8.

Calorimeters
P. FOUNDOS (1982) G. LIPTK (1995) D. LEWKO
(2003)

AT I

AIE

Heat Value

Flow Sheet Symbol

Type of Designs:

A. Direct measurement by burning of fuel gas B. Inferential by calculation from composition and physical analysis, including chromatography (Section 8.12), mass spectrometry (Section 8.29), etc. C. Special designs such as reaction calorimeters of Mettler-Toledo, designs for the measurement of partial molar heat capacities of biopolymers by CSC, and total absorption calorimeters made by Opal 1. 2. 3. 4. 5. Custody transfer Process monitoring and control Blending and mixing of fuel gases Gas and liqueed natural gas (LNG) processing Compliance recording

Applications:

Operation:

a. Continuous b. Cyclic c. Portable (1) Controlled environment (2) Varying ambient (3) High speed of response (4) Inaccuracy 0.5% of full scale or better (5) Inaccuracy 1.0% of full scale or better (6) Inaccuracy 2.0% of full scale or better (a) General purpose (b) Explosion-proof Under $10,000 [A, 2/3, a, (3)/(5)/(6)] $10,000 to $15,000 [A, 2, a, (3)/(5)/(6), (b)] $15,000 to $30,000 [A/B, 2/3, a/b, (1)/(2)/(4), (a)/(b)] Ametek Process & Analytical Instruments (www.thermox.com) Cosa Instrument Corp. (www.cosa-instrument.com) Daniel Measurement and Control (www.danielind.com) Delta Instrument LLC (www.deltainstrument.com) EG & G Chandler Engineering/Ranarex (www.chandlerengineering.com) Galvanic Applied Sciences (www.galvanic.ab.ca)

Performance:

Area Classication:

Cost:

Partial List of Suppliers:

INTRODUCTION This section does not discuss the special calorimeter designs such as reaction calorimeters (Mettler-Toledo), designs for the measurement of partial molar heat capacities of biopolymers

(CSC), or total absorption calorimeters (Opal), but only directs the reader to the web pages of their respective suppliers. Inferential calorimeters, which determine the heat content by calculation from composition and physical analysis, including chromatography (Section 8.12) and mass spectrometry 1235

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Analytical Instrumentation

(Section 8.29), are not covered in detail either, because they are discussed in the above-noted sections. Calorimeters are analyzers that measure the heat value or energy content of gaseous fuels. There are two broad categories of this type of instrument: those that can be considered true calorimeters, because they are actually burning the gas and directly measuring its heating value, and inferential calorimeters, which analyze the composition of the gas or measure a physical parameter to determine the heating value.

Net Caloric Value This the measurement of the actual available energy per unit volume at standard conditions, which is always less than the gross caloric value by an amount equal to the latent heat of vaporization of the water formed during combustion.

Wobbe Index American Gas Association (AGA) 4A denes the Wobbe Index as a numerical value that is calculated by dividing the square root of the relative density (a key ow orice parameter) into the heat content (or BTU/SCF) of the gas. Mathematically, the Wobbe Index is dened by Equation 8.8(2): calorific value specific gravity

TERMINOLOGY Basic terms and denitions used in gas calorimetry are given here and may also be found in the references listed at the end of this section. A summary of the measurement calibration techniques is outlined in Table 8.8a.

Wobbe index =

8.8(2)

British Thermal Unit A British thermal unit (BTU) is the amount of heat required to raise the temperature of 1 lb of water by 1F at or near 60F. The Wobbe Index accounts for composition variations in terms of their effect on the heat value and specic gravity, which affect the ow rate through an orice. In essence, the Wobbe Index is a measurement of the available potential heat, and it can be used in conjunction with the gas ow measurement to produce a measurement of heat ow rate (see Section 2.5). In the following paragraphs, some basic terms and gas calorimeter design variations are described. The American Society for Testing Materials (ASTM) Standards listed in the references serve to compliment this information.

BTU Dry This is the heating value that is expressed on a dry basis. The common assumption is that pipeline gas contains 7 lb (or less) of water vapor per million standard cubic feet (SCF).

BTU Saturated This is the heating value that is expressed on the basis that the gas is saturated with water vapors. This state is dened as the condition when the gas contains the maximum amount of water vapors without condensation, when it is at base pressure and 60F. UNITS, ACCURACY, AND OUTPUT SIGNALS When calorimeters are used for custody transfer of natural gas, the unit of measurement is often the BTU. The Natural Gas Policy Act of 1978 (15USC 3311, Supplement 1981) established the BTU as the basic measurement of natural gas for pricing purposes, supplanting the traditional volume bases measurement. As a result, the market demand for custody transfer type calorimeters increased markedly. In Europe and in other countries where the metric system is used, natural gas calorimeters are calibrated in mega-Joule units. The response time can be a critical consideration in selecting the right analyzer for closed-loop control applications. On the other hand, for custody transfer applications, one should maximize accuracy even at the expense of response time, while improved response time even at the expense of accuracy is justied in some critical process control applications. The analog output of the analyzer may represent the gross caloric value (sometimes referred to as upper heating value or gross heating value), the net caloric value (sometimes referred to as lower heating value or net heating value), or the Wobbe Index.

Combustion Air Requirement Index The combustion air requirement index (CARI), a dimensionless number, indicates the amount of air required (stoichiometrically) to support the combustion of a fuel gas. Mathematically, the CARI is dened by Equation 8.8(1): CARI = Gross Caloric Value This is the heat value of energy per unit volume at standard conditions, expressed in terms of BTU per SCF, kilocalorie 3 per cubic Newton meters (Kcal/N.m ), or other equivalent units. Air/Fuel Ratio s.g. 8.8(1)

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TABLE 8.8a Summary of Calorimeter Features and Specications

Type Area Class Continuously Inferential Application
a

Operation Standard Sample Local Readout Ambient Limits F (C)

Performance Speed of Response (90%) 3 min 15 min 10 min N/A 8 sec 10 min 3.5 min N/A 4.5 min 55 sec

Type

GROSS CALORIFIC VALUE Water T Air T Gas Chromatograph Adiabatic Flame Temperature NET CALORIFIC VALUE Airow Calorimeter Gas Chromatograph Expansion Tube Calorimeter Specic Gravity Process Chromatograph Thermopile Calorimeter WOBBE INDEX Airow Calorimeter Gas Chromatograph Expansion Tube Calorimeter Thermopile Calorimeter
a

7277 (2225) 7277 (2225) 0100 (1838) N/A

1303300 1203600 Any N/A

5090 (1032) 0128 (1853) N/A 0128 (1853) 6090 (1632) N/A

1303300 Any 1203300 Varies 1503600 1503300

Accuracy % of Full Scale 0.5 0.5 0.5 0.5 1.0 0.5 1.0 2.0 2.0 2.0

Range in Btu Full Scale

Remote Transmitters

Ex-Proof

General Purpose

Directt

Empirical Calibration

Cyclic

8.8 Calorimeters

50110 (1043) 0120 (1849) N/A N/A

1303300 Any 1203300 1503300

0.75 0.5 1.0 2.0

8 sec 10 min 3.5 min 55 sec

See feature summary at begining of section.

1237

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Analytical Instrumentation

Water Overflow

Non-Condensible Gas Vent

Water Outlet Thermistor

Combustion Chamber Shell Water Pressure Regulator Water Capillary Water Inlet
Sol V

Calibration Heater Ignition Electrode Insulation Jacket Water Inlet Thermistor

Sol V

Calibration Heater Controller Mixed Gas Tube Gas Capillary

Gas Pressure Regulator Gas Inlet

Sol V

Water Heater Gas Capillary

Sol V

Sol V

Sol V

Oxygen Pressure Regulator Oxygen Oxygen Heater Gas Heater

FIG. 8.8b 1 Water-temperature-rise-type calorimeter provided with electric heater for direct calibration.

DESIGN VARIATIONS In the following paragraphs, a brief description is given of the various gas calorimeter designs that are used to detect the heating value of gaseous fuels and waste gases.

burned, the amount of electric heat introduced matches the heating value of the gas. This type of calibration can be made at any time and for any reading of the calorimeter.

Air-Temperature-Rise Calorimeter Water-Temperature-Rise Calorimeter One variation of this design is illustrated in Figure 8.8b. Here a constant (capillary-controlled) ow rate of the gas is mixed with a constant ow rate of oxygen (or air) and is burned. The resulting heat of combustion is removed by a constant ow rate of water. Both the ow rates and the temperatures of the entering streams are controlled at a constant value. Thermistors measure the temperature of the water entering and leaving. The temperature difference or temperature rise is therefore a direct measure of the heating value of the burned gas. This calorimeter can be compensated for the variations in barometric pressure and can therefore measure the gross caloric value of fuel or waste gases. Figure 8.8b also shows a calibration heater. During the calibration cycle this electrical resistance heater is turned on while the gas ow is off. Thereby a known accurately determined amount of heat is introduced and the corresponding temperature rise on the water side is measured. When the temperature rise is the same as it was when gas was being The measurement is accomplished by continuously transferring all the combustion heat of a metered quantity of gas to a metered quantity of air (see Figure 8.8c). The temperature rise of the air is measured and is related directly to gross caloric value of the gas. The unit can be modied so that the heat-absorbing air is not separated from the products of combustion, thus resulting in a more accurate measurement of the net caloric value.

Airow Calorimeter In this design the variations in the heat released by the continuous burning of the fuel gas are offset by a continuous, varying airow that maintains the temperature of the products of combustion constant (see Figure 8.8d). Thus, the airow is correlated to the heat value of gas or to the Wobbe Index. With the addition of a constant-volume gas-metering pump, and compensating for specic gravity variations, the instrument can be calibrated for the net caloric value.

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8.8 Calorimeters

1239

Pressure Regulator

Gauge Location

Inlet Orifice Sight Plug Inlet Bleeder Burner Flame Orifice

Secondary Air Orifice Cap Piping Metered Primary Gas Art Orifice Cap Gas Meter Overflow Weir Drainpipe Gas and Primary Air Drain Manifolds

(9) Outgoing Air Thermometer Main Burner Flame Heat Exchanger (A) Incoming Air Thermometer Heat Absorbing Air Outlet Connector Heat Absorbing Air Tank Water Level

Combustion Air Combustion Air Meter Meter Orifice Combustion Air Overflow Weir

Bleeder Gas Gas Vent to Outside Thermocouple Tube

Safety Shut-Off Valve

Heat Absorbing Air Meter Burner Water Seal Water Pump Auxiliary Tank Supply

Secondary Air

Condensate Pan

Products of Combustion

FIG. 8.8c Air T calorimeter.

Ambient Compensating Tubes

Thermal Expansion Element Mixing Baffle Flapper/ Nozzle Air Orifice Products of Combustion Heat Exchange Air

Burner Gas Orifice Wobre Index = cv

2g

Air Control Valve Combustion Air Adjustment Safety Shutdown Solenoid Gas Precision Gas Regulator

Air Supply

D/P Transmitter M

Gas Calorific Value-CV

FIG. 8.8d Airow calorimeter.

Residual Oxygen Calorimeter In this design, a continuous gas sample is mixed with dry air at a precisely maintained ratio. The ratio is dependent on the BTU range of the gas to be measured. The fuelair mixture

is oxidized in a combustion furnace, and the oxygen concentration in the spent sample is measured using a zirconia oxide cell. With the addition of a precision specic gravity cell, the analyzer can be calibrated to provide a measurement corresponding to the caloric value of the gas.

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Analytical Instrumentation

Air Breather

derivative of the ame temperature composition that allows calibration for gross caloric value. Thermopile Calorimeter

Precision Oil-Sealed Bell-Regulator

Air Flow

First Regulator

Pressure Set at 1 Inch (25 mm) H2O Sample Flowing to Expansion Tube Calorimeter Burner

The thermopile calorimeter measures the temperature of the hot products of combustion mixed with a constant volume of air supplied by a fan. The sample to the burner is provided with an orice bypass, which is needed for specic gravity compensation; thus, the resulting measurement is in terms of net caloric value. To measure the Wobbe Index, the bleed is blocked and the sample goes through the burner.

APPLICATIONS There are ve general areas of application:

Sample Inlet

Pressure Approx. Atmospheric Air Breather

FIG. 8.8e Precision regulator used for expansion tube-type calorimeter. (Courtesy of Cosa Instrument Corp.)

Chromatographic Calorimeter A conventional chromatograph can also be used to analyze gas composition (see Section 8.12), and a microprocessor can be used to calculate the heating value and specic gravity of the gas from empirical data held in memory by the microprocessor. This information can be used to calibrate for the gross or net caloric value of the Wobbe Index. Expansion Tube Calorimeter In this design, the gas sample is delivered through a precision regulator system (Figure 8.8e), which is independent of specic gravity and atmospheric pressure. The gas is burned at the base of a differential expansion tube unit that responds to the temperature of the products of combustion and excess air. The differential signal is calibrated as the net caloric value. Modication of the regulator to respond to specic gravity changes allows calibration to the Wobbe Index. Adiabatic Flame Temperature The gross caloric value of fuel gas is proportionate to the ratio of air to a fuel that maximizes the adiabatic ame temperature of the mixture. Therefore, in this design, ows are controlled and two burners are used to obtain the mathematical

1. Custody transfer: Sale or purchase of fuel gas with accuracy being the primary consideration. 2. Process monitoring and control: To effect on-line manual or automatic control of process or efcient burning of the gas by using heat value measurement as one of the measured variables. Such applications include feed-forward control of fuel gas-red heaters or boilers, stove-ring control, vaporizer control, and synthetic natural gas (SNG) reactor control. In these applications, measurement of heat value is important as a process measurement for efcient control of energy consumption, or to limit the ow of heat to an energysensitive process. This application requires high speed of responses as well as reliability to achieve effective control. 3. Blending and mixing of fuel gas: To obtain a uniform quality gas or to utilize waste or by-product gases by blending them into the main fuel gas. Blending is often used to achieve a desired ratio of streams such as propane/air or blast furnace gas/coke oven gas. However, when by-product or waste gases are to be injected into a stream and they vary signicantly in quantity, monitoring of the mixture is necessary to make proper use of the fuel. Speed of response and reliability are essential. 4. Processing of gas and liqueed natural gas (LNG) operations: LNG must be vaporized and conditioned for efcient consumption. Coke oven and blast furnace gases are the main fuels used by the steel industry, and renery gas is a major by-product that is used in petroleum rening. All these fuel gases are produced in specic processing operations that require monitoring and conditioning for efcient use. 5. Compliance recording: For government-regulated energy transfer by pipeline and utility distributors to the consumers. Accuracy and traceability are essential criteria.

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8.8 Calorimeters

1241

SAMPLE CONDITIONING The requirements for the sample conditioning system are dependent on the limitations of the selected analyzer and the minimum, normal, and maximum limits of the process stream being monitored. In many industrial applications, fuel gases are generated as by-products of other processes, and these off-gases can be extremely dirty and require sample conditioning. In some cases, special consideration must be given to the dew point of the off-gas when designing the sample conditioning system. Refer to Sections 8.2 and 8.3 for sample system options and design features.

CONCLUSION Gaseous fuel energy is a costly commodity that is being consumed with much more care and efciency than in the past. The key to its efcient consumption is measuring the available heat of the fuel gas. There are several calorimeters available for reliable on-line measurement of gas heating values. For closed-loop control applications, the designs that provide a speed of response of less than a minute (Table 8.8a) are preferred. In addition, there are several manufacturers that offer calorimeters specically for custody transfer applications. These analyzers offer improved accuracy at the expense of response time (Table 8.8a).

Reference
1. Christopher, D. E., Direct Energy Measurement, Measurements and Control, December 1991.

Bibliography
AGA, Report 3. AGA, Report 8. AGA Gas Measurement Manual, Section 11A.2, Determination of Heating Value of Gas, p. 11A2.1. Armstrong, G. T., Standard Combustion Data for the Fuel Gas Industry, AGA, 1972.

ASTM Standard D 900-55(70), Caloric Value of Gaseous Fuels by the Water Flow Calorimeter, Philadelphia: American Society for Testing and Materials, 1970. ASTM Standard D 1826-77, Test for Caloric Value of Gases in Natural Gas Range by Continuous Recording Calorimeter, Philadelphia: American Society for Testing and Materials, 1977. ASTM D 1945, Analysis of Natural Gas by Gas Chromatography, Philadelphia: American Society for Testing and Materials. Bowles, E. B., Small Errors in BTU Measurement Can Add Up to Large Losses in Revenue, Pipe Line & Gas Industry, November 2000. Broadwater, S. R., Columbia Gas Moves toward Heating-Value Measurement, Oil and Gas Journal, August 25, 1980. Christopher, D. E., Direct Energy Measurement, Measurement and Control, December 1991. Distribution Conference 72-D-76, American Gas Association, Arlington, VA, 1972. Foundos, A. P., Measuring Heat Release Rate from Fuel Gases, Instrumentation Technology, Instrument Society of America, 1977. GPA, Calculations of Gross Heating Value, Relative Density and Compressability Factor for Natural Gas Mistures from Compositional Analysis. GPA, Standard 2145-Table of Physical Constants for Hydrocarbons and Other Compounds of Interest to the Natural Gas Industry. GPA Reference Bulletin, Heating Value as a Basis for Custody Transfer of Natural Gas, 1984. Green, D. and Perry, R. H., Perrys Chemical Engineers Handbook, 6th ed., New York: McGraw-Hill, 1984. Hawkins, J. and McGowan, A., Theoretical Introduction to the Use of a Residual Oxygen Measurement Method for the Analysis of Combustion Air Index (CARI) and the Wobbe Index of Fuels, ISA Chicago, October 2002. Kizer, P., Natural Gas Energy Determination Review, ISA Proceedings, 1991. Kizer, P., Energy Measurement Using On-Line Chromatography, in 71st International School of Hydrocarbon Measurement, 1996. Kizer, P., Operation of On-Line Gas Chromatographs, in American School of Gas Measurement, 1998. Lange, N. A. and Forker, G. M., Handbook of Chemistry, 10th ed., New York: McGraw-Hill, 1967, pp. 842843, and Columbia Gas System Data. Larson, B., Heating Value Technologies for 2001, in Winnipeg CGA Gas Measurement School, June 5, 2001. Lide, D. R., Handbook of Chemistry and Physics, 71st ed., 19901991. McCoy, R., BTU Determination by Process Chromatograph, Applied Automation, Inc., a subsidiary of Phillips Petroleum. Melrose, D. C., Comparison of Calculated and Measured Heating Value of Natural Gas, presented at AGA Distribution Conference 72-D-2, American Gas Association, Arlington, VA, 1972. Pannill, W. and Sharples, R. J., Calculation of Gas Heating Value Is Complicated by the Courts, Oil & Gas Journal, July 2, 1984.

2003 by Bla Liptk