurement of the Doppler frequency shifts

associated with the scattering from propagating density (pressure)

fluctuations (Brillouin scattering)

.

Apparatus for photon-counting and digital autocorrelation has been

assembled, interfaced with computer facilities and programmed to

enable on-line data accumulation and analysis. Initial problems

associated with signal modulations from excessive building vibrations

have been solved by levitating the apparatus on an air suspension

system. A small, highly stable capacitor has also been designed,

constructed and installed inside the scattering cell to permit the

dielectric constant of the scattering fluid to be determined, which

should allow more accurate fluid densities to be obtained for use in

the data analysis. Apparatus tests on well characterized, strongly

scattering, test fluids have been made to verify data analysis

programs

.

Extensive thermal diffusivity data have been obtained for methane.

Measurements have been made along the coexistence curve, the critical

isochore, and critical isotherm. The measurements extend outside the

critical region as well as deep into the critical region. In the deep

critical region the effect of temperature gradients and impurities have

been investigated. Outside the critical region, these effects do not

affect measurements beyond experimental accuracy. The range of the

measurements extends from 150 K to 2 30 K and 3 mol/L to 22 mol/L. The

accuracy of the measurements is about 5% in the critical region,

increasing to 10% or greater further away. A detailed analysis of the

data and experimental error has been made and a paper ^-'-^ reporting the

results has been submitted to the Journal of Chemical Physics.

Some preliminary results on a mixture of 70% methane and 30% ethane were obtained very near the vapor-liquid critical point (plait point)

.

The results are interesting in that the thermal conductivity of the

mixture does not exhibit a critical anomaly whereas pure methane does

exhibit an anomaly in the thermal conductivity as the critical point is

approached. The anomalous behavior of pure fluids and non-anomalous

behavior of mixtures is qualitatively and quantitatively in agreement

with theoretical predictions (see preceeding title 'Fluid Transport

Properties'). We hope to be able to perform more definitive measurements

on hydrocarbon mixtures in the near future.

8. Problem Areas . Light scattering has proven to be a valuable tool for

obtaining thermal diffusivity data on fluids. This is particularly

true in a broad temperature and density range around the critical

point, where more conventional experimental methods fail or are severely limited. The intensity of the scattered light however

decreases drastically as one moves away from the critical region.

Data accuracy in this region becomes limited by the statistical nature

of the scattering process and the ability to maintain stability and

precise experimental parameters over the extended periods of time

necessary for data accumulation.

We have investigated other experimental techniques for obtaining widerange thermal conductivity measurements on compressed and liquefied

gases and have decided that the transient hot-wire method offers the

9
clearest advantages. The cell has been constructed and several pieces

of equipment have been ordered. The electronic circuits have been

designed and all drawings have been completed or are in the final

stages of preparation.

9. Funding . July 1 - December 31, 1977

Man-years expended 0.6

Equipment and/or Services Purchased 3.6K$

Total Reporting Period Cost 45.0K$

Balance Remaining 4 0.0K$

10. Future Plans . Objectives and Schedule: Quarter 1 2 Design, construct and performance

test transient hot-wire thermal

conductivity apparatus.

Reference

1. B. J. Ackerson and G. C. Straty, Rayleigh Scattering from Methane,

J. Chem. Phys. (submitted).

10
1. Title . PROPERTIES OF CRYOGENIC FLUID MIXTURES

Principal Investigators . M. J. Hiza, A. J. Kidnay (part-time) , and

R. C. Miller (part-time)

.

2. Cost Center Niimbers . 2750123, 2750129 and 2754574

3. Sponsor Project Identification . NBS , NBS (OSRD) , AGA

4. Introduction . Accurate thermodynamic properties data and prediction

methods for mixtures of cryogenic fluids are needed to design and

optimize low temperature processes and equipment. This project provides

new experimental measurements on equilibrium properties and compilations

of evaluated equilibrium properties data which are suitable for direct

technological use or for the evaluation of prediction methods.

5. Objectives or Goals . The overall objectives of this project are to

provide critically evaluated data on the phase equilibria and thermodynamic properties of cryogenic fluid mixtures. The program has been

divided into the following elements:

a) Preparation of a comprehensive bibliography on experimental

measurements of equilibrium properties for mixtures of selected

molecular species of principal interest in cryogenic technology.

b) Selection and/or development of methods for correlation, evaluation

and prediction of equilibrium properties data.

c) Retrieval and evaluation of experimental data for specific mixture

systems selected on the basis of theoretical and/or technological

importance.

d) Preparation of guidelines for future research based on the

deficiencies noted in (a) , (b) , and (c)

.

e) Performing experimental research to alleviate deficiencies and

provide a basis for improvement of prediction methods.

6. Background . A physical equilibria of mixtures research project was established in the Cryogenics Division in 1959. The initial effort,

based on a bibliographic search and other considerations, was directed

toward the acquisition of new experimental data on the solid-vapor and

liquid-vapor equilibria and physical adsorption properties for a limited

number of binary and ternary mixtures of components with widely separated

critical temperatures. Most of the systems studied included one of the

light hydrocarbon species -- methane, ethane, or ethylene (ethene) -- with one of the quantum gases — helium, hydrogen, or neon. The data

for these systems led to significant improvements in the predictions of

physical adsorption equilibrium and a correlation for the prediction of

deviations from the geometric mean rule for combining characteristic

energy parameters. In addition, significant new information was obtained

for interaction third virial coefficients which was used in a correlation by one of our consultants, J. M. Frausnitz . The approach taken

in this work has been as fundamental as possible with the intention of

having an impact on a broad range of mixture problems.

Recent efforts have been directed toward problems associated with

systems containing components with overlapping liquid temperature

ranges, such as nitrogen + methane, methane + ethane, etc.

n
Program and Results . The recent progress is summarized as follows:

a) A paper ^"'"^ discussing compilation, evaluation, and correlation of

liquid-vapor equilibria data - excess Gibbs energies, liquid phase

heats of mixing, Henry's constants, equation of state representation,

and liquid phase excess volumes - for methane + ethane is now

being reviewed by readers selected by the editor of the Journal of

Physical and Chemical Reference Data. These reviews are in lieu

of the outside review for the NBS (Boulder) Editorial Review Board.

b) The Peng-Robinson equation of state, optimized to the selected

data in a) , has now been used to generate methane + ethane K-values

and liquid-vapor equilibrium compositions for inclusion in the LNG

Materials and Fluids user's manual. In addition, graphs of

orthobaric liquid densities of methane + ethane, methane + propane,

and ethane + propane over the entire composition range from

105-130 K were prepared from a temperature dependent Redlich-Kister

representation of NBS data obtained in the LNG density project.

These graphs are also to be included in the LNG Materials and Fluids

user's manual.

(2

)

c) A paper discussing the development of an excess volume model to

predict orthobaric densities of LNG mixtures has been accepted for

publication in the journal Fluid Phase Equilibria. The model has

been programmed and is available for use. In the program

Redlich-Kister constants for methane + ethane obtained in a) are now being used which extends the low temperature limit at least

down to 95 K vs. 105 K in the original form.

d) Evaluation of the molar volume measurements made at the University

of Wyoming on one methane + ethane binary mixture and on four

multicomponent mixtures has been completed. The results were compared with the excess volume model in c) , the optimized hardsphere model of Rodosevich and Miller, and a revised and optimized

version of the Klosek and McKinley model. A paper communicating

these results and comparisons with predicted values, has been

submitted to the journal Fluid Phase Equilibria.

e) In conjunction with the correlation and evaluation of mixtures

data, various computer programs are needed. In the past several

months, fifteen programs have been written or modified for this

purpose. Properties include liquid-vapor equilibrium, orthobaric

liquid mixture densities, enthalpy departures, and derived excess Gibbs energies. Most of these programs will be used in the

compilation, evaluation, and correlation of methane + propane

data.

f) As mentioned in b) above, graphs have been prepared for density

and phase equilibria properties of several mixtures for the "LNG

Materials and Fluids Data Book." The first edition of the book

contained four graphs covering the methane-nitrogen system. The

supplement will include similar graphs covering methane-ethane,

methane-propane and ethane-propane systems as well as several

density graphs for LNG and LNG-like multicomponent systems.

Problem Areas . None.

Funding. July 1 - December 31, 1977

Man-years expended 1.1

Equipment and/or Services Purchased 4.1K$

Total Reporting Period Cost 89.3K$

Balance Remaining 64.2K$

12
10. Future Plans.

Objectives and Schedule: Quarter 1 2 Prepare and report graphs of

liquid-vapor equilibrium

K-values and equilibrium phase >

compositions for methane + ethane.

Prepare and report graphs of

orthobaric liquid densities for

methane + ethane, methane + ^

propane, and ethane + propane.

Compile and evaluate liquid-vapor

equilibrium properties data for — >

methane + propane.

Design and construct a phase

equilibria apparatus for total

vapor pressure r.easurem.ents

(methane + isobutane)

.

References

1. M. J. Hiza, R. C. Miller, and A. J. Kidnay, A Revievr, Evaluation, and

Correlation of the Phase Equilibria, Heat of Mixing, and Change in

Volume on Mixing for Liquid Mixtures of Methane + Ethane, J. Phys . Chem.

Ref . Data (to be submitted)

.

2. M. J. Hiza, An Empirical Excess Volume Model for Estimating Liquefied

Natural Gas Densities, Fluid Phase Equilibria ;in press).

3. R. C. Miller and M. J. Hiza, Experimental Molar Volum.es for Some

LNG-Related Saturated Liquid Mixtures, Fluid Phase Equilibria (submitted

September 1977) .

13
1. Title . DENSITIES OF LIQUEFIED NATURAL GAS MIXTURES

Principal Investigators . M. J. Hiza, W. M. Haynes, R. D. McCarty and

W. R. Parrish

2. Cost Center Numbers . 2751574

3. Sponsor Project Identification . LNG Density Project Steering

Committee; American Gas Association, Inc., Project BR-50-11.

4. Introduction . Accurate density measurements and calculational methods

for liquefied natural gas mixtures are needed to provide a basis for

custody transfer agreements and for mass, density, and heating value

gauging throughout the fuel gas industry.

The basis for the custody transfer of natural gas is its heating value.

It is difficult to determine and agree on the heating value of extremely

large volumes of natural gas in the liquid state. For example, methods

for calculating the heating value of a liquefied natural gas mixture

require knowing its density, which in turn depends on its composition,

• temperature, and pressure. As the compositions of LNG mixtures vary

considerably, depending on the sources of the gas and the processing

conditions, accurate methods are needed for calculating liquid densities

at arbitrary compositions, temperatures and pressures. The accuracy is

„ ; important because of the extremely large volumes of liquid involved.

5. Objectives or Goals . The objectives of this work are to perform

' accurate (0.1%) and precise (0.02%) measurements of the densities of

saturated liquid methane, ethane, propane, butanes, nitrogen and their

mixtures mainly in the temperature range 105-140 K, and to test and

optimize mathematical models for calculating the densities of LNG

mixtures at arbitrary compositions and temperatures.

6. Background . This project is being carried out at NBS because of the

realization that equitable custody transfer agreements could be reached

more readily if the density measurements and the evaluation and development of calculational methods were performed by independent professionals.

An apparatus incorporating a magnetic suspension technique has been

developed for absolute density measurements on liquids and liquid

mixtures, particularly at saturation, for temperatures between 90 and

300 K. The estimated imprecision of measurement is less than 0.02%

and the estimated inaccuracy is less than 0.15%.

7 . Program and Results . 7.1 Measurements. All measurements on pure fluids and on selected

binary mixtures have been completed and reported. ^-^ ' '

' ^' Inconsistencies found in the butane-containing multicomponent mixtures (without

nitrogen) were mentioned in the last report. These have been identified

as probably arising from inadequate mixing within the cell. Previous

data, published and unpublished, from the University of Wyoming and

Elf Aquitaine in France tend to support this supposition. This

hypothesis was further supported by additional measurements performed

on the Wyoming apparatus (9' by a member of the NBS staff. (See report

of Project 2750123 for more details.) The LNG Density Project Steering

Committee has funded additional measurements to fully resolve the

inconsistencies as well as to include data on additional mixtures. The

report on the previous NBS multicomponent mixtures data has been delayed.

The magnetic densimeter has been extensively modified to allow measurements to higher pressures. This work and the new apparatus is fully

- described in the report for cost center number 2750574.

14
A two part paper (experimental and calculational) was presented at

the Fifth International Conference on Liquefied Natural Gas in

Diisseldorf, Germany in August 1977.

7.2 Calculational Methods . Four promising methods for calculating the

densities of liquid mixtures have been tested, modified and optimized

utilizing the pure component and binary mixture data reported above.

The four methods are a corresponding states method, a cell model, a hard-sphere model and an excess volume model. Computer programs have

been written for all four methods and these have been used to calculate

densities for comparisons with the data for the mixtures measured. The

calculated results agree with the experimental data to within 0.1% for

all multicomponent mixtures except those containing methane and butanes

but no nitrogen. If nitrogen is present the differences reduce to

0.1% or less. Comparisons of the four methods with both published and

\inpublished data from the University of Wyoming and Elf Aquitaine in

France show deviations of less than + 0.15% between measured and

calculated densities. It is felt that only small corrections to the

four methods will likely need to be made as a result of the new measurements proposed in 7.1 above.

Two of the four methods have been modified to account for the presence

of small amounts of the pentanes. The modifications were based on published data for pure, normal and iso-pentane.

The results of the calculational efforts were presented to the Fifth

International Conference on Liquefied Natural Gas^^) as mentioned in

7.1 above. A more complete account of the calculational methods study

(including the four computer programs) has been prepared. This report

was published as NBSIR 77-867(10^. Approximately 100 copies have been

distributed

.

8. Problem Areas . Several experimental problems have delayed the

planned measurements on the new apparatus.

9. Funding. July 1 - December 31, 1977.

Man-years expended

Equipment and/or Services Purchased

Total Reporting Period Cost

Balance Remaining

0. 3 1. 0K$

21. 1K$

55. 9K$

10. Future Plans . Objectives and Schedule; Quarter

Performance test new magnetic

densimeter PVTx apparatus.

Measure, analyze, and report

multicomponent mixture data,

including selected LNG-like

mixtures

.

References

1. W. M. Haynes and M. J. Hiza, Orthobaric Liquid Densities of Normal

Butane from 135 to 300 K as Determined with a Magnetic Suspension

Densimeter, Advan. Cryog. Eng. Vol 21, 516-21 (Plenum Press, New York,

1976) .

2. W. M, Haynes and M. J. Hiza, Measurements of the Orthobaric Liquid

Densities of Methane, Ethane, Propane, Isobutane, and Normal Butane,

J. Chem. Thermodynamics Vol 9, 179-87 (Feb 1977).

15
3. M. J. Hiza, W. M. Haynes and W. R. Parrish, Orthobaric Liquid Densities

and Excess Voliimes for Binary Mixtures of Low Molar Mass Alkanes and

Nitrogen Between 105 and 14 0 K, J. Chem. Thermodynamics Vol 9, No. 9,

873-96 (Sep 1977)

.

4. W. M. Haynes, M. J. Hiza and N. V. Frederick, Magnetic Suspension

Densimeter for Measurements on Fluids of Cryogenic Interest, Rev. Sci.

Instrum. Vol 47, No. 10, 1237-50 (Oct 1976).

5. W. M. Haynes, A Simplified Magnetic Suspension Densimeter for Absolute

Density Measurements, Rev. Sci. Instrum. Vol 48, 39 (1977).

6. W. M. Haynes, M. J. Hiza, and R. D. McCarty , Densities of LNG for

Custody Transfer, Proc. Fifth International Conference on Liquefied

Natural Gas, Diisseldorf, Germany, Aug 29-Sep 1, 1977, Session III,

Paper No. 11, Vol 2 (1977).

7. D. E. Diller, LNG Density Determination, Hydrocarbon Proc. Vol 56, No. 4,

142-4 (Apr 1977)

.

8. M. J. Hiza, An Empirical Excess Volume Model for Estimating Liquefied

Natural Gas Densities, Fluid Phase Equilibria (to be published).

9. R. C. Miller and M. J. Hiza, Experimental Molar Volumes for Some

LNG-Related Saturated Liquid Mixtures, Fluid Phase Equilibria (to be

published)

.

10. R. D. McCarty, A Comparison of Mathematical Models for the Prediction

of LNG Densities, Nat. Bur. Stand. (U.S.), Interagency Rept. 77-867

(Oct 1977)

.

16
1. Title . PROGRAM FOR REDUCING THE COST OF LNG SHIP HULL CONSTRUCTIOi^ -- PHASE II SHIP STEEL IMPROVEMENT PROGRAM

Principal Investigators . H. I. McHenry, M. B. Kasen, and R. P. Reed

2. Cost Center Number . 2753430 - LNG Ship Hull Materials (Shipyard Contracts)

2751430 - LNG Ship Construction Materials (Metallurgical Evaluation)

2752430 - LNG Ship Hull Materials (Fracture Properties)

3. Sponsor Project Identification . Maritime Administration Misc. P. 0.

400-58073.

4. Introduction . Construction of LNG tankers requires the use of fine

grain normalized steels for the part of the hull structure that is

cooled by the cargo to temperatures in the range of 0 to -50°F. Several

ABS steels have satisfactory base plate properties but extreme care must

be exercised during welding to avoid degradation of the steel adjacent

to weld (the heat affected zone) to a level of toughness below U. S.

Coast Guard requirements. Significant cost problems are being encountered by U. S. shipyards due to the resulting inefficient low-heat-input

welding procedures that must be employed to meet the fracture requirements in the heat affected zone. The feasibility of reducing the cost of LNG ship hull construction was investigated in Phase I of this project, leading to the Phase II program described below.

5. Ob j ective . The objectives of the Phase II program are 1) to have the

four major plate producers supply three LNG shipyards with production

heats of ABS steels modified to possess improved transverse fracture

properties at low temperatures, 2) to have the LNG shipyards evaluate

these plates by qualifying optimum welding procedures in accordance with

the USCG requirements, and 3) to provide a metallurgical evaluation of

factors that influence heat affected zone toughness in the improved

steels

.

6. Background . Early in 1974, the Welding Panel of MarAd ' s Ship Production

Committee recommended that a program be conducted to reduce the cost of

ship hull construction. NBS was requested by MarAd to propose such a program to the LNG subcommittee of the Welding Panel at a meeting in

Boulder in August. In mid-October, MarAd approved the initial phase of

NBS ' s recommended program, i.e., to survey the problem and the technology available for its solution. On the basis of this survey and as the result of a meeting of the Welding Panel in March, 1975, a coordinated program involving the LNG shipyards, the steel suppliers, and NBS was recommended to MarAd and to the Welding Panel. This' program was approved and work started in May 197 5. Cost-sharing contracts for the

evaluation of the improved steels were awarded in 1975 to the three

participating shipyards: Avondale Shipyards, Inc., Newport News Shipbuilding and Drydock Co. and General Dynamics-Quincy Shipbuilding Division.

A similar contract was signed with Lukens Steel Company to evaluate Cbtreated V-051 steel with and without sulfide shape control. The three participating shipyards completed the shipyard evaluation phase o^= the

program in the spring of 1977. The ABS steels with sulfide shape con- trol had excellent toughness and the HAZ toughness was imuroved, par- ticularly for shielded metal arc (SxMA) and gas metal arc \gma) welds.

17
Program and Results . During this reporting period, the evaluation of

ABS grade V-051 steel (Cb treated with and without sulfide shape (SSC)

control) was completed and contracts were awarded for further evaluation

of selected ship steels by the three participating shipyards.

The results of Lukens evaluation of V-051 (Cb, SSC) were particularly

encouraging. The 1-inch thick plates were welded using the 3-wire tandemarc submerged-arc process. One pass per side at 125 kJ/in was required

to fill the joint. The travel speed was 40 in/min. The test weldment

passed the USCG requirements at -40, -60 and -75 °F. Two complete Charpy

traverses were taken -- one with the notch on the root side and one with

the notch on the face side. Of the 108 Charpy tests only two individual

specimens fell below 20 ft lb and one of those was in the weld metal.

The normal sulfur plate of the same steel did not meet the USCG requirements at any of the temperatures; however, the degradation relative to the

base metal properties was minimal. These results suggest that the Cbtreatment may be having a significant beneficial effect. In 0.5 inch

thick plate of V-051 (Cb, SSC) , two passes per side were needed to meet

the USCG requirements.

The follow-on work with the three shipyards will consist of an evaluation

of the following steels:

Steel Type

V-062 (low sulfur)

V-062 (SSC)

V-062 (Cb-treated,

V-062 (Cb-treated,

V-051 (Cb-treated,

Thicknesses

low sulfur)

SSC)

SSC)

C-Mn-Mo-Cb (line pipe skelp)

1/2 and

1/2 and

1/2 and

1/2 and

1/2 and

1.2 inch

inch

inch

inch

inch

inch

Source

Armco/Avondale

Armco/Avondale

Armco

Armco

Lukens

Climax Molybdenum

Evaluation of the Cb-treated steels is considered essential for this program because of the promising results obtained by Lukens. These steels

will be sub-arc welded, one pass per side, using either single or multiple

arc techniques. In addition, one test plate from each steel will be

welded using the SMA process in the vertical position. The SMA welds are advisable in order to avoid low heat-input problems similar to those

encountered with A537 steel during the original shipyard evaluation.

Tests will be conducted at -60 and -75°F. Each shipyard will weld 24 test

plates and conduct complete Charpy traverses (15 specimens) on each test

plate. As in the original shipyard evaluation, a few additional tests

will be conducted as the need develops.

Problem Areas . None

Funding . July 1, 1977 to December 31, 1977.

Cost Center Cost to 12/31/77 Balance

2753430 180 K 0

.c- - - 2751430 65 K 15 K

2752430 58 K 22 K

Future Plans . Work should be completed on the follow-on testing program

(Phase II of the Ship Steel Improvement Program) in 1978.

18
1. Title . CUSTODY TRANSFER - LNG SHIPS

Principal Investigators . J. D. Siegwarth and R. S. Collier.

2. Cost Center Number . 2750460, 2751575, 2752575 and 2753575.

3. Sponsor Project Identification . tMaritime Administration, Misc. P.O.

#400-79005.

4. Introduction . In response to a request from the U.S. shipbuilding

industry, NBS is conducting an independent design review of the shipboard custody transfer systems under the sponsorship of the Maritime

Administration and in cooperation with the major U.S. shipbuilding

companies

.

5. Ob j ectives . The objectives of this program are to 1) Identify the

major technical areas relating to uncertainties in the measurement of

total mass and total heating value, 2) Estimate uncertainties in the

total mass and total heating value due to these identified factors,

3) Develop a proposed testing program for custody transfer system com- ponents, and 4) Investigate improved gauging techniques.

6. Background . Previous funding provided for the initial design review

of ships designated by MA Design LG8-S-102a MA Hulls 289, 290, 291.

The current funding provides for an extension of this program to include

ships of other designs which are being built by the major U.S. shipbuilding companies and also to verify tank survey and gauging methods

for LNG custody transfer.

7. Program . The LNG Aquarius ship tank ^4 was chosen to evaluate the

tank survey techniques and capacity tables for spherical tank LNG carriers;

this was done in cooperation with the General Dynamics Quincy Shipyards

Division. Work was started on the verification of tank calibration of

the three membrane type LNG ships under construction at Newport News and

the three ships being built at Avondale Shipyards using prismatic tanks.

Gage rods and tapes, which are used by NBS for independently verifying

coordinate distances, have been calibrated in the NBS Dimensional Metrology Labs. Gage rod distances were determined to v;ithin + 0.1 mm {3c

standard deviation)

.

For the spherical tanks, the target coordinate data was received from

the surveyor and used to analyze the tank shape factors. Capacity tables

were determined independently and compared with those provided by the

surveyor. A report of this evaluation is being prepared and will be

submitted to the Maritime Administration during the next report period.

For RF gaging research, data from the LNG Aquarius tank =4 was compared

with a scale model of that tank. The data for the resonance spectrum

is within the known uncertainty of the tank dimensions. This data is

shown in table 1. The first column shows the measured resonance spectum for the large tank; the second column shows the resonance spectrum

for the scale model; the third column shows the ratio of the corres- ponding frequencies which should equal the scale factor if the tank is

modeled perfectly; the fourth column is theoretical results for a perfect sphere with no center column, this is for mode I.D. only. Some

of the resonances split when the spherical symmetry is broken due to the

degeneracies of the sphere. These results verify the RF scaling laws

and have proven the utility of the RF technique for large tanks.

Other work on large land based cylindrical tanks have shown that these

results are independent of construction material.

19
Mode

Designation

Large Tank Frequencies

(Experimental

)

R = 18.288M

Scale Model Frequencies

(Experimental

)

r = 0.2429M

Scale Factor

c - r/R = Fn/fn

1 .328 x 10"'

Perfect Sphere

Theoretical

R = 18.288M

TM,i F, = 7.120 MHz fi = 540 MHz 1 .318 X 10"2 7.14 MHz

TM21 F2 = 10.145 MHz f2 = 764.9 MHz 1 .326 X 10"2 10.07 MHz

TEii

Split

F3 = 11 .525 MHz

F, = n .827 MHz

fs = 867.2 MHz

fu = 894 MHz

1.329 X 10"'

1 .323 X 10"2

11.691 MHz

TM31

Split

F5 = 13.10 MHz

Fg = 13.51 MHz

F7 = 14.69 MHz

fs = 987.4 MHz

fe = 1021 .3 MHz

fj = 1103.2 MHz

1.327 X 10'2

1 .323 X 10"2

1.332 X 10"2

12.94 MHz

TE21 Fe = 14.925 MHz fa = 1127 MHz 1 .324 X 10"2 14.99 MHz

TM,2 Fg = 15.838 MHz fg = 1193.5 MHz 1 .327 X 10"2 15.917 MHz

Resonance Spectrum Showing RF Scaling Law For A Sphere Containing A Cylindrical Column

Table 1

8. Problem Areas . None.

9. Funding . July 1 - December 31, 1977.

Funds Available $36.5 K

Balance Remaining $ 0.0 K

10. Future Work . The ship tank capacity table determinations for six El

Paso Marine LNG Co. ships are being reviewed. NBS will be monitoring

the calibration process and will do some independent tank volume calibrations, both to verify the present techniques and to develop improved

techniques

.

The feasibility will be determined for using the RF technique to determine shape changes in prismatic LNG tanks with extensive internal supporting structure. This will be done in cooperation with the Avondale

Shipyards.

20
1. Title . HEATING VALUE OF FLOWING LNG

Principal Investigators . J. A. Brennan.

2. Cost Center Number . 2756579

3. Sponsor Project Identification . Pipeline Research Committee (American

Gas Association) PR-50-48.

4. Introduction . This project will test instrumentation for making heating

value measurements on flowing LNG in actual applications. Information

from projects currently underway by Siegwarth (cost center 2757574) on densimeters, by Haynes and Hiza (cost center 2751574) on mixture

densities and by Parrish (cost center 2750575) on LNG sampling v/ill be

utilized where appropriate to provide state of the art information.

5. Objectives . The objective of this project is to measure total heating

value of LNG flowing in a pipeline by the integration of individual

measurements of flow, density and specific heating value. Flow measurement requires determination of flowmeter performance in line sizes

larger than presently available calibration facilities. Therefore, a secondary objective is to establish appropriate flowmeter scaling laws.

6. Background . The LNG flow facility at NBS was used to evaluate the re- sponse and the integration of the individual elements of the heating

value measurement. Different compositions of LNG were tested to provide

a range of densities and temperatures sufficient to determine any dependencies. Sampling work was combined with the sampling project ("cost

center 2750575) to better define the important criteria of this phase

of the measurement problem.

Flowmeter scaling work utilizes the cryogenic and water flow facilities

at NBS as well as private LNG peak shaving and import facilities.

7 . Program and Results . A. Tests at NBS.

LNG flow tests run at NBS in conjunction with the sampling project re- sulted in a marked decrease in the discrepancies described in the

last report. These discrepancies were between the heating values calculated from gas analysis and measured with the calorimeter. The differences were an indication that the sampling and/or the gas analysis

were not correct. Therefore, a correct density could not be calculated

to check the densitometer if a sampling error were involved.

Once the sampling-gas analysis problems were solved it was possible to

check the densitometer over an 11% density range with LNG. It was not

possible to accumulate large amounts of data but the data obtained tested

several parameters that could have affected densitometer performance.

One parameter, thermal cycling, had been shown to be a problem in

earlier tests but did not appear to be a problem during the last test.

The stabilizing effect of repeated thermal cycling that was observed in

the earlier liquid nitrogen tests did continue during the LNG tests.

All the measurement elements functioned properly during the LNG flow test

but the test was designed primarily to investigate the sampling problem.

Therefore, the amount and kind of data obtained v;as somewhat limited as far as the flow measurement station was concerned. Within those re- straints the test results were all good.

B. Tests at Transco.

All the test equipment, except the eight inch flowmeter, has been removed

from the Transco site. The flowmeter was left installed so that the LNG

line would not have to be opened up and also to allow the possibility of

future testing, if required.

21
A paper [1] describing some of the test results will be published in the

January 30, 1978 issue of The Oil and Gas Journal. Complete test results

have been reported to the PRC Supervisory Committee [2]

.

C. Tests at Southern Energy.

Water calibration of the 12 inch flowmeter test section was completed at

NBS Gaithersburg. The flowmeter performance was not as linear as the

eight inch flowmeter installed at Transco but was repeatable.

The test section has been installed at Southern Energy without the densitometer. The densitometer is a retractable model and will be installed

after a relief valve has been attached. It was also necessary to repair

some wiring in the densitometer before cryogenic testing could be completed. All this work should be completed in January 1978 and the densitometer installed at the test section.

8. Problem Areas . The problems described above have resulted in delays in

performing all the desired tests and in the delivery of equipment to

Southern. These delays should end in January 1978.

9. Funding . July 1 - December 31, 1977.

.25

$14K

$ IK.

10. Future Plans . Installation of the equipment required to run tests at

Southern Energy will be completed during the next reporting period. LNG

flow tests will be run when appropriate, consistent with the start-up

of the terminal.

References

1. J. A. Brennan, Better LNG flow measurement sought. Oil and Gas Journal

T6_, 168 (1978).

2. J. A. Brennan, C. H. Kneebone and J. E. Cruz, 1976-1977 Summary Report

to Pipeline Research Committee on Project PR-48-50, report to sponsor

(Dec. 1977).

Man-years expended

Total reporting period costs

Balance remaining

22
1. Title . LNG DENSITY REFERENCE SYSTEM

Principal Investigators . J. D. Siegwarth and J. F. LaBrecque

2. Cost Center Number . 2757574, 2750154

3. Sponsor Project Identification . American Gas Association, Inc.,

Project BR-50-10; National Bureau of Standards

4. Introduction . A density reference system has been developed to evaluate

the ability of commercially available instruments to measure densities

of LNG directly. Density is an essential measurement in determining the

total energy content of natural gas reservoirs. This effort is oriented

towards metrology, whereas the output from cost center 2751574 will provide basic reference data on pure liquids and mixtures to evaluate

methods for calculating the density indirectly.

5. Objectives . The objective of this research is to evaluate the density

measurement capability of commercially available meters. From the com- mercial meters we will attempt to select one or two capable of performance

as transfer standards, in order to provide traceability of accuracy to

field density measurement systems.

6. Background . The density reference system project was initiated in 1973.

Since that time the reference system has been designed, constructed, and

is now in operation, evaluating commercial density metering systems.

7. Program and Results . The report describing the density reference system

has been completed and printed. The report describing results of the

tests of four commercial densitmeters has been completed and has also

been printed. These two reports are:

Siegwarth, J. D. , Younglove, B. A. and LaBrecque, J. F., Cryogenic fluids

density reference system: provisional accuracy statement, Nat. Bur.

Stand. (U.S.) Tech. Note 698, 24 pages (1977), and

Siegwarth, J. D. , Younglove, B. A. and LaBrecque, J. F., An evaluation

of commercial densimeters for use in LNG, Nat. Bur. Stand. (U.S.) Tech.

Note 697, 43 pages (1977), respectively.

The density reference system is being prepared to test two additional

densimeters of the Archimedes type. These densimeters will be used in

the custody transfer of LNG.

8. Problem Areas . The DRS is performing in a satisfactory manner but the

sample container is too small and too inflexible to permit testing some other densimeters which we would like to test.

9. Funding . July 1 - December 31, 1977.

Man-years expended 0.1

Total reporting period cost 6 . 0K$

Balance remaining O.OKS

10. Future Plans . The DRS will be used to evaluate and calibrate transfer

standards. A transfer standard will be sent to Gaz de France, Paris

to intercompare our two calibration systems.

23
Title . LNG SAMPLING MEASUREMENT STUDY

Principal Investigators . W. R. Parrish, J. M. Arvidson and J. D. Siegwarth

Cost Center Number . 2750575 and 2755574.

Sponsor Project Identification . LNG Sampling Measurements Supervisory

Committee and A. G. A. -PRC LNG Supervisory Committee.

Introduction . Composition is used to determine both the heating value

and the quantity (through density) of LNG shipments. Thus, any error

in composition doubles when calculating the total heating value and

dollar value of a LNG tanker cargo. Compositions are determined by

sampling LNG, on either a batch or continuous basis, and analyzing the

vaporized mixture. Although several sampling techniques exist, none

have received widespread acceptance in the LNG industry. Also, a standard technique has not been established for analyzing the vaporized

sample

.

Objectives or Goals . The objectives of this work were to evaluate existing sampling techniques appropriate to LNG systems and to recommend the

most accurate analytical technique. Only sampling devices applicable

to pipelines were considered. The sampling techniques were judged on:

,.'5 a) representativeness of sample,

b) insensitivity of results to composition, temperature, pressure,

degree of liquid subcooling, flow rate and operator, aAd

c) simplicity.

Initial evaluations were made in a laboratory-scale apparatus; final

evaluation of the most promising sampling techniques was performed

in the LNG flow facility and aboard an LNG tanker.

Background . This work was performed because there is a need to

determine the best means for obtaining the composition of LNG shipments. Current LNG buying contracts include specifications on when and

how many liquid samples are to be taken but omit the sampling technique

to be used. The evaluation of sampling techniques by NBS is expected to

lead to the acceptance of the most accurate composition determination

method by all parties involved in LNG custody transfer.

Program and Results . A. LNG Flow Facility Tests.

The final set of sampling tests were made in the Flow Facility in August.

These tests showed that a sampling and analysis precision of + 0.15 percent (based on three standard deviations) in the computed heating value

was readily obtainable. Comparisons between computed heating values and

those measured using combustion calorimetry were well within the precision of the calorimeter.

The tests showed that:

1. steam and electrically heated sample vaporizers gave comparable

sampling precision,

2. using uninsulated sample lines produces unrepresentative samples

which are lean in nitrogen and methane, and

3. the sampling system should be at steady state conditions before

collecting samples.

24
B. Final Report.

A final report [1] detailing all of the LNG sampling work was written and

will be available in early 1978. .

8. Problem Areas . None.

9. Funding . July 1 - December 31, 1977.

Man-years expended .75

Total reporting period cost 53. K$

Balance remaining 0.0

10. Future Plans . The work under this cost center (2750575) is complete.

However, additional work is being supported by the Pipeline Research

Committee, A.G.A., to improve the sample vaporizer design (2755574).

References

1. W. R. Parrish, J. M. Arvidson and J. F. LaBrecque, Development and

evaluation of the LNG sar.pling measurement system (NBSIR, in preparation) .

25
1. Title . SURVEY OF CURRENT LITERATURE ON LNG AND METHANE

Principal Investigator . Neil A. Olien

2. Cost Center Nxjmber . 2759574

3. Sponsor Project Identification . American Gas Association, Inc.,

Project BR-50-10.

4. Introduction . It is important that all NBS personnel working in LNG, as well as the AGA and others, keep up with what is going on throughout the

world in the LNG field. This project is designed to provide the Current

Awareness and other information services to allow workers to keep

abreast of new research and other developments.

5. Objectives or Goals . We will publish and distribute each April, July,

October, and January a listing of all significant papers, reports, and

patents relating to methane and LNG properties and technology. The

references will be listed under convenient subject headings. The

Quarterly will be distributed to all interested AGA member companies and

be made available to the general public on a subscription basis. In

addition, LNG related information will be entered into the Cryogenic

Data Center's Information System for quick retrieval. A continuing

awareness of the current publication scene is maintained for any new periodicals to be reviewed cover-to-cover. Finally we will update and

make available comprehensive bibliographies on the properties and

technology of LNG. There are four bibliographies involved: methane

properties, methane mixtures properties, processes and equipment

involving methane and LNG, and patents relating to methane and LNG

technology. These four will be updated annually.

6. Background . In 1969 we made a thorough review of the world's publications to determine which periodicals and abstracting services should be

scanned cover-to-cover to adequately encompass the LNG field. The

result is that we now scan over 330 primary publications and nearly 25

secondary publications. Of these, approximately one-third are directly

related to LNG. In addition, we have increased our coverage of the

energy field to include hydrogen as a future fuel. Much of this

information is also pertinent to LNG and as such is listed in our LNG-related publications. Our Current Awareness Service has been

published weekly since 1964 (beginning in 1975 the publication became

biweekly) and the Liquefied Natural Gas Survey has been published

quarterly since 1970.

7. Program and Results . Four issues of the LNG Quarterly are prepared each

year and distributed. There are now 122 subscriptions going to AGA

Member Companies and 166 to other subscribers.

The four comprehensive bibliographies mentioned in section 5 have been

reviewed and shortened, and more selective bibliographies have resulted.

The latest versions were completed as of January 21, 1977.

B-152 5 THE THERMOPHYSICAL PROPERTIES OF METHANE AND DEUTERO-METHANE

IN THE SOLID, LIQUID AND GASEOUS PHASES - A SELECTED BIBLIOGRAPHY. Indexed by property, phase and author, 100 pages

(Jan 1977) . ($10.00) . B-1526 THE THERMOPHYSICAL PROPERTIES OF METHANE MIXTURES - A

SELECTED BIBLIOGRAPHY. Indexed by property, system and

author, 166 pages (Jan 1977). ($15.00).

B-1524 PROCESSES AND EQUIPMENT INVOLVING LIQUEFIED NATURAL GAS AND

METHANE - A SELECTED BIBLIOGRAPHY. Indexed by subject and

author, 285 pages (Jan 1977). ($25.00).

26
B-1527 PATENTS RELATING TO METHANE AND LNG TECHNOLOGY - A SELECTED

BIBLIOGRAPHY. Indexed by author, 150 pages (Jan 1977)

.

($15.00) . Over the past six years we have distributed over 500 copies of these

and the comprehensive bibliographies.

8. Problem Areas . None.

9. Funding . July 1 - December 31, 1977.

Labor 8.4K$

Other Costs 1 . 3K$

Total 9. 7K$

Remaining . 6K$

10. Future Plans . Issue 77-4 was delivered to the printer the first week

of January and should be distributed before the end of January. The

four bibliographies described above will be updated and made available

in early February.

27
1. Title . LIQUEFIED NATURAL GAS TECHNOLOGY TRANSFER

Principal Investigators . Douglas B. Mann and Dwain E. Diller

2. Cost Centers . 2750403, 2751403, 2752403, 2750570, 2754574, 2758574,

2750127, and 2750461.

3. Sponsor Project Identification . Maritime Administration, Miscellaneous

Purchase Order No. 400-79005; American Gas Association, Inc. Project

BR 50-10; American Bureau of Shipping letter dated 21 November 1975; and

NBS-Office of Standard Reference Data.

4. Introduction . The liquefied natural gas program at the Cryogenics

Division of NBS-IBS/Boulder represents an investment by industry and

government agencies of over $5 million over the past six years. This

investment was designed to develop reference quality properties data for

both fluids and materials and instrumentation and measurement technology

for the use of the LNG and related industries. Information developed

under this program must be transmitted to the ultimate user in a timely

and useful format. The classical publication methods of NBS most

certainly provide the scientist and research engineer information in a form most useful to the academic or near academic community. However,

as a result of extensive assessments of user requirements, it was found

that an additional effective mode for technology transfer would be an LNG Materials and Fluids User's Manual. A complete outline and planned

table of contents has appeared in previous semi-annual reports. The

Maritime Administration of the Department of Commerce and the American

Bureau of Shipping have agreed to sponsor the first year's efforts on the

materials section, and the American Gas Association, Inc. and the NBS Office of Standard Reference data have agreed to sponsor the section on fluids and fluid mixtures. The project was begun on April 1, 1976.

5. Objectives . The Liquefied Natural Gas Materials and Fluids User's Manual

will provide a method of rapid dissemination of property data and related

information for the effective generation, utilization and transportation

of LNG. The object is to improve technology transfer from the current

NBS Cryogenics Division LNG physical measurements program to the users,

including federal agencies, the states and industry. For the purpose of

this data book, liquefied natural gas is defined as a liquefied mixture

(at less than approximately 150 K) of hydrocarbons, predominantly methane,

with less than a total of 20% of the minor components ethane, propane,

iso and normal butane, and nitrogen as an inert contaminant. LNG materials

will be those associated with the liquefaction, transport and storage of

liquefied natural gas.

6. Background . The user's manual is only one of a number of information dissemination methods used to provide workers in the liquefied natural gas

(LNG) industry with properties data of known quality in a format consistent with the requirements of the intended user. In the case of the

LNG user's manual the intended audience is the field engineer, plant

manager, ship designer or process engineer interested in a ready reference

of assessed quality for data to be used in conceptual design, process

monitoring, process analysis, and intercomparisons where precision and

accuracy are secondary to specific problem solutions. The hierarchy of

accuracy and precision will be defined and traceable through references

to scientific and engineering literature.

Data is classified into three groups by the NBS Cryogenics Division.

Group 1 . Data which has been generated experimentally by NBS, or has been

assessed, evaluated or experimentally verified by NBS.

Group 2 . Data which has been assessed and evaluated by NBS.

28
Group 3 . Data available in the scientific engineering literature

through the NBS Cryogenic Data Center or elsewhere. No NBS evaluation

or assessment has been made at this date.

In general, most data included in the LNG user's manual will be from groups

1 and 2. Few new assessments or correlations are anticipated or required

for this work.

Data will be presented primarily in graphical form. Tables and analytical

expressions will be used only where absolutely necessary. Graphs and

charts will be in loose-leaf form for ease of updating and additions.

This form will also allow immediate implementation for data already

available under the NBS LNG program and will provide a convenient format

for the output of data from existing projects. The user's manual will not

be a substitute for traditional publications in the scientific literature

where measurement science, technique, precision and accuracy are paramount,

but will provide the data and references for the necessary assessment by

the user. The publication of both graphical and tabular data will be in a dual

system of physical units. These units will be the traditional LNG industry British System of BTU, pound, degree Fahrenheit and the SI system

of joule, kilogram and kelvin. It is the intent to give equal weight

to each system of units.

Nine structural metals have been selected with additions possible upon

consultation with the sponsors. Primary emphasis in the fluids section

will be on data for pure methane, pure nitrogen, and methane-nitrogen mixtures.

7. Program and Results . The first edition of the user's manual became

available for distribution in September. A complete description and

ordering information is included as part of this report. Of the original

750 first printing over 250 copies have been distributed to sponsors or sold directly.

Work on the first supplement to the user's manual is in progress. Ethane

thermophysical properties graphs are now being printed. Mixture thermophysical property graphs are nearly complete. Thermal insulation property graphs and materials specification t-ables are being prepared.

In addition to the tasks described above, the U.S. Maritime Administration

has asked NBS to assist with planning and coordination of an expanded

MarAd LNG research program in the areas of safety, economics and LNG

technology. A draft report "Maritime Administration LNG Research Program

Plan" identifying suggested program areas and describing suggested subprograms and projects has been prepared and submitted to the sponsor.

8. Problem Areas . None.

9. Funding . July 1 - December 31, 1977.

Labor - man-years expended 0.5

Funds expended 20.0K$

Balance remaining (first edition) 0.0K$

10. Future Plans . The first supplement, which will include additional

materials properties (thermal insulations and additional ferrous alloys)

and specifications, properties of ethane, additional binary mixtures data

and densities of commercial LNG compositions, will be available in 1978.

This supplement will be distributed to current holders of the first

edition on request.

The draft report "Maritime Administration LNG Research Program Plan"

will be revised and updated as appropriate.

29
LNG MATERIALS AND FLUIDS

A USER'S MANUAL OF PROPERTY DATA IN GRAPHIC FORMAT

The National Bureau of Standards Cryogenics Division is distributing a loose-leaf LNG Materials and

Fluids User's Manual. The User's Manual is designed to provide property data and related information for the effective generation, utilization and transport of LNG.

The total edition is planned to include: — pure fluids data on methane, nitrogen, ethane, propane and iso and normal butane, — fluid mixtures data involving methane with nitrogen, ethane, propane and iso and normal

butane, including commercial LNG compositions, — LNG materials data on structural metals and alloys, and — materials data on thermal insulations, joining compounds, structural composite materials and aggregates, polymeric materials, and miscellaneous non-structural materials.

The first edition and expandable binder contains 138 two-color (8Vi x 1 1-inch) charts and six wall charts (22 x 34-inch). This edition's property data are pressure-density-temperature, thermodynamic, transport and electromagnetic properties of pure methane and nitrogen; fluid mixtures of

methane with nitrogen; and, the elastic, thermal and mechanical properties of aluminum alloys

(3003, 5083 and 6061), stainless steels (304, 304L, 310 and 316), nickel steels (2.25, 3.5, 5 and 9%

nickel) and invar. The wall charts are of the thermodynamic properties enthalpy-entropy (H-S),

pressure-enthalpy (P-H) and temperature-entropy (T-S) for pure methane and pure nitrogen.

Both British and SI (International System) units are used throughout, easily discemable by printing

in separate colors.

^ The expandable binder allows for future supplements. Purchasers of the first edition will be noti- fied upon completion of addtitional supplements and their respective prices. All charts are printed on a high wet strength lithographic map paper designed for a strong durable life.

Copies of the first edition @ $35 each and additional rolled wall charts ^: $1 each may be obtained

by forwarding the order form below with payment. For additional information contact LNG

Materials and Fluids; National Bureau of Standards; Cryogenics Division; 325 Broadway; Boulder,

Colorado 80302.

ORDER FORM QUANTITY PRICE

First Edition LNG Materials and Fluids User's Manual

Additional Rolled 22 x 34 Charts: Nitrogen thermodynamic data Enthalpy-entropy wall chart (H-S)

Pressure-enthalpy wall chart (P-H)

Temperature-entropy wall chart (T-S)

Methane thermodynamic data Enthalpy-entropy wall chart (H-S)

Pressure-enthalpy wall chart (P-H)

Temperature-entropy wall chart (T-S)

C"' $35 ea.

(" $

(S $ ^ $

(& $

(1 $

(a $

I ea.

1 ea.

1 ea.

1 ea.

I ea.

1 ea.

Mail form and remittance to:

TOTAL

LNG Materials and Fluids; National Bureau of Standards; Cryogenics Division; 325 Broadway;

Boulder. Colorado 80302.

30
1. Title . omi JOINT SECRETARIAT ON LNG MEASUREMENTS

Principal Investigators . Douglas Mann and James A. Brennan.

2. Cost Center Number . 2750104

3. Sponsor Project Identification . American Gas Association, Inc.,

NBS-Office of International Standards; and NBS-Cryogenics Division.

4. Introduction . The liquefied natural gas program of the National Bureau

of Standards Cryogenics Division has, over the past five years, provided

the gas industry and interested Government agencies with properties data

on materials and fluids, instrumentation, and measurement assistance in

the support of commerce in this significant and growing segment of the

supplementary fossil energy supply. Support of this program by the

American Gas Association, Inc. and Federal Governm.ent agencies such as the Maritime Administration (MarAd) , NASA, GSA, Federal Power Commission

and the NBS-Office of Standard Reference Data has provided a basis for

the national acceptance of the results of the NBS LNG program. Through

the U.S. membership in the International Organization of Legal Metrology

there exists, at the present time, an opportunity to extend, interna-

. tionally, the utility of data and measurement practice developed under

our joint Government/industry program. We have been requested (by OIML

membership) to establish an LNG Measurement Secretariat within OIML which,

if implemented, would provide a significant international forum for the

results of our joint work. It is believed that a joint Secretariat with

the LNG industry would provide the most effective means of accomplishing

these objectives.

5. Objectives or Goals . Our objective is to accomplish the following goals

within the next three years.

a) To establish U.S. (NBS) thermophysical properties data for LNG as the standard data in international usage.

b) To establish U.S. (NBS) materials property data used in fabrication

and construction of LNG facilities (liquefiers, storage, transport) as the standard data in international usage.

c) To establish U.S. (NBS) approved measurement technology and

instrumentation as related to LNG (pressure, temperature, density, liquid

level, flow) as the standard in international LNG trade. The precedent

has been established with the successful completion of the joint NBS-CGA

cryogenic flow measurement program which has resulted in the adoption of

a cryogenic flow measurement code by the National Conference on Weights

and Measures. We wish to extend this code on an international basis.

d) To establish and maintain the leadership of U.S. science, engineering,

and industry in the research, technology, manufacture and marketing of

instruments and measurement systems for liquefied natural gas.

6. Background . OIML was founded in 1955 to promote intergovernmental

cooperation in the field of legal metrology which relates to the com- patibility of standards of measurement and the legislation and government

regulations which may affect such standards of measurement. OIML

recommends uniform international requirements for scientific and measurement instruments used in industry and commerce and works out model laws

and regulations for consideration by member nations; and, in addition,

serves as a center of documentation and information exchange in legal

metrology. At present 4 3 nations are members of this intergovernmental

organization

.

The United States joined OIML in 1972 (the Senate by resolution of

August 11, 1972 gave its advice and consent to the accession of the U.S.

to the convention establishing OIML) . The responsibility for managing

U.S. participation in OIML was assigned to the Department of Commerce

31
and has since been delegated by the Department to the National Bureau of

Standards (NBS) . Under the general guidance of the Department of State

and the Secretary of Commerce, NBS is directly responsible for formulating and implementing U.S. policy towards OIML. U. S. participation in

the organization is deemed important for two reasons: First, to protect

and enhance some $1 billion worth of scientific and measurement instruments

exported each year by U. S. firms and to insure equity in the trade of

commodities measured by these instruments; and second, to maintain the

U.S. as the world leader in the field of metrology.

In the spring of 1975 at a meeting in Paris of the International Committee

of Legal Metrology, the French and U.S. representatives discussed the

possibility of creating a new Reporting Secretariat No. 13 on "Liquefied

Natural Gas (LNG) Measurement". The U. S. representative, W. E. Andrus,

Jr. of NBS, agreed to explore the possibility with U. S. industry and

interested government agencies. These discussions resulted in a decision

to propose a joint Secretariat with the American Gas Association and

NBS-Cryogenics Division in order to best accomplish the tasks. These

conclusions were reached during several meetings extending through the

latter part of 1975 and early 1976.

Program and Results . Representatives of NBS met with PTB (West Germany)

and SIM (France) to discuss the proposed scope and to explore expansion

of the effort to include cryogenic fluids in general. Results of those

discussions indicate some resistance to including different physical

measurements (flow, density, etc. ) under a single recommendation for a specific group of fluids.

The proposed plan and scope were presented at the meeting of The Advisory

Committee for International Legal Metrology held at NBS-Boulder in September. The committee encouraged NBS to proceed with the present scope

and to continue to explore the possible inclusion of other cryogenic

fluids.

Problem Areas . None.

Funding . July 1 - December 31, 1978.

Labor - Man-years expended 0.1

Funds expended 11.0K$

Balance remaining 0.0K$

Future Plans . Two areas will continue to be explored. The first con- cerns expanding the scope of the LNG measurements to include other cryogenic fluids and thereby taking advantage of existing codes and standards

within the U.S. and Europe. Second, continued development of the scope

for LNG measurements to identify recommendations already available under

OIML and those which must be written separately.

32
1. Title . FEDERAL POWER COMMISSION CONSULTATION

Principal Investigators . D. B. Chelton, T. R. Strobridge and A, F.

Schmidt.

2. Cost Center Number . 2750404

3. Sponsor . Federal Power Commission - Bureau of Natural Gas -- letter

agreement dated 4 June 1973.

4. Goals . The Cryogenics Division has provided consultation and advisory

services to the Federal Power Commission on the cryogenic safety and

the design aspects of current applications before the FPC for authorization of LNG terminal and storage facilities. These services covered

properties of cryogenic environments, insulation systems, cryogenic

safety, thermodynamics, heat transfer, instrumentation, and cryogenic

processes such as refrigeration and liquefaction.

5. Background . Cost Center initiated July 7, 1973.

6. Program and Results . The status of those facilities under the

jurisdiction of the Federal Power Commission and subjected to our review are outlined in the following table (updated through December 31,

1977) . Elements of the facilities that were subject to review are the land-based

cryogenic storage tank components, bounded by the tanker or barge, the

inlet and distribution pipelines. These included, but were not limited

to the transfer lines, the storage tanks, the vaporizers and the process

piping as it interacts with the storage tanks. It was essential that

the reviews covered the operation, maintenance and emergency procedural

philosophies for each terminal. Based upon these studies, reports were

submitted to the staff of the FPC setting forth the technical evaluations

and conclusions on each proposal.

Emphasis was placed on the safety aspects of the facilities including

their possible interactions with the surrounding areas. The impact of

engineering design such as appropriate use of existing technology and

material selection for structural integrity were assessed. The basis

of review included various codes and standards, prior experience,

precedent and engineering knowledge. Vapor cloud generation and plume

dispersion was considered a subject beyond our area of expertise.

7 . Funding . FY 77 Allocation 70K$

Balance remaining 0K$

8. Future Plans . This cost center was terminated at the end of FY 1977 at

the discretion of the National Bureau of Standards. Further reviews

by the National Bureau of Standards will be negotiated as required.

33
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35
KBS-n4A (REV. 7-73)

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. l^UBl.ICATION OR RKPORT NO.

NBSIR 78-878

2. Gov't Accession

No.

3. Recipient's Accession No.

4. T1TLF-: AND SUBTITLE 5. Publication Date March 1978

LIQUEFIED NATURAL GAS RESEARCH AT THE NATIONAL

BUREAU OF STANDARDS

6. Performing Organization Code

275.

7. AUTHOR(S)

D. E. Diller, Editor

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OP COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 2750104

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

See block 16 below.

13. Type of Report & Period

Covered Semi'-Annual

July 1 -December 31 , 1977

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less factual summary ol most sigpiiicant information. If document includes a significant

bibliography or literature survey, mention it here.)

Twenty-nine cost centers, supported by seven other—agency sponsors in addition to

^BS, provide the basis for liquefied natural gas (LNG) research at NBS. During this

six-month reporting period the level of effort was over 20 man-years/year with funding

expenditures of over $500,000. This integrated progress report, to be issued in

January and July, is designed to:

1) provide all sponsoring agencies with a semi-annual report on the activities

of their individual programs;

2) inform all sponsoring agencies on related research being conducted at the

Cryogenics Division;

3) provide a uniform reporting procedure which should maintain and improve

communication while minimizing the time, effort and paperwork at the

cost center level

The contents of this report will augment the quarterly progress meetings of some sponsors, but will not necessarily replace such meetings. Distribution of this document is limited and intended primarily for the supporting agencies. Data or other

information must be considered preliminary, subject to change and unpublished, and

therefore not for citation in the open literature .

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons)

Cryogenics; liquefied natural gas; measurement; methane; properties; researcS^.j^

18. AVAILABILITY Unlimited

|X ! For Official Distribution. Do Not Release to NTIS

I I Order From Sup. of Doc, U.S. Government Printing Office Washington, D.C. 20402, SD Cat- No. CI3

I I Order From National Technical Information Service (NTIS)

Springfield, Virginia 22151

19. SECURITY CLASS

(THIS REPORT)

UNCL ASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF PAGES

22. Price

USCOMM-DC 29042-P74


I