ASTM D5468-95
(Test Method)Standard Test Method for Gross Calorific and Ash Value of Waste Materials
Standard Test Method for Gross Calorific and Ash Value of Waste Materials
SCOPE
1.1 This test method covers the determination of the gross calorific value of waste materials by either an isoperibol, aneroid, air-jacketed isoperibol, or adiabatic bomb calorimeter using electronic temperature sensors, automatic calorimeter controllers, and subsequent analysis of the residue for ash. After calorific analysis, the bomb washings may be collected for subsequent elemental analysis.
1.2 The values stated in SI units are regarded as the standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 8.
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Designation: D 5468 – 95
Standard Test Method for
Gross Calorific and Ash Value of Waste Materials
This standard is issued under the fixed designation D 5468; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope expressed in this test method in joules per kilogram (J/kg).
Calorific value may also be expressed in calories per gram
1.1 This test method covers the determination of the gross
(cal/g) or in the British thermal units per pound (Btu/lb), when
calorific value of waste materials by either an isoperibol,
required. The unit equivalents are given in Table 1.
aneroid, air-jacketed isoperibol, or adiabatic bomb calorimeter
3.1.2 calorimeter—as used in this test method, is not only
using electronic temperature sensors, automatic calorimeter
the bomb and its contents, but it also includes the bucket,
controllers, and subsequent analysis of the residue for ash.
electronic temperature sensing devices, ignition leads, water,
After calorific analysis, the bomb washings may be collected
and stirrer when using water.
for subsequent elemental analysis.
3.1.2.1 adiabatic calorimeter—a calorimeter that has a
1.2 The values stated in SI units are regarded as the
jacket temperature adjusted to follow the calorimeter tempera-
standard.
ture as closely as possibly so as to maintain zero thermal head.
1.3 This standard does not purport to address all of the
3.1.2.2 calorimeter jacket—the insulating medium sur-
safety concerns, if any, associated with its use. It is the
rounding the calorimeter.
responsibility of the user of this standard to establish appro-
3.1.2.3 isoperibol calorimeter—the calorimeter has a jacket
priate safety and health practices and determine the applica-
of uniform and constant temperature.
bility of regulatory limitations prior to use. Specific hazard
3.1.3 gross calorific value (gross heat of combustion), Qv
statements are given in Section 8.
(gross)—the heat produced by combustion of unit quantity of
2. Referenced Documents
a solid or liquid fuel when burned at constant volume in an
oxygen bomb calorimeter under specified conditions with the
2.1 ASTM Standards:
resulting water condensed to a liquid.
D 121 Terminology of Coal and Coke
3.1.4 heat capacity—the quantity of heat required to raise a
D 240 Test Method for Heat of Combustion of Liquid
system one degree in temperature either at constant volume or
Hydrocarbon Fuels by Bomb Calorimeter
constant pressure.
D 1018 Test Method for Hydrogen in Petroleum Fractions
3.1.5 heat of formation—the increase in heat content result-
D 1193 Specification for Reagent Water
ing from the formation of 1 mole of a substance from its
D 3177 Test Method for Total Sulfur in the Analysis Sample
elements at constant pressure.
of Coal and Coke
3.1.6 net calorific value (net heat of combustion at constant
D 4239 Test Method for Sulfur in the Analysis Sample of
pressure), Qp—the heat produced by combustion of unit
Coal and Coke Using High Temperature Tube Furnace
quantity of a solid or liquid fuel when burned at a constant
Combustion Methods
pressure of 0.1 MPa (1 atm), under conditions such that all the
E 144 Practice for Safe Use of Oxygen Combustion
water in the products remain in the form of vapor.
Bombs
3.1.7 static calorimeter—a calorimeter without a thermo-
3. Terminology
stated jacket.
3.2 Definitions of Terms Specific to This Standard:
3.1 Definitions:
3.2.1 corrected temperature rise—the temperature of the
3.1.1 calorific value—the heat produced by combustion of a
calorimeter caused by the process that occurs inside the bomb,
unit quantity of a specimen under specified conditions. It is
which is, the observed temperature change corrected for
various effects.
This test method is under the jurisdiction of ASTM Committee D34 on Waste
3.2.2 heat capacity, energy equivalent, or water
Management and is the direct responsibility of Subcommittee D34.06 on Recovery
and Reuse. equivalent—the energy required to raise the temperature of the
Current edition approved March 15, 1995. Published May 1995. Originally
calorimeter one arbitrary unit. This is the quantity that, when
published as D 5468 – 93. Last previous edition D 5468 – 93.
multiplied by the corrected temperature, rises, then when
Annual Book of ASTM Standards, Vol 05.05.
adjusted for extraneous heat effects and divided by the mass of
Annual Book of ASTM Standards, Vol 05.01.
Annual Book of ASTM Standards, Vol 11.01.
the sample, gives the gross calorific value.
Annual Book of ASTM Standards, Vol 14.02.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 5468
TABLE 1 Calorific Value
at the same temperature as the calorimeter (adiabatic), or is
1 Btu = 1055.06 J 1 J/g = 0.430 Btu/lb monitored continuously for temperature changes (aneroid).
A
1 cal = 4.1868 J 1 J/g = 0.239 cal/g
6.6 Temperature Sensing Device—Thermometers such as
A
International tables calorie.
platinum resistance, thermistors, or mercurial thermometers are
satisfactory and may be used if properly calibrated.
4. Summary of Test Method
NOTE 1—Temperature is measured in either degrees Celsius, degrees
4.1 Calorific value is determined in this test method by
Fahrenheit, ohms, or other arbitrary units instead of degrees. Consistent
burning a weighed sample under controlled conditions, in
units must be used in standardization and the actual calorific value
determination.
oxygen, in a calibrated calorimeter. The calorimeter is stan-
dardized by burning a specified amount of benzoic acid. The
6.7 Sample Holder— An open crucible of platinum, quartz,
calorific value of the test specimen is computed from tempera-
or acceptable base-metal alloy. The base metal crucibles should
ture observations made before, during, and after combustion
be heat-treated for4hat 500°C to ensure the capsules are
and making proper allowances for heat contribution by other
completely oxidized.
processes.
6.8 Ignition Fuse— The ignition fuse shall be 100 mm of
4.2 After disassembly of the bomb, estimate the ash content
0.16-mm diameter or smaller (No. 34B&S gage), nickel-
by one of two of the following procedures:
chromium alloy (Chromel C) alloy, platinum, cotton thread, or
4.2.1 Dry the fuel capsule at 200°C for 5 to 10 min and
iron wire. The same length or mass of ignition fuse shall be
weigh to provide an estimation of the ash content of the waste
used for all calibrations and calorific value determinations.
material.
6.9 Firing Circuit— A 6 to 24-V alternating or direct current
4.2.2 Wipe any moisture from the exterior surface of the
is required for ignition purposes. A step-down transformer
capsule and weigh to provide an estimation of the ash content
connected to an alternating current lighting circuit, capacitors,
of the waste material.
or batteries may be used.
6.10 Buret—Used for the acid titration and shall have 0.1
5. Significance and Use
mL divisions.
5.1 This test method is used to compute the calorific value
6.11 Gelatin Capsules or Cellulose Tape—Used to mini-
and estimated ash content of the waste material represented by
mize vaporization of volatile samples. These items should be
the sample for incineration purposes or as fuel for cement
halogen free.
kilns.
6.12 pH Titrators or mV Meters—May be used for pH
5.2 The gross calorific and ash value may be used for
titration of wash solution.
evaluating the effectiveness of any beneficiation process.
7. Reagents
6. Apparatus and Facilities
7.1 Reagent Water— Conforming to conductivity require-
6.1 Test Room—A room or area free from drafts and that can
ments for Type II of Specification D 1193, it shall be used for
be kept at a constant temperature equal to 6 3°C, for all
preparation of reagents and washing of the bomb interior.
calorimetric tests. The apparatus shall be shielded from direct
7.2 Purity or Reagents—Reagent-grade chemicals conform-
sunlight and radiation from other sources. Thermostatic control
ing to the specifications of the Committee on Analytical
of room temperature and controlled relative humidity are
Reagents of the American Chemical Society shall be used in all
desirable.
tests.
6.2 Combustion Bomb— Constructed of materials that are
7.3 Benzoic Acid, Standard (C H —COOH)—Use pellets
6 5
not affected by the combustion process or products sufficiently
made from benzoic acid available from the National Institute of
to introduce measurable heat input or alteration of end prod-
Standards and Technology (NIST) or benzoic acid calibrated
ucts. The bomb shall be designed so that all liquid combustion
against NIST standard material. The value of heat of combus-
products can be completely recovered by washing the inner
tion of benzoic acid, for use in the calibrations calculations,
surfaces. There shall be no gas leakage. The bomb shall be
shall be in accordance with the certified value.
capable of withstanding a hydrostatic pressure test of 20 MPa
7.4 Methyl Orange, Methyl Red, or Methyl Purple
(3000 psig) at room temperature without stressing any part
Indicator—May be used to titrate the acid formed during
beyond its elastic limit.
combustion. The indicator used shall be the same for both
6.3 Balance—A laboratory balance having the capability to
calibration and calorific value determinations.
weight the sample to the nearest 0.0001 g. The balance shall be
7.5 Oxygen—Shall be free of combustible matter. Only
checked for accuracy at the beginning of each week that the
oxygen manufactured from liquid air, guaranteed to be greater
calorimeter tests will be made.
than 99.5 % pure, shall be used. Oxygen made by the electro-
6.4 Calorimeter Vessel (Bucket)—Made of metal with a
lytic process may contain a small amount of hydrogen,
tarnish-resistant coating, with all outer surfaces highly pol-
ished. For calorimeters having a bucket it may be a separate
component or integral component of the bomb. It shall be of
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
such construction that the environment of the calorimeter’s
listed by the American Chemical Society, see Analar Standards for Laboratory
entire outer boundaries is maintained at a uniform temperature.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.5 Jacket—An insulated container that keeps the inner
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
perimeter of the jacket at constant temperature (isoperibol), or MD.
D 5468
rendering it unfit without purification by passage over copper 10.2 Determine heat capacity as the average of a minimum
oxide at 500°C. of 6 individual runs made over a period of not less than 3 days
7.6 Standard Solution—Sodium carbonate (Na CO)or nor more than 5 days. To be acceptable for highprecision work,
2 3
other suitable standard solution. Dissolve 3.76 g of sodium the relative standard deviation of the series shall be 0.15 % or
carbonate that has been dried for 24 h at 105°C in water and less. See Table 2. For users of static-type calorimeters, an
dilute to 1 L. One millilitre of this solution is equivalent to 4.2 acceptable relative standard deviation would be 0.40 % or less.
J (1.0 cal) in the acid titration when the entire rinse solution is For this purpose, any individual test may be discarded only if
used as the analytical sample. Alternatively, the titrant volume there is evidence of incomplete combustion. If this limit is not
is to be corrected by the volume fraction of the rinse that is met, the entire series shall be repeated until a series is obtained
used as the analytical sample. (See 10.4.2.) with a relative standard deviation below the acceptable limit.
10.3 Procedure:
8. Hazards
10.3.1 Control the mass of the pellets of benzoic acid in
8.1 The following precautions are recommended for safe
each calibration series to obtain the same temperature rise as
calorimeter operation. Additional precautions are given in
obtained with the waste specimen tested in the same laboratory.
Practice E 144. Also consult the calorimeter equipment manu-
Weigh the pellet during the same test day and to the nearest
facturer’s installation and operating instructions before using
0.0001 g in the sample holder in which it is to be burned, and
the calorimeter.
record the weight.
8.2 The mass of waste sample and the pressure of the
10.3.2 Rinse the bomb with water to lubricate internal seals
oxygen admitted to the bomb must not exceed the bomb
and dry surfaces. Add approximately 1 mL of water or desired
manufacturer’s recommendations.
amount of other appropriate solution (see Note 2) to the bomb
8.3 Inspect the bomb parts carefully after each use. When
prior to assembly for a test.
halogenated organic compounds are being tested, replace all
NOTE 2—If the washing will be used for elemental analysis, then add 5
O-rings and valve seats after 100 firings. If no halogenated
mL of a 10 % sodium carbonate solution or other solution of desired
organic compounds are being tested, replace all O-rings and
amount rather than 1 mL of water to the bomb prior to assembly for both
valve seats after 500 firings. At least every 3000 firings, check
standardization and analysis procedures.
the bomb for thread wear on any closures or return to the
10.3.3 Connect a measured fuse to the ignition terminals, in
manufacturer for these tests. These are recommendations for
accordance with the manufacturer’s guidelines. (See 6.8.)
worst case situations. For more details, contact the manufac-
10.3.4 Assemble the bomb and charge it with oxygen to a
turer.
consistent pressure of 3 MPa (30 atm). Lower charging
8.4 Equip oxygen supply cylinder with an approved type of
pressures may be used if they will not result in incomplete
safety device, such as a reducing valve, in addition to the
combustion as evident by visual inspection for carbon residues
needle valve and pressure gage used in regulating the oxygen
or the formation of carbon monoxide rather than carbon
feed to the bomb. Valves, gages, and gaskets must meet
dioxide. This pressure must remain the same for each calibra-
industry safety codes. Suitable reducing valves and adapters
tion and each calorific value determination. Admit the oxygen
for 3 to 4-MPa (300 to 500-psi) discharge pressure are
slowly into the bomb so as not to blow powdered material from
obtainable from commercial sources of compressed gas equip-
the sample holder. If the pressure exceeds the specified
ment. Check the pressure gag
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