ASTM E776-87(2009)
(Test Method)Standard Test Method for Forms of Chlorine in Refuse-Derived Fuel
Standard Test Method for Forms of Chlorine in Refuse-Derived Fuel
SIGNIFICANCE AND USE
The standard is available to producers and users of RDF for determining the content and forms of chlorine present in the fuel.
SCOPE
1.1 This test method covers the determination of the forms of chlorine in refuse-derived fuel-three (RDF): total chlorine, water-soluble chloride, and water-insoluble chlorine.
1.2 This test method may be applicable to any waste material from which a laboratory analysis sample can be prepared.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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. For specific precaution statements see Section 6 and 11.2.1.
FIG. 1 Graph From a Potentiometric Titration of Chloride
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: E776 − 87(Reapproved 2009)
Standard Test Method for
Forms of Chlorine in Refuse-Derived Fuel
This standard is issued under the fixed designation E776; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 3.1.1 refuse-derived fuels—solid forms of refuse-derived
fuels from which appropriate analytical samples may be
1.1 This test method covers the determination of the forms
prepared are defined as follows in ASTM STP 832:
of chlorine in refuse-derived fuel-three (RDF): total chlorine,
RDF-1—Wastes used as a fuel in as-discarded form with
water-soluble chloride, and water-insoluble chlorine.
only bulky wastes removed.
1.2 This test method may be applicable to any waste
RDF-2—Wastes processed to coarse particle size with or
material from which a laboratory analysis sample can be
without ferrous metal separation.
prepared.
RDF-3—Combustible waste fraction processed to particle
1.3 The values stated in SI units are to be regarded as sizes, 95 % passing 2-in. square screening.
RDF-4—Combustible waste fraction processed into powder
standard. No other units of measurement are included in this
standard. form, 95 % passing 10-mesh screening.
RDF-5—Combustible waste fraction densified (compressed)
1.4 This standard does not purport to address all of the
into the form of pellets, slugs, cubettes, or briquettes.
safety concerns, if any, associated with its use. It is the
3.1.2 total chlorine—all chlorine as determined in the
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- refuse-derived fuel.
bility of regulatory limitations prior to use. For specific
3.1.3 water-insoluble chlorine—water-insoluble chlorides
precaution statements see Section 6 and 11.2.1.
and chlorine in the refuse-derived fuel.
3.1.4 water-soluble chloride—those chlorides which are
2. Referenced Documents
water-solubilized by water extraction as determined in the
2.1 ASTM Standards:
refuse-derived fuel.
D1193 Specification for Reagent Water
E144 Practice for Safe Use of Oxygen Combustion Bombs
4. Summary of Test Method
E180 Practice for Determining the Precision of ASTM
4.1 The forms of chloride and chlorine are determined. The
Methods for Analysis and Testing of Industrial and Spe-
various procedures in the method convert the forms of chlorine
cialty Chemicals (Withdrawn 2009)
into a water-soluble chloride form that can be quantitated by
E287 Specification for Laboratory Glass Graduated Burets
titration.
E711 Test Method for Gross Calorific Value of Refuse-
4.1.1 Total Chlorine—The sample is combusted in an oxy-
Derived Fuel by the Bomb Calorimeter (Withdrawn
gen atmosphere. The chlorine is converted to chloride and
2011)
absorbed in an alkaline solution.
E829 Practice for Preparing Refuse-Derived Fuel (RDF)
4.1.2 Water-Soluble Chlorides—A portion of the analysis
Laboratory Samples for Analysis (Withdrawn 2002)
sample is successively extracted with hot chloride-free water.
4.1.3 Water-Insoluble Chlorine—Water-insoluble chlorine
3. Terminology
is calculated from the results of the total chlorine and the
3.1 Definitions of Terms Specific to This Standard:
water-soluble chloride determination where:
water 2 insoluble chlorine 5 total chlorine 2 water 2 soluble chlorides
This test method is under the jurisdiction of ASTM Committee D34 on Waste
(1)
Management and is the direct responsibility of Subcommittee D34.03 on Treatment,
Recovery and Reuse.
4.2 The chlorides contained in the alkaline solution (4.1.1)
Current edition approved July 1, 2009. Published August 2009. Originally
and the extraction solution (4.1.2) are determined by potentio-
approved in 1981. Last previous edition approved in 2004 as E 776 – 87 (2004).
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
metric (see Section 13) or modified Volhard titration (see
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Section 14).
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
3 4
The last approved version of this historical standard is referenced on Thesaurus on Resource Recovery Terminology, ASTM STP 832, ASTM, 1983,
www.astm.org. p. 72.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E776 − 87 (2009)
FIG. 1 Graph From a Potentiometric Titration of Chloride
5. Significance and Use excess of sulfide is easily removed by gently boiling the acid
solution for a few minutes. Sulfite can be eliminated in the
5.1 The standard is available to producers and users of RDF
same way.
fordeterminingthecontentandformsofchlorinepresentinthe
7.2.3 Cyanide is also precipitated by silver nitrate. It is
fuel.
usually determined separately by the Liebig-Deniges method
6. Precautions and a correction is applied to the results of the Volhard
titration.
6.1 Due to the origins of RDF in municipal waste, common
7.2.4 The Volhard method, as with the potentiometric
sense dictates that some precautions should be observed when
method, directly applied to a mixture of halides can determine
conducting tests on the samples. Recommended hygienic
only total halide content excluding fluoride. Preliminary treat-
practices include use of gloves when handling RDF; wearing
ment is necessary for the determination of chloride alone in a
dust masks (NIOSH-approved type), especially while milling
mixture.
RDF samples; conducting tests under negative pressure hood
when possible; and washing hands before eating or smoking.
8. Apparatus
7. Interferences
8.1 Balance, having a sensitivity of 0.1 mg.
7.1 Potentiometric Titration Method A:
8.2 Apparatus for Bomb Combustion of the Sample.
7.1.1 Iodide and bromide are also titrated as chloride.
8.2.1 Oxygen Bomb, similar to that used in the determina-
Ferricyanide causes high results and must be removed. Chro-
tion of the calorific value of refuse-derived fuels as described
mate and dichromate interfere and should be reduced to the
in Test Method E711.
chromic state or be removed. Ferric iron interferes if present in
8.2.2 Capsule, for holding the sample, approximately 25
an amount substantially higher than the amount of chloride.
mm in diameter at the top, approximately 12 mm deep, and
Chromic ions, ferrous ions, and phosphates do not interfere.
conforming to Test Method E711.
7.1.2 Grossly contaminated sample solutions usually re-
8.2.3 Firing Wire, as specified in Test Method E711.
quire pretreatment. Where contamination is minor, some con-
8.2.4 Firing Circuit, as specified in Test Method E711.
taminants can be destroyed simply by the addition of nitric
8.2.5 Metal Vessel, cylindrical, such that the bomb will be
acid.
fully immersed when approximately 2 L of water are added.
7.2 Volhard Titration Method B:
8.3 Magnetic Stirrer and Stirring Bars.
7.2.1 Compounds that have a strong oxidizing action inter-
8.4 Apparatus for Potentiometric Titration:
fere by reacting with thiocyanate. These compounds should be
reduced beforehand by treatment with ferrous sulfate or a
similar reducing agent.
Scott’s Standard Method of Chemical Analysis, edited by M. H. Furman, D.
7.2.2 Salts of mercury and palladium interfere by reacting
Van Nostrand Co., Inc., New York, NY.
with thiocyanate. They may be removed by precipitation with
Koltoff, I. M., and Stenger, V. A., Volumetric Analysis II, Interscience
hydrogen sulfide before the addition of silver nitrate. The Publishers, Inc., New York, NY.
E776 − 87 (2009)
8.4.1 Potentiometric Titration Assembly, using a silver indi- 9.13 Potassium Thiocyanate, Standard Solution (0.025
cator electrode and a calomel reference electrode containing a N)—Dissolve3gof potassium thiocyanate (KCNS) in freshly
saturated sodium nitrate solution as a bridge. distilled or boiled water, dilute to 1 L, and standardize against
0.025 N AgNO solution as directed in 14.1.2.
NOTE 1—All glassware and graduated apparatus should be Class A or
equivalent as described in Specification E287.
10. Sampling
9. Reagents
10.1 RDF products are frequently nonhomogeneous. For
9.1 Purity of Reagents—Reagent grade chemicals shall be this reason significant care should be exercised to obtain a
used in all tests. Unless otherwise indicated, it is intended that representative laboratory sample from the RDF lot to be
all reagents shall conform to the specifications of the Commit- characterized.
tee on Analytical Reagents of the American Chemical Society
10.2 The sampling method for this procedure should be
where such specifications are available. Other grades may be
based on agreement between the involved parties.
used, provided it is first ascertained that the reagent is of
10.3 The laboratory sample must be air-dried and the
sufficiently high purity to permit its use without lessening the
particle size reduced to pass a 0.5-mm screen as described in
accuracy of the determination.
Practice E829. This procedure must be performed carefully to
9.2 Purity of Water—Unless otherwise indicated, reference
preserve the sample’s representative characteristics (other than
to water shall be understood to mean at least Type III reagent
particle size) while preparing the analysis sample to be used in
water conforming to Specification D1193.
the procedures.
9.3 Potassium Hydroxide Solution (0.2 N)—Dissolve 13.2 g
PREPARATION OF CHLORINE SOLUTIONS FOR
of potassium hydroxide (KOH) in water and dilute to 1 L with
ANALYSIS
water.
9.4 Oxygen—The oxygen used for combustion shall be free
11. Total Chlorine (Oxygen Bomb Method)
of combustible matter. Oxygen manufactured from liquid air,
11.1 Preparation of Sample and Bomb (see Note 3):
guaranteed to be greater than 99.5 % pure, will meet this
11.1.1 Sample Weight—Weigh to the nearest 0.1 mg about 1
requirement.
g of thoroughly mixed air-dried analysis RDF sample into the
9.5 Sodium Chloride (NaCl)—Primary standard quality (pu-
bombcapsule.Apelletmaybemadefromtheair-driedanalysis
rity of 100 6 0.02 %).
RDF sample, accurately weighed, and placed into the bomb
9.6 Sodium Chloride, Primary Standard Solution (0.025
capsule. Place the capsule containing the sample into the
N)—Crush 10 to 20 g of primary standard sodium chloride capsule holder.
(NaCl) to 100-mesh fineness and dry in a glass container at
NOTE 2—There is a tendency for chlorine to adhere to the bomb walls,
120°C for 2 h. Stopper and keep desiccated. Dissolve 5.844 g
especially if the bomb is pitted or has been used previously to determine
6 0.1 mg of dried primary standard NaCl in water and dilute
high levels of chlorine. Unless the bomb is thoroughly cleaned before use,
to 1 L. Dilute 25.00 mL of this solution to 100.0 mL. the blanks may have values in excess of reality.
11.1.2 Firing Wire—Connect a length of firing wire to the
9.7 Methanol.
ignition terminals in such a manner that the loop of firing wire
9.8 Nitric Acid(1+1)—Mix equal volumes of concentrated
is in contact with the sample.
nitric acid (HNO , sp, gr, 1.42) and water.
11.1.3 Bomb Preparation—Add 20 to 25 mL of 0.02 N
9.9 Silver Nitrate, Standard Solution (0.025 N)—Dissolve
potassium hydroxide solution to the bomb and wet the entire
4.247 g of silver nitrate (AgNO ) in water and dilute to 1 L.
3 internal surface of the bomb with this solution (see Note 3).
Store in an amber glass bottle. Standardize against 0.025 N
Assemble the bomb.
sodium chloride solution as directed in 13.1.1 and 14.1.1.
NOTE 3—Sodium hydroxide solution at appropriate concentration may
9.10 Potassium Chromate – Potassium Dichromate
be used.
Indicator—(K CrO –K Cr O )—Dissolve 4.2gofK CrO
2 4 2 2 7 2 4
11.2 Addition of Oxygen—Admit oxygen to the bomb
and 0.7 g of K Cr O in 100 mL of water.
2 2 7
slowly to avoid blowing the sample from the capsule until a
9.11 Nitrobenzene. pressure of 25 atm is reached.
11.2.1 Warning—The following precautions are recom-
9.12 Ferric Ammonium Sulfate Indicator Solution—Add
mended for safe calorimeter operation. Additional precautions
sufficient concentrated HNO (sp gr 1.42) to a cold saturated
are given in Practice E144.
solution of ferric ammonium sulfate [FeNH (SO ) ·12H O] to
4 4 2 2
11.2.1.1 The weight of RDF sample and the pressure of the
remove the brown color.
oxygen admitted to the bomb must not exceed the bomb
manufacturer’s recommendations.
11.2.1.2 Bombpartsshouldbeinspectedcarefullyaftereach
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
use. Threads on the main closure should be checked frequently
listed by the American Chemical Society, see Annual Standards for Laboratory
for wear. Cracked or significantly worn parts should be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
replaced. The bomb should be returned to the manufacturer
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. occasionally for inspection and possibly proof firing.
E776 − 87 (2009)
NOTE 6—When high concentrations of chlorides are anticipated, dilute
11.2.1.3 The oxygen supply cylinder should be equipped
the cooled extraction solution to volume in a suitably sized volumetric
with an approved type of safety device, such as a reducing
flask and continue the analysis with a suitably sized aliquot.
valve, in addition to the needle valve and pressure gage used in
NOTE 7—If the chloride solution is highly colored or turbid the
regulating the oxygen feed to the bomb. Valves, gages, and
potentiometric method (Section 13) should be used. If theVolhard method
gaskets must meet industry safety codes. Suitable reducing
is to be used (Section 14), the color and turbidity must first be removed by
aluminum hydroxide [A1(OH) ] coagulation or by some other suitable
valves and adaptors for 300 to 500 psi (2070 to 3450 kPa) 3
method of turbidity or color removal without interfering with the chloride
discharge pressures are obtainable from commercial sources of
content of the solution.
compressedgasequipment.Thepressuregageshallbechecked
periodically for accuracy.
ALTERNATIVE PROCEDURES
11.2.1.4 During ignition of a sample, the operator must not
13. Potentiometric Titration (Method A)
permit any portion of his body to extend over the calorimeter.
13.1 Standardization of Reagents—Prepare a standard solu-
11.3 Preparation of the Chlorine Solution—Immerse the
tion of silver nitrate by adding 10.0 mL o
...
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