EPA-670/2-73-053-h
August 1973
Environmental Protection Technology Series
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY OR
DISPOSAL OF HAZARDOUS WASTE
Volume VIII Miscellaneous Organic and Inorganic Compounds
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
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EPA-670/2-73-053-h
August 1973
RECOMMENDED METHODS OF
REDUCTION, NEUTRALIZATION, RECOVERY
OR DISPOSAL OF HAZARDOUS WASTE
Volume VIII. National Disposal Site Candidate
Waste Stream Constituent Profile Reports -
Miscellaneous Inorganic and Organic Compounds
By
R. S. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
6. I. Gruber, M. J. Santy, and C. C. Shih
TRW Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-03-0089
Program Element No. 1D2311
Project Officers
Norbert B. Schomaker
Henry Johnson
Solid and Hazardous Waste Research Laboratory
National Environmental Research Center
Cincinnati, Ohio 45268
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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REVIEW NOTICE
The Solid Waste Research Laboratory of the National Environmental
Research Center - Cincinnati, U.S. Environmental Protection Agency has
reviewed this report and approved its publication. Approval does not
signify that the contents necessarily reflect the views and policies of
this Laboratory or of the U.S. Environmental Protection Agency, nor does
mention of trade names of commercial products constitute endorsement or
recommendation for use.
The text of this report is reproduced by the National Environmental
Research Center - Cincinnati in the form received from the Grantee; new
preliminary pages and new page numbers have been supplied.
ii
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FOREWORD
Man and his environment must be protected from the adverse
effects of pesticides, radiation, noise and other forms of pollu-
tion, and the unwise management of solid waste. Efforts to protect
the environment require a focus that recognizes the interplay between
the components of our physical environment—air, water, and land.
The National Environmental Research Centers provide this multidisci-
plinary focus through programs engaged in:
• studies on the effects of environmental
contaminants on man and the biosphere, and
• a search for ways to prevent contamination
and to recycle valuable resources.
Under Section 212 of Public Law 91-512, the Resource Recovery
Act of 1970, the U.S. Environmental Protection Agency is charged
with preparing a comprehensive report and plan for the creation of
a system of National Disposal Sites for the storage and disposal of
hazardous wastes. The overall program is being directed jointly by
the Solid and Hazardous Waste Research Laboratory, Office of Research
and Development, National Environmental Research Center, Cincinnati,
and the Office of Solid Waste Management Programs, Office of Hazard-
ous Materials Control. Section 212 mandates, in part, that recom-
mended methods of reduction, neutralization, recovery, or disposal
of the materials be determined. This determination effort has been
completed and prepared into this 16-volume study. The 16 volumes
consist of profile reports summarizing the definition of adequate
waste management and evaluation of waste management practices for
over 500 hazardous materials. In addition to summarizing the defini-
tion and evaluation efforts, these reports also serve to designate a
material as a candidate for a National Disposal Site, if the material
meets criteria based on quantity, degree of hazard, and difficulty of
disposal. Those materials which are hazardous but not designated as
candidates for National Disposal Sites, are then designated as candi-
dates for the industrial or municipal disposal sites.
A. W. Breidenbach, Ph.D., Director
National Environmental Research Center
Cincinnati, Ohio
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TABLE OF CONTENTS
VOLUME VIII
NATIONAL DISPOSAL SITE CANDIDATE
WASTE STREAM CONSTITUENT PROFILE REPORTS
Miscellaneous Inorganic and Organic Compounds
Page
Inorganic Compounds
Antimony Pentafluoride (36), Antimony Trifliioride (43) 1
Chlorine (105) 11
Contaminated Electrolyte (118) 23
Fluorine (200) 25
Nickel Carbonyl (293) 35
Perchloric Acid (To 72 Percent Strength) (324) 45
Organic Compounds
Acrolein 51
Diemthyl Sulfate (160) 59
Pentachlorophenol (322) 67
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PROFILE REPORTS ON
THE ANTIMONY FLUORIDES
Antimony Pentafluoride (36), Antimony Trifluoride (43)
1 . GENERAL
Introduction
Antimony pentafluoride and antimony trifluoride are included in a
combined Profile Report because of similarities in chemistry, toxicology,
other hazards and industrial uses.
Antimony Pentafluoride
Antimony pentafluoride is a colorless, hygroscopic, corrosive
moderately viscous, oily liquid. The compound has an appreciable vapor
pressure at room temperature, and fumes in air, with hydrolysis to HF.
The physical and chemical properties of SbFg are summarized in the
attached worksheet.
The large scale production of SbFg is accomplished by the addition
of an excess of anhydrous hydrogen fluoride to antimony pentachloride in
I QQQ
an all-aluminum apparatus. The mixture is agitated during the addition
of the HF, except for the mid-stage of the reaction, during which inter-
mediate solid chlorofluorides are formed. The anhydrous HF is refluxed
over the mixture until all of the chlorine has been displaced as HC1 , in
accordance with the reaction:
SbCl5 + 5HF«^» 5HC1 + SbFg
The HC1 is driven off by distillation, followed by the excess HF.
-------
The major uses of antimony pentafluoride are:
(1) the preparation of organic fluorine compounds, either alone or
in combination with hydrogen fluoride, iodine pentafluoride,
or antimony pentachloride;
(2) the substitution of fluoride for chlorine in chlorinated
hydrocarbons;
(3) the formation of complex compounds with other metal salts and
halogens;
(4) the preparation of inorganic fluorides by reaction with P^-IQ,
MoCl5, Cr02Cl2, PC13, and other similar compounds.
The most important fluorinating agent for industrial fluorinations
is hydrogen fluoride in the presence of antimony (V) compounds. Sb (V)
is the most useful and most effective catalyst, and SbF,- is the most
effective fluorinating agent.
Antimony Trifluoride
Antimony trifluoride is a white deliquescent crystalline solid. The
commercial salt frequently contains antimony oxide or a basic salt. The
crystal lattice is molecular in character, although the chemical reactions
1988
of the compound are most frequently ionic. SbF-j is extremely soluble
in water, in which it undergoes a limited hydrolysis. The physical and
chemical properties of SbF- are summarized in the attached worksheet.
-. J
Antimony trifluoride may be prepared by crystallization from a solution
of SbpOg in excess hydrofluoric acid. The more common method of manufacture
is by reacting SbCl3 and excess anhydrous HF. Hydrogen chloride is evolved
at 0 to 15 C; excess hydrogen fluoride is distilled off at 40 to 50 C;
unreacted SbCl3 is removed by extraction with carbon tetrachloride.
The major uses of antimony trifluoride are:
(1) to catalyze fluorination of organic compounds by anhydrous HF;
(2) to manufacture organic chlorofluroides by metathesis;
2
-------
(3) in the form of the sodium fluoride and ammonium sulfate
double salts, in dyeing;
(4) in the manufacture of pottery and porcelains.
The fluorinating power of the antimony fluorides varies from rela-
tively mild antimony (III) fluoride through mixtures of antimony (III)
fluoride and antimony (V) chloride to very powerful antimony (V) fluoride.
A moderately high degree of selectivity is achieved in the substitution
2027
of fluorine for the other halogens by proper choice of antimony fluoride.
Antimony (III) fluoride is only slightly more active than hydrogen
fluoride and behaves similarly when mixed with HF. It will, however, give
substitution in a dialkyldichloromethane, in contrast to HF. The order
2027
of strengths ci.ted above has been summarized as follows:
SbF3< (SbF3 + SbCl3)< (SbF3
2. TOXICOLOGY
Human Toxicity
The antimony florides produce physiological responses exhibiting
the combined effects of soluble antimony compounds and soluble fluorides.
For antimony (V) fluoride (SbF5), caustic effects similar to those of
hydrofluoric acid are superimposed upon the toxicity due to soluble
1492
antimony and soluble fluoride compounds.
Specifically, exposure to soluble antimony compounds causes derma-
1492
titis, keratitis, ulceration of the nasal septum, complaints referable
to the nervous system (irritability, sleeplessness, fatigue and diz-
ziness), pneumonitis, fatty degeneration of the liver, a decreased
leucocyte count, and damage to the heart muscle. Symptoms in most
cases include intense gastric and intestinal irritation, with epigastric
pains, dysphagia, a metallic-like taste, vomiting of blood-stained material,
tenesmus, watery diarrhea, rapid pulse, profuse sweating, and spasms of
-------
the muscles of the extremities. In fatal cases, cyanosis, subnormal
temperature, delirium and collapse may also occur. A lethal dosage as
low as 3 grains, taken in 1-1/2 grain increments over a 24-hr interval
2028
has been reported, but larger doses have been non-lethal.
Chronic poisoning due to ingestion/inhalation of soluble antimony
compounds may occur, with symptoms of anorexia, nausea, vomiting, thirst,
2028
diarrhea, muscular cramps and cold sweats.
The TLV for antimony compounds is 0.5 mg/cubic meter.
The effects of soluble fluorides include nausea and vomiting, salivation,
burning, cramp-like abdominal pains, diarrhea, dehydration and thirst-, muscle
weakness, central nervous depression, cyanosis, shock, weak and thready
pulse, shallow unlabored respiration, weak heart tones, paralysis of the
muscles of deglutation, carpopedal spasm, spasm of the extremities, and, in
extreme cases, death. Anhydrous SbFg, or highly concentrated solutions,
produces burns similar to those of HF; these burns are usually more
I QQQ
severe than those from the other mineral acids. External contact causes
onoq
severe irritation of the eyes and eyelids, resulting in prolonged or
permanent visual defects or total destruction of the eyes. Inhalation may
cause extreme-irritation of the respiratory tract, pulmonary inflammation, and
congestion. Ingestion causes necrosis of the esophagus and stomach, with
2023
the additional symptoms npted above. The skin is burned by SbF,-, and
1492
severely irritated by SbF3-
Lethal dosages of 1-1/2 to 2 grams (25 to 30 grains), expressed as F,
1QQQ
of soluble fluoride have been reported ro; prompt treatment has averted
•I QQO
death with much larger quantities. Chronic fluoride poisoning, reported
for other soluble fluorides from exposures to relatively large (but sub-acute)
dosages of fluoride over protracted periods, is improbable with the antimony
fluorides, since the acute toxic effects due to antimony would supervene at
the dosages indicated (ranging from 20 to 80 mg or more of fluoride per
day1988).
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The Federal Water Pollution Control Administration (FWPCA) report on
"Water Quality Criteria"0536 did not establish concentration limits for
antimony in public water supplies, although mention was made of potential
toxicity.
Aquatic Toxicity
Antimony fluoride has been reported as lethal to fish in concentrations
1 QftR
which range from 100 to 200 parts per million. A dose of 5 mg (injection)
was lethal to frogs.1988
3. OTHER HAZARDS
Antimony trifluoride and antimony pentafluoride solutions are highly
corrosive to most metals, due to the highly acid properties of the salt-water
1492
systems. Antimony pentafluoride, anhydrous, corrodes glass, copper and lead,
I QQO
and attacks paper, wood, rubber, and many plastics. Neither salt is
flammable, but both are easily volatilized, to give toxic fumes.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation .
r-
Great care must be exercised in handling antimony pentafluoride, because
of its volatility and hazardous, highly reactive character. A face shield,
neoprene gloves, and protective clothing are recommended in the handling of
pnpo
SbFg. Material spilled on the skin should be immediately flushed away
with large quantities of cold water until all of the compound is removed
(up to 4 hours, or until medical attention is obtained), paying particular
attention to the skin under the nails. Prompt medical attention is
required. Where medical attention is delayed, a mixture of glycerin and
2023
magnesium oxide should be applied. Clothing which has been contaminated
should be removed and washed before re-use. If any SbFg gets into the eyes,
prompt medical attention is absolutely necessary. The eyes should be
2023
flushed immediately with cool water for 15 to 30 minutes. • Personnel
handling SbF,- should avoid breathing the vapor.
5
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Antimony pentafluoride is shipped in steel cylinders (1,5,25, and 200
Ib SbF,- content) and, in accordance with Department of Transportation (DOT)
O
regulations, must carry a "Corrosive liquid" white label when shipped in
interstate commerce or by boat. The cylinders should be stored outdoors,
protected from the weather, or in a well -ventilated room. Exposure to
2023
fire or direct heat should be avoided.
Since antimony trifluoride is a solid, handling hazards are less than those
involved with antimony pentafluoride. The same general precautions should,
however, be taken in handling SbF3 as are listed above for SbF5-
There are no current Department of Transportation or Coast Guard
regulations which cover shipment or labeling of antimony trifluoride.
Polyethylene containers are used for shipping the material.
Criteria for acceptable disposal of the antimony fluorides, defined
in terms of the recommended provisional limits in the atmsophere, in
potable water sources, and in marine habitats, are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
SbF5 0.005 mg Sb/M3 0.01 TLV
SbF3 0.005 mg Sb/M3 0.01 TLV
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
0.05 ppm Sb(mg Sb/1) Chronic toxicity drinking
SbF3 0.05 ppm Sb(mg Sb/1) water studies
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The major use of the antimony fluorides is as catalysts and fluorine
carriers in the manufacture of fluorcarbons. The amounts of all fluorides
emitted to the environment from the fluorcarbon manufacturing processes
are extremely small. Because of the highly toxic and corrosive nature
of the feed and catalyst materials, extreme care is taken to control
spills and leakage. All product streams are scrubbed to meet purity
-------
specifications; the unreacted HF is removed as solid CaF9 and disposed
1 cog ^
of in that form. There are no gaseous effluent streams. For these
reasons, current practices for prevention of antimony fluoride waste
discharge from the fluorocarbon manufacturing processes are deemed
completely satisfactory.
There are no procedures reported for the disposal of small quantities
of the antimony fluorides, with the exception of advice not to use water
on fires involving antimony pentafluoride.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Manufacturing process effluent streams containing the antimony fluorides
can best be handled at the sites where they originate by the continuation
of current, acceptable disposal processes. Small contaminated or surplus
quantities of antimony trifluoride and antimony pentafluoride should either
be returned to the manufacturers for reprocessing, or disposed of at
National Disposal Sites. The disposal method to be employed at the National
Disposal Sites will require development. A proposed disposal process is
to combine Methods 27d and 11 of the Manufacturing Chemists Association
Laboratory Waste Disposal Manual. Briefly stated, the disposal
concept is as follows: Dissolve the antimony fluoride in the minimum
quantity of dilute hydrochloric acid. Saturate with hydrogen sulfide. .
Filter, wash and dry the antimony sulfide precipitate; sell the precipitate
to a primary antimony metal producer. Air strip the filtrate of dissolved
H2S,passing the effluent air into a controlled incineration device,
equipped with a lime scrubber. React the stripped filtrate with an excess
of lime; evaporate to dryness, and dispose of the lime-CaFg-CaC^ mixture
by land burial.
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7. REFERENCES
0094. Bureau of Explosives Association of American Railroads. Dangerous
articles emergency guide. Association of American Railroads, New
York. Mar. 1970. 183 p.
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
3d ed. 1970. Washington, Manufacturing Chemists Association. 174 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Apr. 1, 1968, Washington.
Federal Water Pollution Control Administration. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Interscience Publishers, 1966.
1492. The Merck Index of chemicals and drugs. 7th ed. Railway, New Jersey,
Merck Co. Inc., 1960. 1,643 p.
1668. Robinson, J. M. G. I. Gruber, W. D. Lusk and M. J. Santy. Engineering
and cost effectiveness study of fluoride emissions control. Jan.
1972. McLean, Virginia. Office of Air Programs, Environmental
Protection Agency. 560 p.
1988. Simons, J. H. Fluorine chemistry. New York, Academic Press, 1950.
3,000 p.
1996. Personal communication. S. J. Muller, Allied Chemical Corporation
to G. I. Gruber, TRW Systems, June 19, 1972. Antimony penta-
fluoride.
2023. Allied Chemical Corporation. Antimony pantafluoride SbFr DA--
85621. Product information data sheet. Morristown, New Jersey.
2 p.
2027. Sheppard,,W. A., C. M. Swarts. Organic fluorine chemistry. New
York, W. A. Benjamin, Inc., 1969. 602 p.
2028. Gonzales, T. A. et. al. Legal medicine, pathology and toxicology.
New York, Appleton-Century-Crofts, Inc. 1954. 1,349 p.
8
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Antimony Tr1 fluoride
IUC Name Antimony (III) Fluoride
Common Names Antlmonous Fluoride
Structural Formula
SbF,
Molecular Wt. 178.75
Melting Pt. 292 C
Boiling Pt. 376 C
Density (Condensed) 4.379(s) @?Q.Q r. Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
_ 3mm @ 17 C^ 1Q7mm 9 _ 62
Flash Point
Auto1gn1t1on Temp.
FlammablHty Limits In Air (wt %) .Lower
Explosive Limits in Air (wt. %) Lower
Upper.
Upper_
Solubility
Cold Water 384.7g/lQQg 9 Q C
Others:
Hot Water
Ethanol.
Acid, Base Properties Undergoes limited hydrolysis with water to form HF.
Highly Reactive with
Compatible with Glass and steel. 1f drv.
Shipped in Glass containers or steel drums
ICC Classification None
Coast Guard Classification None
Comments SbF, is used as a fluorlnating agent in the Swarts Reaction. Forms salts of the
typp K,ShFcl Na.SKF, with metal flunrfrit
manufacture of pottery and porcelains.
Dnuhle caltc arp ncoH in flvo
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Antimony PentafluoMde
IUC Name Antimony t\l) Fluoride
Common Names Antimony PentafluoHde
Structural Formula
SbFE
Molecular Wt.
216.74
Melting Pt. 8.3 C
Boiling Pt.142.7C
(1)
Density (Condensed)3.145 (Ho.) @ 15.5 _£1
Vapor Pressure (recommended 55 C and 20 0
Density (gas)
4.3mm
25
.(4)
18mm
50
.(1)
170mm
100
Flash Point
Auto1gn1t1on Temp.
FlammabiHty Limits In Air (wt %) 'Lower_
Explosive Limits in Air (wt. %) Lower_
Upper_
Upper_
Hot Water
Solubility
Cold Water Sol., with reaction.
Others:
Acid, Base Properties Solution in water strongly add.
Ethanol Reacts
Highly Reactive with water, to form SbFr.2HoO(s). Corrodes glass, copper and lead.^ '
Attacks skin, paper, wood, rubber.
'
Compatible with steel when dry. May be stored in aluminum when dry.
Shipped in 1. 5. 25. 200 Ib. steel cylinders.
Corrosive liquid;
ICC Classification Corrosive liquid; white label Coast Guard Class1f1cat1onwhite label.
Comments Fumes in air, with hvdrolvsis to HF^ '. Forms
with HF-
oy.
fluoroantimonate salts are known. Used as flunHnatinn agent Paartt with P_nim Mnri
^ ^*M*-.«*^^^—in J i 9*^^*r*.m W i-^Wf~^ _ | (J •
CrOoClo and organochlorine compnnnHg tn yio^ii f\uoro-compounds Hygroscopicr cnrrnglvc,
moderately viscous liquid. Forms addition compounds with hainjanc and many organics.
References (1) 1988
(2) 1996
(3) 1492
(4) 2023
10
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PROFILE REPORT
Chlorine (105)
1. GENERAL
Liquid chlorine is a clear amber-colored liquid about 1.5 times as
heavy as water. Gaseous chlorine is greenish-yellow, about 2.5 times as
heavy as air. Chlorine has a disagreeable and suffocating odor with an
irritating effect on the nose and throat. Chlorine is not flammable.
It is shipped as a liquid in steel cylinders under its own vapor pressure
of about 85 psig at 70 F.
i Rfi"^
In 1969, 9.5 million tons of chlorine were produced with an
increase in 1972 to 10.6 millions tons projected. Over 99.5 percent was
produced electrolytically with the remainder accounted for by various
chemical processes. The diaphragm and mercury electrolytic cells gener-
ated approximately 65 percent and 30 percent respectively; molten salt
cells produced slightly less than 5 percent. In 1969 it was estimated
1 cc o
that 78,200 tons of chlorine were emitted into the atmosphere. A
summary of the chlorine emissions is presented below:
SOURCE CHLORINE EMISSIONS. TONS
Chlorine Manufacture 47,000
Hydrochloric Acid Manufacture 800
Chemical and Industrial Processes
Organic Chlorinations . 8,500
Pulp Bleaching 18,000
Metallurgical Processing 2,000
Bleach Manufacture 900
Miscellaneous 1,000
The physical/chemical properties of chlorine are summarized in the
attached worksheet.
• 11
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2. TOXICOLOGY
Human Toxicity
Chlorine is an extremely powerful vessicant and respiratory
irritant. Its action is that of a severe irritant, rather than as a
specifically toxic agent. High concentrations of chlorine cause pulmonary
edema which may have fatal termination. Inhalation of lower concentra-
tions causes coughing, smarting of the eyes, a general feeling of dis-
comfort in the chest, nausea, and vomiting. The effects of different
concentrations of chlorine gas are shown below.
EFFECT CHLORINE, ppm
Min. concentration detectable by odor 3.5
Min. concentration causing throat irritation 15
Min. concentration causing coughing 30
Min. concentration causing slight symptoms 1
after several hours
Max. concentration that can be breathed 4
for one hour without damage
Concentration dangerous in 30 minutes 40-60
Concentration likely to be fatal after a few 1000
deep breaths
Threshold limit value for 8-hour exposure (ACGIH) 1
Liquid chlorine causes severe irritation and blistering of the skin.
Toxicity Toward Aquatic Life
The toxicity of chlorine solutions in water is usually not con-
sidered a problem. Dissolved chlorine reacts rapidly with organic and
other oxidizable substances in natural streams and chlorine escapes
from water at pH < 7 at a rather rapid rate. Some species of fish are
sensitive to dissolved chlorine, i.e., tropical fish in home tanks are
sensitive to 0.1 ppm of chlorine. Limits for residual chlorine in
1562
effluents to streams in various states are usually set at 0.5 to 1.5 ppm.
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Toxicity Toward Plant Life
The effect of various concentrations, 300 to 4,500 yg/m (0.1 to 1.5
ppm) of chlorine gas on 26 different species of plants was studied.
The most common symptoms of chlorine poisoning were necrosis and bleaching
of the foliage, which occurred a day or two after the chlorine exposure.
Bleaching of the leaves was a typical symptom which developed from exposure
to low concentrations of chlorine.
3. OTHER HAZARDS
Moist chlorine is very corrosive to all of the common materials of
construction except high silica iron, monel, Hastelloy C, silver, and
the noble platinum metals. At low pressures wet chlorine can be handled
in chemical stoneware, glass, procelain, and certain plastics.
Although chlorine is nonflammable, it is capable of supporting the
combustion of many materials including hydrogen, the reactive metals and
many organic compounds. Chlorine reacts with most non-metallic elements,
sometimes very rapidly. With basic materials chlorine reacts to form
chlorides and hypochlorites. Chlorine has a great affinity for combined
hydrogen to yield hydrogen chloride. Many organic compounds are extremely
reactive, yielding chlorinated organic derivatives and hydrochloric acid.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Adequate procedures for safe handling, transportation and storage of
chlorine are provided by Matheson in the Gas Data Book. This document
provides recommended procedures for equipment design, employee safety,
design of shipping and storage containers, federal classification and
regulations, emergency rescue, first aid and material specifications.
13
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Chlorine is Department of Transportation (DOT) classified as a non-
flammable compressed gas taking a green label. It is shipped in 100- and
150-lb steel cylinders, single unit tank cars of 30,000 pounds and multi-
unit tank cars of 15 one-ton units.
Disposal/Reuse
A definition of acceptable criteria for the disposal of chlorine also
takes into account acceptable criteria for the release of chlorine to the
environment. Current practice in chlorine disposal usually involves:
(1) recycling, (2) recovery, (3) alkaline scrubbing, or (4) venting. The
safe disposal of chlorine is defined in terms of the recommended provisional
limits for chlorine in the atmosphere, in potable water sources, and in
marine habitats. These are:
Basis for
Contaminant in Air Provisional Limit Recommendation
Chlorine 0.03 mg/M3 0.01 TLV
Contaminant in Basis for
Water and Soil Provisional Limit . Recommendation
Chlorine 0.15 mg/1 • Stokinger and
Woodward Method
Contaminant in . Basis for
Marine Habitats Provisional Limit Recommendation
Chlorine 0.003 0.01 F1sh Toxicity
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Litton Systems Inc. has provided a Technical Report which identi-
fies, by process, the sources of chlorine emissions and estimated the
quantities of chlorine emitted. A summary of these emissions are presented
in Section 1. Current disposal practices for the various sources are
briefly described in the following paragraphs together with recommendations
as to their adequacy.
14
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Chlorine Manufacture
Potential sources of chlorine emissions from electrolytic chloro-
alkali plants and approximate quantities emitted15 are as follows:
EMISSION*, Ibd2/ton C12
SOURCE PRODUCED CONCENTRATION
Cell Operation 0.1 0-100%
Acidifying, air blowing, and
vacuum treating depleted brine 7.5 to 10 0-10%
"Blow Gas" from chlorine 2 to 16 20-50%
liquefaction process
Vents from storage tanks, .1 to 6.0 0-100%
process transfer tanks,
tank cards, and shipping
containers
Leaks and spills due to Variable 0-100%
corrosion, wear and
accidents
*Some emissions are recovered
In all cases, chlorine emissions can be reduced to virtually z'ero
by recovery and/or alkaline scrubbing, when the recovery and scrubbing
systems are properly designed and used. The particular technique used
for controlling a chlorine emission source depends upon the concentration
of chlorine in the vent stream, the quantity of chlorine emitted and
the markets for possible by-products such as hydrogen chloride, sodium
hypochlorite, or chlorobenzene.
If the chlorine content of the effluent stream is greater than
10 percent, recovery as chlorine is economical and is usually employed.
Alkaline scrubbers are normally used for dilute streams such as
those resulting from air blowing of depleted brine. Packed bed, counter-
current flow scrubbers are commonly used for more concentrated streams.
IS
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Chemical and Industrial Processes
Organic Chi ori nation. Approximately 80 percent of the chlorine produced
is used in the manufacture of organic chemicals. In some processes, the
chlorinated compound is an intermediate, while in other processes chlorine
is a part of the final product. In most modern organic chlorination pro-
cesses, the exit gas streams are recycled and only low levels of chlorine
are emitted in purge gas streams. Control of emissions from these vent
streams is accomplished by the use of alkaline scrubbing systems.
Paper Pulp Bleaching. During 1969, approximately 1,400,000 tons of
1
chlorine were used by the pulp and paper industry for bleaching. With-
out vent gas control systems, chlorine emissions are about 18 to 42 Ib per
1 ^ifa'%
ton of chlorine used. • Cerstle and Timothy indicates that the alkaline
scrubbers used typically remove only 96 percent of the chlorine emissions.
This indicates that the scrubbers in use are probably underdesigned for peak
load service.
Manufacture of Bleaches and Sanitizing Agents. In 1969, approximately
180,000 tons of chlorine were used in the manufacture of bleaches and sani-
tizing agents such as liquid bleach (sodium hypochlorite solution), bleach
liquor (lime bleach), chlorinated tri-sodium phosphate, chlorine dioxide,
l Rfi^
chlorinated isocyanates and chloroamines. Under normal operating con-
ditions for the manufacture of these compounds, little or no chlorine is
emitted. However, process upsets will occasionally occur and the batch may
decompose to liberate chlorine. Scrubbers, although required to take care
of these upsets, are not normally used.
Other Uses. Other significant uses of chlorine include non-ferrous
metallurgical processing, water and sewage treatment, and production of
metal chlorides and reactive metals.
Approximately 30,000 tons per year of chlorine are consumed in aluminum
I EC O
and other metal production and treating processes. The chlorine is used
to prepare metal chlorides, fluxes for degassing and purification of the metal,
16
-------
In metal smelting and processing little or no chlorine is emitted; the pol-
lution results from the evolution of metallic chloride fumes such as zinc,
magnesium, or aluminum chlorides and the evolution of hydrogen chloride.
Chiorination is the basic process in water and sewage treatment. In
1969, 330,000 tons of chlorine were used for water treatment with large
quantities being used to treat sewage at some stage of the disposal process.
Since most chlorine used in water treatment ends up as a chloride salt,
especially in alkaline water, chloride emissions from water treatment are
negligible. When waste streams, such as those from plating shops, are over-
chlorinated, the excess chlorine is customarily removed by treatment of the
waste stream with sodium acid sulfite.
Abatement Processes
The processes recommended for abatement of gaseous chlorine emissions
and disposal of the recovered chlorine are water scrubbing, followed by
alkali scrubbing, with recycle of chlorine stripped by heating from water
solution, and carbon reduction of the hypochlorite bleed off from alkali
scrubbing. These are discussed in the following paragraphs.
Water Scrubbers. If water scrubbers are used for effluent control,
the chlorine-containing vent gas is passed countercurrent to the water stream
in a tower filled with ceramic packing. Characteristic water scrubber re-
ductions in vent gas are from an initial 15 percent chlorine by volume to
an effluent gas containing 15 to 30 g/m (0.5 to 1.0 volume %) of chlorine.
Common practice is either to pass the tail gases from water scrubbers
through more efficient alkali scrubbers, or to tall stacks for disposal.
The chlorine-rich scrubber solution is heated so that the chlorine may be
stripped and recovered. An alternate method of treatment is to pass
the chlorine-rich water over iron filings or activated charcoal, or to add
ferrous chloride solution. The result is an oxidation-reduction reaction
that converts the chlorine to the noninjurious chloride ion. If ferrous
chloride solution is used, additional iron filings (scrap iron) are employed
17
-------
to reduce a portion of the ferric chloride formed to ferrous chloride. The
bulk of the ferric chloride produced is sold. Used alone, water scrubbing
does not reduce chlorine emissions to permissible levels. It is therefore
recommended that water scrubbing be followed by scrubbing with alkaline
solution.
Alkaline Scrubbers. Contact of chlorine with alkaline solutions,
usually caustic or lime, produces an effluent gas with a lower residual
chlorine concentration than can readily be attained by water scrubbing.
The reaction products are sodium or calcium hypochlorite, and sodium or
calcium chloride. The major disadvantages of this method are the cost and
the difficulty of disposing of the hypochlorite solution. The hypochlorite
solution is either sold, used in another part of the plant, treated with
carbon to reduce the hypochlorite to chloride ion, or disposed of by dumping
into rivers and streams. The last practice is not recommended. If properly
designed, the alkaline scrubbers, used alone or after a water scrubber, can
reduce the chlorine concentration of effluent streams to below 1 ppm.
Carbon Tetrachloride Scrubbers. The advantages of using carbon tetra-
chloride as an absorbent are that its absorbing capacity for chlorine gas
is 10 to 12 times greater than water and the recovery of chlorine is com-
plete. However, losses of carbon tetrachloride have been reported under
uncontrolled conditions to be as great as 30 Ib per ton of recovered chlorine.
The carbon tetrachloride scrubber is operated at 100 psig and the chlorine
stripped by reducing the pressure to 35 psi. A condenser is required to
remove vaporized carbon tetrachloride before compression and liquefaction
of the stripped chlorine.
Silica Gel Absorption. Small quantities of chlorine are collected on
silica gel; the absorbed chlorine is recovered by heating. Though
satisfactory, this method is not widely used because of excessive costs
when large quantities of chlorine must be recovered.
Reaction with Sulfur. High strength vent gases are infrequently
reacted with sulfur to form sulfur chlorides. This method is not recommended
unless there is a specific market for the sulfur chlorides. The disposal of
sulfur chlorides is more difficult than the disposal of chlorine.
18 '
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that systems to handle the great majority of
the chlorine containing effluents generated in the manufacture of
chlorine and in process industries will continue to be located at the
source of effluent generation rather than at National Disposal Sites
in view of the economics involved. However, some capacity to process
chlorine and chlorine-contaminated wastes with minimum environmental
impact is required at National Disposal Sites for the following
requirements:
(1) Occasional tank-car or smaller lots of liquid chlorine
which for reasons are required to be disposed of in a safe,
pollution-free manner.
(2) Secondary gas streams generated within the National Disposal
' Site as a result of processing other wastes (e.g., from
disposal of interhalogen compounds).
It is suggested that the following unit operations will be required for
these purposes at National Disposal Sites:
(T) Water Scrubbing and Stripping Units
Chlorine-containing gas will be stripped of most of its chlor-
ine content by passing the gas stream countercurrent to a water
stream in a tower filled with ceramic packing. Chlorine is
stripped from the recirculating liquor by heating the
absorption tower exit stream, and using the standard drying,
refrigeration, and compression systems for liquefaction of
the chlorine. The collected chlorine is then available for
use at the National Disposal Site, or for sale. The tail
gas from the water scrubber is treated as noted under (2)
below.
19
-------
(2) Alkaline Scrubbers
The vent gas from the water scrubbers above must be followed
with an alkaline scrubber to remove the residual chlorine.
In some cases it will be more convenient to convert chlorine
present at low concentrations in waste gas streams to
sodium hypochlorite in an alkaline scrubber, without prior
use of the water scrubbers. Any hypochlorite made can be
used in cyanide disposal processes at the National Disposal
Sites.
20
-------
7. REFERENCES
0625. Stahl, Q« R. Air pollution aspects of chlorine gas. Technical
Report. PB-188-087. Bethesda, Maryland, Litton Systems, Inc.,
Sept. 1969. 90 p.
1301. Matheson Company, Inc. Matheson gas data book. 4th ed. East
Rutherford, New Jersey, 1966. 500 p.
1562. Graham, H. K. Electroplating engineering handbook. 2d ed.
Westwood, New Jersey, Metals and Plastics Publications, Inc.,
1962. 773 p.
1563. Cerstle, R. W. and W. D. Timothy. Chlorine and hydrogen chloride
emissions and their control. Paper presented at 64th Annual Meeting
of the Air Pollution Control Association, Atlantic City, New Jersey,
June 27 - July 2, 1971. Paper No. 71-25. Cincinnati, Ohio, PEDCO-
Environmental Specialists, Inc. 23 p.
21
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Chlorine (105)
Structural Formula
IUC Name Chlorine
Common Names
Cl
2
Molecular Wt. 7n ong Melting Pt. -im^A. Boiling Pt. .34.OR r
Density (Condensed) 1.468 q/cc @ 0 C Density (gas) 3.214 q/1@ p_ C
Vapor Pressure (recommended 55 C and 20 0
85.46 psia@ 70 F 151.12 psia 9 ]05 F 174.69 psia @ 115 F
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water 0.8% at 10 C Hot Water 0.54% at 30 C Ethanol Reacts
Others: Alkaline Water
Acid, Base Properties Water solutions are slightly acid.
Highly Reactive with Wet-reacts with most metals. Reacts wet or dry with many organic
compounds. ___^
Compatible with With most metals when dry.
Shipped in 100» 150-pound steel cylinders. 15-1 ton units.
ICC Classification N.onflammable gas Coast Guard Classification Nonflammable gas
Comments Critical Temperature 44.0 C
Critical Pressure 76.1 aim
References (1) 1301
22
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PROFILE REPORT
Contaminated Electrolyte (118)
1. GENERAL
All elements which could normally make up a contaminated electrolyte
residue are covered in one of the following Profile Reports:
Cadmium Cyanides, (84)
Chrome (113)
Copper Cyanides (120)
Cyanides (129)
Nickel Cyanide (295)
Silver Cyanide (370)
Zinc Cyanide (457)
Hexavalent Chromium -
(21), (22), (343), (345),
(379), (386)
With the one exception of chrome, all of the above are recommended
as candidate waste stream constituents for National Disposal Sites.
23
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PROFILE REPORT
Fluorine (200)
1. GENERAL
Fluorine is a highly toxic and corrosive pale yellow gas, with a sharp,
penetrating, and characteristic odor. It is shipped in cylinders as a non-
liquified gas in commerce, but may be shipped as a cryogenic liquid for
rocket propel 1 ant use. Fluorine is the most powerful oxidizing agent known,
reacting with practically all organic and inorganic substances with the ex-
ception of the inert gases, metal fluorides in their highest valence state
and a few pure completely fluorinated organic compounds. Even the latter
may burn in a fluorine atmosphere if contaminated with a combustible material
or if subjected to high flow rates of fluorine or excessive mechanical forces,
Hydrogen and fluorine combine with extreme violence forming hydrogen fluo-
ride. Oxygen does not ordinarily react with fluorine, but two oxygen
fluorides, OFp and O^F^ are known.
Fluorine is now manufactured by electrolysis of a liquid mixture of
potassium fluoride and hydrogen fluoride. It is used as a rocket propellant
and for the production of uranium hexafluoride, sulfur hexafluoride, boron
trifluoride and the metal fluorides, silver difluoride, cobalt trifluoride
and manganese trifluoride. The metal fluorides are used in the preparation
of fluorocarbons.
Fluorine will not usually appear in a waste stream unless there is an
accidental excess over the stoichiometric quantity required by a preparation
reaction. However, fluorine frequently becomes contaminated with volatile
fluorides such as silicon tetrafluoride, carbon tetrafluoride, and hydrogen
fluoride and carbon dioxide. Though the impurities can be removed, it is
sometimes desirable to dispose of the contaminated fluorine. It also may be
desirable to dispose of excess fluorine on hand at the Department of Defense
facilities.
-------
The chemical and physical properties of fluorine are summarized in the
attached worksheet.
2. TOXICITY
Fluorine is severely toxic in both liquid and gaseous forms. The pri-
mary effects are local discomfort and irritation to the eyes, lungs and
skin. Industrial experience and animal studies indicate that acute expo-
sure causes pathological lung changes prior to liver damage, kidney damage,
or significant biochemical, hematological, weight, or skeletal changes.
Because of the extreme toxicity and high probability of permanent injury
from exposure, all affected persons should be removed from the contaminated
area, and referred to a physician after local emergency treatment in all
cases. Emergency treatment procedures are the same as those listed for
Chlorine Trifluoride.106 The Threshold Limit Value (TLV) is 0.1 ppm
(0.2_mg/M3). The odor of fluorine ts detectable ato.Oll to 0.014 ppm. 130°
Therefore, there is little danger or hazard to personnel from undetected
or insidious leaks. Emergency exposure limits are as follows:
Time Concentration
10 min 15 ppm
30 min 10 ppm
60 min 5 ppm
3. OTHER HAZARDS
If fluorine is allowed to react with hydrogen, such as in a hydrogen-
fluorine rocket engine, or with a hydrocarbon, hydrogen fluoride is
produced. Hydrogen fluoride is less toxic than fluorine; the Threshold
Limit Value is 3 ppm, thirty times that of fluorine. Hydrogen fluoride is
also formed when fluorine reacts with water. The rate at which water and
fluorine react increases with the concentration of fluorine.
-------
The reaction of fluorine with many metals is slow at room temperature
1154
and often results in the formation of a metal fluoride film. This film
retards further attack in the case of certain metals such as brass, iron,
aluminum, magnesium and copper. Hence, these metals are quite satisfactory
for handling fluorine at room temperatures. Nickel and monel are by far the
best materials to use at high temperatures.
Fluorine is a highly reactive oxidizing agent. As such, it must be
considered a fire hazard. It reacts with many substances not normally con-
sidered combustible, such as sand and glass at elevated temperatures, and
asbestos at room temperature. High concentrations of gaseous fluorine, as
well as the liquid itself, will spontaneously initiate combustion with an
inflammable material.
4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage, and Transportation
Adequate procedures for the safe handling, transportation and storage
of fluorine are described by JANAF, Hazards Working Group, by F. S.
Cakle,1154 and in the military specification for fluorine, MIL-P-27405,1503
June 28, 1968. Liquid fluorine may be shipped, but there are no published
regulations regarding the shipment of liquid fluorine. Insulated tank
trucks have been developed and used under special DOT permits (DOT SP-1479,
1956). Refrigeration is achieved and maintained by using a liquid nitrogen
jacket or cooling coils. Gaseous fluorine is packaged, shipped and stored
in DOT approved, seamless, high pressure, returnable steel cylinders (Depart-
ment of Transportation Specification 3AA 1000). Gaseous fluorine is classi-
fied by the ICC as a flammable compressed gas and is shipped under a red
gas label.
Disposal/Reuse
If fluorine becomes contaminated at the manufacturer, it is either
1304
purified and collected or it is fed to a reactor making a fluoride.
However, if disposal of excess or contaminated fluorine (normal contaminants
27
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are volatile fluorides such as carbon tetrafluoride and silicon tetrafluo-
ride, carbon dioxide and hydrogen fluoride) is to be accomplished at another
site, any definition of acceptable criteria must include processes for dis-
posal of compounds formed during treatment of fluorine. Except for liquid
fluorine (none is known to be in storage) fluorine can be transported to
National Disposal Sites in ICC approved cylinders that are used for its
storage.
The safe disposal of fluorine is defined in terms of the recommended
provisional limits in the atmosphere, in potable water and in marine
habitats. These recommended provisional limits are as follows:
Contaminant Basis of
in Air Provisional Limit Recommendation
Fluorine 0.001 ppm .01 TLV
Contaminant in
Water
Hydrogen fluoride 0.10 ppm
(as Fp/HpO reaction (Stokinger and
product Woodward Method)
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of fluorine in the gaseous
state are briefly described in the following paragraphs together with recom-
mendations as to adequacy. Detailed discussions of the processing operations
are presented in the referenced fluorine disposal reports.
Option No. 1 - Venting
JANAF recommended disposal of residual fluorine from storage tanks
or cylinders by venting slowly as a gas. This is not considered a satis-
factory method.
-------
Option No. 2 - Burning With Fuel
In addition to venting, JANAF recommends burning residual fluorine
from storage tanks or cylinders by means of a fluorine-hydrocarbon-air bur-
ner followed by a caustic scrubber and stack. The caustic scrubber solution
is then treated with lime. Large quantities are disposed of by firing in
an actual rocket motor and treatment of the exit gases with lime to remove
the hydrogen fluoride. These two combustion techniques are usually con-
sidered satisfactory.
Option No. 3 - Reaction With a Charcoal Bed
The classic fluorine disposal unit for small quantities is a charcoal
bed of 3/8-in. charcoal bits. The product of the reaction is carbon
tetrafluoride a chemically inert and relatively nontoxic compound. The
carbon tetrafluoride produced is usually vented. The charcoal disposal
system has proven successful for quantities up to 30 Ib of fluorine in
approximately 3 min (600 Ib per hour). Continuous operation requires a
number of parallel disposal reactors. Approximately 17 Ib of charcoal is
required to treat 100 Ib of fluorine. This method has been widely used and
1414
can be considered satisfactory for fluorine disposal. If the fluorine
is contaminated with large quantities of hydrogen fluoride, the carbon will
initially absorb it and then the hydrogen fluoride is released as the char-
coal is consumed. If highly contaminated with hydrogen fluoride, the char-
coal reactor must be followed by a limestone bed to remove the hydrogen
fluoride. If silicon tetrafluoride is present in large quantities, the
charcoal reactor must be followed by a caustic scrubber. This method is
satisfactory for the disposal of contaminated fluorine.
Option No. 4 - Discharge into a Water Spray
Fluorine has been disposed of by discharge in.to a water spray which
produces hydrogen fluoride as a product. The water then was treated
with lime to remove the fluorides. The use of this method may result in
an explosion, and is therefore not recommended.
29
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Option No. 5 - Absorption by a NaOH, NapCCL, or NaHCO^ Solution
Small quantities of fluorine have been treated in the laboratory by
passing the fluorine diluted with nitrogen through a solution of NaOH,
1154
NapCCL or NaHCOo- This method offers no apparent advantage over the
charcoal reactor and, further, the passage of fluorine through NaOH
solution produces some oxygen difluoride, a highly toxic material. This
method is not recommended.
Option No. 6 - Reaction_With. Sodium or Calcium Chloride
Vapors of fluorine passed through a reactor tube filled with dry
sodium or calcium chloride convert fluorine quantitatively to chlorine.
1304 1154
' The chlorine product is recovered by absorption in a caustic
scrubber. The resulting sodium hypochlorite can be used for the treat-
ment of wastes, or stored. This method is satisfactory and can be used
if desired.
Option No.7 - Treatment With Steam
^
Steam in a 300 to 1,000 percent excess is used at 500 F to treat
fluorine. This method produces hydrogen fluoride, and has only
limited use since a limestone bed is also required.
Option No. 8 - Reaction With Silicon Carbide
Fluorine has been destroyed by treatment with silicon carbide packed
in an aluminum tube 24 ft long and 2 in. in diameter. The reaction pro-
duct is silicon tetrafluoride which requires treatment by a caustic
115^
scrubber.
recommended.
1154
scrubber. This method has not found wide acceptance and is not
The dispositions of compounds formed by the various alternative
disposal processes and of probable fluorine contaminants are as follows:
30
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Contaminant and Source
Hydrogen fluoride (gas from
combustion or reaction with
water)
Carbon tetrafluoride (gas from
carbon or hydrocarbon burning)
Chlorine (gas from reaction
with sodium chloride)
Silicon tetrafluoride (gas
impurity in fluorine which
does not react in the char-
coal bed disposal process)
Carbon dioxide (gas impurity
in fluorine as above)
Disposition
React with lime or limestone.
Place calcium fluoride formed
in land fill (see Profile Report
on hydrogen chloride [217])
Vent
Scrub with caustic solution
(see Profile Report on chlorine
[105])
If large amount, scrub with
caustic solution
Vent
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is recommended that National Disposal Sites have a unit operation
capable of handling fluorine and interhalogen compounds. The recommended
method for fluorine is Option No. 3, Reaction with a Charcoal Bed, but
Oj-tion No. 2, Burning with Fuel, can be used. Option No. 3 is recommended
because the method can be used for disposal of both fluorine and the
interhalogens, and because there is adequate engineering data for
construction of a disposal unit for fluorine.
31
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7. REFERENCES
1154. Cackle, F. S. Design handbook for liquid fluorine, general handling
equipment. WADC Technical Report 60-159, Sacramento, California,
Aerojet General Corporation, Contract AF33(616)6588, Dec. 1960.
1300. JANAF Hazards Working Group. Chemical rocket propel!ant hazards
liquid propellent handling, storage and transportation. V. 3.
Silver Springs, Maryland, CIPA Publication No. 194, May 1970.
1301. The Matheson Company, Inc. Matheson gas data book. 4th ed. New
York, 1966. 500 p.
1304. Personal communication. Mr. Stansfield, Allied Chemical Corporation
to J. R. Denson, TRW Systems, Mar. 3, 1972.
1414. General Dynamics, Convair Division. A study of prelaunch operations
for a space storable propel!ant module. Final Report No. GDC-BNZ
69-013-7. San Diego, California, Mar. 1970.
1503. Specification, propel!ant, fluorine, type I gaseous fluorine,
type II liquid fluorine. MIL-P-27405, June 28, 1968.
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I
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Fluorine (200)
Structural Formula
IUC Name Fluorine
Common Names
F
2
Molecular Wt. 38-°° Melting Pt. -219.02 c Boiling Pt. -188.13 C
Density (Condensed) 1.90g/cc @-227 C Density (gas) 1.3 @ 0 C
Vapor Pressure (recommended 55 C and 20 C)
19.7 psia G> -300 F 164.7 psia @ -250 F 794.7 PSV -200
Flash Point - Autoignition Temp. -
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water reacts Hot Water reacts Ethanol reacts
Others: reacts with most
Acid, Base Properties
Highly Reactive with Almost all materials upon heating
Compatible with liquid N? and liquid 0? ; can be contained in copper, stainless steel,
monel. nickel, brass, aluminum
Shipped in pressure tanks
liquid - none nni SDPT lAAinnn
ICC Classification flammable - gas P toast Guard Classification.
Commen ts TLV 0.1 ppm __
Critical oressure 809.7 osia
critical temperature -128.65 C
References (1) 1300
33
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PROFILE REPORT
Nickel Carbonyl (293)
1. GENERAL
Nickel carbonyl, Ni(CO)., is a colorless to straw yellow liquid. Ex-
tremely small vapor concentrations in air are very toxic.
The primary processes which utilize the material are the basic Mond
process for the refining of nickel (Figure 1) or the improved pressure
carbonyl process (Figure 2). In both of these cases the reaction which
"gives wings to a heavy metal", is readily reversible. The carbonyl mole-
cule decomposes to nickel metal and carbon monoxide at temperatures in the
300 to 600 F range:
120 F
Ni + 4 CO = Ni(CO)4
450 F
Ni(CO)4 = Ni + 4 CO
An examination of the flowsheets (Figures 1 and 2) show how this re-
action is utilized for the refining of nickel. The carbon monoxide and
the residual nickel carbonyl is recycled for further extraction purposes.
Thus the only concern, and a very real one because of the toxicity of the
nickel carbonyl, is leakage from the system.
Other processes which utilize nickel carbonyl take advantage of the
decomposition reaction to remove the hazard by running the waste gas stream
through a flame or decomposition furnace, collecting the fine nickel (a
suspected carcinogen) and wasting the carbon monoxide to the atmosphere.
35
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NICKEL OXIDE
GRANULES
Water Gas
REDUCERS
(3 in Series)1
Producer
Gas
CO
ABSORBER
300 psig
Combustion Gas
to Atmosphere
Cooling
Water
VOLATILIZERS
(8 in Series)
Residue to
Sulfating Roast -«»
& Leach
NICKEL PELLETS TO MARKET
Figure 1. Flowsheet of Atmospheric pressure carbonyl process at Clydach
36
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NICKEL OXIDE
GRANULES
STORAGE
HOPPERS
Cooling
Water
Hydrogen Enriched
Water Gas
^— Combustion Gas
to Atmosphere
Inert
. Gas
Reaction Gas
Cooling
Water
(CO & Carbonyls) f
BATCH
VOLATILIZER
(300 psig)
Cooling ||||| CONDENSER
Water
CO
CO
BLOWER
Liquid
Carbonyls
COMPRESSOR
Return CO
Liquid Nickel
CarbonylI
Hot Water
VAPORIZER
DISTILLATION
COLUMN |
DECOMPOSER
VaP°r Hot"GaT
Vapor
Residue to
Sulfating Roast
& Leach
CO From
Copper Liquor Plant
Iron Carbonyl Residue
NICKEL POWDER
TO MARKET
Figure 2. Flowsheet of medium pressure carbonyl process at Clydach
37
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2. TOXICOLOGY
Human Toxlcity
The recommended ACGIH Threshold Limit Value (TLV) for Ni(CO)4 is 0.001
ppm in air (0.007 mg/cubic meter) because of the extremely toxic inhalation
effects of this material. Exposure results in giddiness and headache ac-
companied at times by rapid shallow breathing and vomiting. Exposure to
fresh air brings relief of symptoms. In a period from 12 to 36 hours after
exposure the symptoms recur along with other signs of disturbance of the
central nervous system. Death occurs in fatal cases between 4 and 11 days.
3. OTHER HAZARDS
Nickel carbonyl/air mixtures are ignitable and explosive in a wide
range. The range lies between 3 and 34 percent volume in air. It is auto-
igniting at contact with oxygen in the air. Based on these properties it
is impossible to establish the ignition temperature as the partial pressure
curve at -34 C is already within the lower explosive limit and ignition
occurs immediately.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
All rooms in which work with nickel carbonyl takes place must be
well equipped for intake and exhaust ventilation. A 30 to 40 times air
change per hour appears to be sufficient. In the laboratories, under no
conditions should more than a day's supply of nickel carbonyl be in stor-
age. Organic solvents and other, flammable fluids may not be kept or
used in such rooms.
38
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The in-plant storage (at nickel refineries) of liquid and gaseous
nickel carbonyl utilizes alloy steel storage vessels sized for the parti-
cular refinery concerned (normally with a CO blanket). Recommendations
for laboratory or small plant storage specify steel containers with a
2/5 ullage space filled with CO. The recommendations also specify that
steel containers with nickel carbonyl must be stored upright in a special
remote shed. The storage shed must be provided with the following
essential capabilities: It must protect the contents against weather.
The cylinders must be stored in cylinder racks. A functional air handling
system, both intake and exhaust must provide for an optimal air movement
in the room. A double roof should remove the excessive heat of the sun.
The doors must be equipped with security locks. Warning plaques should
advise of the danger of fire and poisoning. The storage area must be
separated from the surroundings by a wall or fence, 5 meters distant.
The storage area may be entered only with the knowledge of the person
responsible and only with respiratory protective devices on. The respon-
sible person is the keeper of the keys to the installation and is com-
pletely responsible for the enforcement of all safety measures. At least
two persons must be participating whenever work in the storage area takes
place. A third person must control the trace analyzer for nickel carbonyl
Before entry into the storage area, the exhaust fan must be working.
A complete inventory log must be kept on the fate of the stored
amounts, including small quantities as well as large quantities which
have been reworked into other materials or destroyed. The log must be
complete and it has to describe the location, the time, and the manner
in which the material was either used or destroyed.
The air in the room should be changed once every minute and the air
in the glove box or similar confinement device should be changed 9 times
per minute. Besides these general installations for ventilation of the
room, the areas in which specially strong concentrations of nickel
carbonyl could be expected such as the storage shed and the manifold
39
-------
connections and gas drain valves should be equipped with special exhaust
ducts. In these areas, respiratory protection devices for individual
protection against nickel carbonyl should be used. The preferred device
for respiratory protection is the self-contained oxygen breathing apparatus.
Special protective clothing is not considered necessary. Nickel car-
bonyl laboratory activities require normal laboratory coats made from cotton
which in case of fire can be immediately removed from the body. Rubber
gloves can be recommended for possible skin damage and perhaps absorption
through the skin; however, nothing reliable is known about whether nickel
carbonyl, besides the respiration danger, also carries the danger of pen-
etrating skin in dangerous quantities. Therefore, the danger of percutaneous
poisoning shrinks considerably in the background in view of the much greater
danger of inhalation poisoning. The inhalation of nickel carbonyl is in-
siduous as there is no odor or (immediate) irritation of the respiratory
organs.
The Department of Transportation (DOT) classification as a "flammable
liquid, red label, not accepted for shipping" and the U. S. Coast Guard
classification of "Inflammable Liquid, Red Label" are indicative of the
hazard concerned. The recommended method of transport of small amounts of
the material in steel containers is an open truck. The truck should be
open with weather covering for the cylinders which are strapped in the
vertical position. The truck should also be equipped with self-contained
oxygen breathing apparatus, a resuscitator and C02 fire extinguishers.
Disposal/Reuse
As previously described, and demonstrated by an examination of the
flowsheets (Figures 1 and 2) the primary process utilizing nickel carbonyl
utilizes a complete recycle system. Nickel carbonyl is also inadvertently
generated in many processes where CO passes over finely divided Ni. In
these cases the small quantities generated are normally dissipated by
increased ventilation. In other cases where small quantities of Ni(CO)4
are generated as part of the process they are either regenerated in a
40
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manner similar to that used for the recycling in the Mond process for the
recovery of Ni or small quantities are burned to release Ni and CO. The
particulate Ni is scrubbed from the gas stream and the CO is normally re-
leased from a tall stack to atmosphere so that normal atmospheric dispersion
will reduce the concentration of CO to well below toxic levels. Known dis-
charge of liquid nickel carbonyl into sewer systems is prohibited because of
the extreme hazard of the vapors. The provisional limits for nickel
carbonyl in the environment are:
Contaminant and ' Basis for
Environment Provisional Limit Recommendation
Nickel carbonyl . 0.00001 ppm (0.00007 mg/M3) 0.01 TLV
in air
Nickel carbonyl 0.00035 ppm (mg/1) Stokinger and
in water and soil Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
As described above, the present waste management practices fall into
two categories:
(1) Recycle where large quantities of Ni(CO), are utilized for
extraction purposes.
(2) Thermal decomposition and wet scrubbing for disposal of
small quantities.
Neither of these methods constitute a threat to the environment in a
normal operating mode. In a recycle system, leakage from a portion of the
system can normally be isolated until the operation can be shut down for
repair. Decomposition heaters for small quantities are normally fitted
with alarms in case the flame goes out.
41
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The present methods for the handling and treatment of large quantities
of nickel carbonyl are adequate. Only small quantities are found at any one
place in the United States as the main producer of Ni (Hanna Mining, Riddle,
Oregon) mines a laterite ore and does not use a nickel carbonyl process re-
fining. However, because of the high degree of toxicity and hazards associ-
ated with Ni(CO)*, it is recommended that National Disposal Sites be equipped
to dispose of small quantities by thermal decomposition and wet scrubbing.
42
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7. REFERENCES
0376. Stokinger, H. E. Metal carbonyls. ln_ Industrial Hygiene and Toxicology.
Ed. by F. A. Patty. New York, Interscience Publishers, 1963.
p. 1,104-.! ,112.
0633. Sullivan, R. J. Air pollution aspects of nickel and its compounds.
Technical. Report. PB-188-070. Bethesda, Maryland, Litton Systems,
Sept. 196^9. 76 p.
1570. Chemical Rubber Company. Handbook of chemistry and physics. 47th ed.
Cleveland, 1966. 1,500 p.
1797. Bo'idt, J. Rf. The winning of nickel, its geology, mining, and extractive
metallurgy. Princeton, New Jersey, D. Van Nostrand Company, 1967.
1798. Hackert, 0.. W., H. Claus, and A. Meyer. Nickel tetracarbonyl.
Sozialversicherung/Arbeitsschutz, Issue 3, 1969. p.. 24-25.
43
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nickel Carbonvl (293)
Tnr .. ,.. Structural Formula
IUC Name Nickel Carbonyl
Common Names
Ni(CO)
4
Molecular Wt. 170.73 Melting Pt. -25 C Boiling Pt. 43.2 C
Density (Condensed) S.G. 1.31 @ 25_C Density (gas) .9
Vapor Pressure (recommended 55 C and 20 0
261 mmHg @ 15.C 400 mm § 25.8 C 760^mm @ 42.5 C
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %} Lower 3 Upper 43 *see comments
Solubility
Cold Water 0-018 g/IQOml Hot Water Ethanol soluble
Others:
Acid, Base Properties Unreactive with aqueous acids and alkalies
Highly Reactive with Oxygen
Compatible with steel containers are used, synthetic rubbers are considerably more
resistant than natural rubbers which harden
Shipped in steel containers under C0? blanket w/2/5 ullage
ICC Classification pl. Red Label, not accepted coast Guard Classification 1L; red label
Comments Extremely toxic but decomposes readily with heat to Ni and CO - liquid colorless
to straw yellow. Explosive limits: nickel carbonyl/a:ir mixtures are ignitable and explosiv
in a wide range.it lies between 3 and 34 percent volume in air.Nickel carbonyl is auto^
igniting at contact with oxygen in the air. Based on these properties it is impossible to
establish tne ignition temperature as the partial pressure curve at -34 C is already within
the lower explosive limit and ignition occurs immediately.
References (1) 1570
(2) 0376
-------
PROFILE REPORT
Perchloric Acid (To 72 Percent Strength) (324)
1. GENERAL
In its usual commercial form, 70 to 72 percent aqueous solution,
perchloric acid has no oxidizing power when cold. Its properties are
those of a strong acid. The cold 72 percent acid reacts with active
metals with the liberation of hydrogen and formation of perch!orates.
When heated, reduction of the perchlorate ion begins to take place and
hydrogen chloride becomes a product. The lack of oxidizing power of
cold perchloric acid permits the preparation of numerous organic salts of
the acid thus establishing its wide use in the titration of organic bases
in non-aqueous solvents. The hot, concentrated acid, however, is a strong
oxidizing agent which makes it useful in analytical work for wet ashing
organic matter and in the determination of chromium in steel.
Most commercial perchloric acid is made by the Permet Process in
which sodium perchlorate is dissolved in water and reacted with an excess
of concentrated hydrochloric acid to precipitate sodium chloride. The
sodium chloride is filtered off to give a filtrate containing about
32 percent perchloric acid. The hydrogen chloride is boiled off, condensed
and returned to react with additional sodium perchlorate. The dilute
perchloric acid is then concentrated by evaporation to about 57 percent
while any remaining hydrogen chloride is lost in the vapors which should
be scrubbed. The crude perchloric acid is vacuum distilled in a glass or
glass-lined still to produce a product of 70 to 71 percent perchloric acid.
Sodium perchlorate crystals form as a waste product, but these are recovered
and added to the sodium perchlorate used in the initial reaction.
The physical/chemical properties for perchloric acid are summarized
in the attached worksheet.
45
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2. TOXICOLOGY
Perchloric acid is considered only slightly toxic. However like
other strong acids, perchloric acid in the form of liquid, mist or vapor
is highly corrosive to the skin, eyes and mucous membranes. The amount
of damage will depend upon the concentration, temperature, and duration'
of contact. Perchloric acid is considered to be a primary skin irritant.
Since perchloric acid is not very volatile, the types of injury most
likely to occur in industry are irritation of the respiratory tract
through inhalation of the mist or spray, and severe burns of the eyes and
skin through contact with the liquid.0766' 1156
When diluted and neutralized with sodium, potassium, or calcium
hydroxides or carbonates, the perchlorate ion is slightly toxic. Oral
doses of 200 to 400 mg of potassium perchlorate every 8 hr for
periods up to 52 weeks were given to treat hyperthyroidism in humans. •
Other than a decrease in the serum concentration of protein-bound iodine,
no significant changes in the subjects were noted.
Goldfish in water containing 0.1 percent sodium perchlorate were
not affected; but when the sodium perchlorate concentration was raised
to 0.2 percent, one in five fish died after 24 hr exposure.
3. OTHER HAZARDS
Anhydrous perchloric acid undergoes spontaneous explosive decomposition
in storage, and will explode as the result of violent reaction with trace
contaminants. For this reason anhydrous HCIO^ should not be prepared
except in small quantities for research purposes, and anything which will
dehydrate 72 percent HC10, should be avoided. Dehydration takes place
upon vacuum distillation, and (explosively) on contact with concentrated
HoSO,. Perchloric acid in excess of 72 percent concentration is prohibited
from shipment and in some areas a special permit is required to prepare
anhydrous perchloric acid. Even the aqueous solution of 72 percent
46
-------
perchloric acid requires special precautions in its use. Contact of
perchloric acid solution with easily oxidized or combustible materials
or with dehydrating or reducing agents may result in fire or explosion.
If used in wet combustion of organic material, the sample must first be
treated with nitric acid to destroy easily oxidized organic matter. '
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Cold 72 percent perchloric acid reacts with active metals with the
liberation of hydrogen and formation of the perch 1 orates. Marked
passivity is noted in certain cases, e.g., iron, chromium and nickel.
Only the platinum metals and glass are not attacked by hot perchloric
acid limiting the materials of construction for equipment used in handling
perchloric acid.
Perchloric acid, providing the concentration does not exceed 72 percent
by weight, is classified by the U. S. Department of Transportation (DOT) for
shipment as a corrosive liquid under a white Acid label. Perchloric acid
solutions, in bottles having a capacity not over 1 Ib or 16 oz by volume,
enclosed in a metal can, are exempt from special packaging, marking and
labeling requirements. Each box with larger inside containers and carboys
must bear a white Acid label.
Waste streams containing perchloric acid must be neutralized to a pH
of 6.5 to 9.2 before discharging into streams or lakes. The
concentration of perchlorate ion discharged should not exceed O.lg/lOOg
of water.
The safe disposal of perchloric acid is defined in terms of the
recommended provisional limits in the atmosphere, and in water and soil.
These recommended provisional limits are as follows:
47
-------
Contaminant in Provisional Limit Basis for Recommendation
Air
Perchloric Acid 0.01 mg/M Based on similar compounds
Contaminant in Provisional Limit Basis for Recommendation
Mater and Soil
Perchloric Acid 0.05 ppm Based on similar compounds
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The recommended disposal procedure by the Manufacturing Chemists
Association for packaged lots of perchloric acid is to add the ac.id to
a large volume of a reducer such as sodium thiosulfate, a bisulfate or
a ferrous salt acidified with SM-H^SO.. The reported reduction
takes place when the solutions are heated. The reduction of perchloric
ion to chloride with Keated ferrous sulfate is recommended for use with
extreme care. The reduction products must be tested to determine that
complete reduction of the perchlorate ion has occurred.
6. ..APPLICABILITY TO NATIONAL DISPOSAL SITES
It is not anticipated that large quantities of aqueous perchloric
acid solutions (up to 72 percent in concentration) will require disposal
However, because of the hazards associated with the destruction of per-
chloric acid, treatment of excess or waste perchloric acid at National
Disposal Sites is recommended. The process recommended is the hot
reduction with ferrous sulfate and dilute sulfuric acid.
48
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7. REFERENCES
0095. Manufacturing Chemists Association. Laboratory waste disposal manual.
3d ed. Washington, Manufacturing Chemists Association, 1970. 176 p.
0536. Water quality criteria. Report of the National Technical Committee
to the Secretary of the Interior. Washington, Federal Water
Pollution Control Administration. Apr. 1, 1968. 234 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1156. Schumacher, J. C. Perchlorates, their properties, manufacture and
uses. New York, Reinhold Publishing Corporation, 1960. 257 p.
49
-------
H. H. Name Perchloric acid (
IUC Name Perchloric acid
Common Names
Molecular Wt. 100.47
Density (Condensed) 1.764
Vapor Pressure (recommended 55
9
Flash Point
Flammability Limits in Air (wt
Explosive Limits in Air (wt. %)
Solubility
Cold Water soluble^1 }
Others: acetic add, most
Acid, Base Properties strong a
HAZARDOUS WASTES PROPERTIES
WORKSHEET
324)
Structural Formula
HC10
Melting Pt. -112 C(1) Boiling Pt.™ C(8 torr)(1)
9 20 Cl|j Density (gas) 9
C and 20 0
9 9
Autoignition Temp.
%) Lower Upper
Lower Upper
Hot Water soluble^ Ethanol soluble^1?
polar organic solvents - soluble^ J
c1d(D
Highly Reactive with Reducing
substances and active metal s^'J
Compatible with
Shipped in Glass bottles 1 and
5-1 b, carboys 2,5 and 10-gal(i;
,-,} torrosive nquia,
ICC Classificationcorrosive liquid, white 1 a be r Coast Guard Classification White Label '}*
Comments Forms constant boiling mixture containing 71.6 percent acid.
References (1) 1156
50
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PROFILE REPORT
Acrolein
1. GENERAL
Acrolein is a clear, colorless, volatile liquid, soluble in many
organic liquids; it is a powerful lacrimator and is highly toxic. It is
also one of the most reactive organic chemicals available to industry.
The extreme chemical reactivity of acrolein is attributed to the conju-
gation of a carboxylic group with the vinyl group within its structure.
Because of its toxic nature and because both the liquid and the vapor
1317 1434
are flammable, acrolein must be handled with extreme care. '
Acrolein is manufactured on a commercial scale by the direct oxidation
of propylene or by the cross-condensation of acetaldehyde with formal-
1433
dehyde. It is used in the manufacture of Pharmaceuticals, amino acids,
odorants, dyestuffs, textile finishing resins, paper chemicals, polyesters,
and polyurethanes.
Large scale commercial facilities for the manufacture of acrolein are
operated by Union Carbide Chemicals and Shell Chemical Corporation.
Physical/chemical properties are summarized in the attached worksheet.
2. TOXICOLOGY1317
Acrolein is a highly toxic chemical and is poisonous by ingestion,
inhalation, and absorption through the skin. It is intensely irritating
to the eyes, respiratory tract, and lungs and should be handled only in
a closed system or under conditions that provide ample ventilation.
51
-------
Exposure to one part per million of acrolein in air produces
detectable eye and nose irritation in 2 or 3 min., moderate eye irritation
1433
with lachrymation in 4 min and is tolerable in 5 min. The Threshold
Limit Value (TLV) quoted in the current Occupational Safety and Health
Standards (Fed. Reg. 1971) of 0.1 ppm is sufficiently low to minimize,
but not entirely prevent, irritation to all exposed individuals. The TRW
assessment of the toxicological information recommends a limit in air
of 0.001 ppm (0.0025 mg/M^) for 24 hr exposure.
The liquid can be absorbed through the skin causing severe burns. It
also causes severe burns to the eyes. Care should be exercised in handling
to prevent contact of the liquid with the skin, eyes, or clothing.
3. OTHER HAZARDS
Acrolein monomer is a dangerous substance due to its flammability and
high reactivity. The explosive limits in air are between 2.8 and 31 percent
by volume of acrolein. Inadequately inhibited acrolein may also be subject
to explosive polymerization. For this reason, it is shipped under an
1317
oxygen-free atmosphere and inhibited with hydroquinone.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage and Transportation
Special methods of handling and storage of acrolein are required.
Preferably, all processing equipment, as well as storage facilities
should be located outdoors to afford adequate ventilation. All
electrical equipment, motors, lights, and flashlights used in an area
in which acrolein is handled should be vapor tight or explosion proof.
Static electricity should be guarded against by properly grounding all
1317
equipment, tanks, piping, loading racks, etc. Iron and steel
are satisfactory materials of construction for handling inhibited acrolein.
Copper metal or its alloys is recommended in distillation systems because
of the additional inhibiting effect conferred by these materials.^34
-------
Suitable storage and handling facilities should be available to keep
acrolein under an oxygen-free atmosphere since inadequately inhibited
acrolein is subject to explosive polymerization. It is recommended
that any appreciable quantity of acrolein be stored or handled in a non-
draining, diked area in order to confine this very toxic chemical in the
event of spillage. For large scale operations, workers should wear
protective equipment such as glasses and gas masks. Shipping regu-
lations are found in the Code of Federal Regulation 49CFR73.122 for 1-gal.
containers (2A), 55-gal. drums (5A) and 6- and 10-thousand-gallon tank
cars (105A-500).
Disposal/Reuse
Criteria for the disposal of acrolein in waste aqueous streams must
take into account the products formed during neutralization of these dilute
(parts per billion) solutions. The reaction with the carbon-carbon double
bond is catalyzed by base.
1 on o
Current techniques utilize neutralization of the acrolein with
base and lagooning (secondary treatment). Low molecular weight oligomers
containing hydroxyl and aldehyde functionalities are formed in base
catalyzed reactions. These structures are generally biodegradable.0314
The waste acrolein streams are too dilute to be amenable to incineration,
therefore, secondary treatment or deepwell disposal is presently used.
Acrolein appears as an organic waste stream constituent in varied
forms and compositions. A typical organic liquid waste stream (generated
in the petrochemical industry) containing acrolein has the following
composition:
Light naphtha containing 1 to 5 percent acrolein; up to
5 percent acrolein dimers and trimers.
Information relating to the quantities of acrolein containing wastes
generated annually is presented in Volume XIV "Waste Forms,
and Quantities". '
-------
Recommended provisional limits for acrolein in effluent streams re-
leased to the environment from acrolein waste disposal processes are as
follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Acrolein 0.001 ppm (0.0025 mg/M3) 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Acrolein 0.01 ppm (mg/1) Stokinger & Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Acrolein appears primarily as aqueous waste streams in low concen-
trations and only rarely as concentrated waste. The processing options
are briefly described in the following paragraphs together with recommen-
dations as to their adequacy.
Concentrated Acrolein
In the event it becomes necessary to dispose of a significant
quantity (55-gal. drum or 10,000-gal. tank car) of concentrated acrolein,
two disposal options are available. The first option is to contact the
manufacturer and determine if it is possible to return the material.
Union Carbide Corporation has indicated a willingness to accept
concentrated acrolein for reprocessing. The second option is incineration
since acrolein is highly flammable and amenable to this treatment. In
fact, many plants using this material maintain incinerators for disposal
of combustible liquid byproducts and these same facilities can and are
used to dispose of waste acrolein. It is expected that any liquid
combustion unit operated at a minimum temperature of 1,500 F (0.5 seconds
minimum residence time) followed by secondary combustion at a minimal
temperature of 2,000 F for 1.0 second would completely convert acrolein
to carbon dioxide and water. Complete combustion of acrolein would not
require subsequent scrubbing of the combustion products. Both options
present adequate ways to handle the concentrated waste but it is strongly
urged that all possible effort be directed toward recycling the material
and that incineration be used only as a back-up option.
54
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Dilute Aqueous Haste
Acrolein appears as waste in water at concentrations in the order
1431
of parts per billion in the manufacturing process. Other sources
of waste are from water used in the cleaning of equipment used in acrolein
1317
service. Methods for adequately handling the disposal of dilute
aqueous solutions of acrolein are currently under study by Union Carbide
1318
Corporation under the partial sponsorship of EPA.
Option No. 1 - Secondary Treatment. Secondary treatment procedures
comprised of neutralization and subsequent lagooning are currently being
1318
used by Union Carbide Corporation. Sufficient information is not
available at this time to make a recommendation as to its adequacy.
Option No. 2 - Deepwell Disposal. Although deepwell disposal is
currently utilized as a means of dilute aqueous acrolein waste disposal,
the method is judged to be inadequate. This judgement is based primarily
on three factors. First, the problem of assuring that a deepwell will
operate satisfactorily over a long period of time is extremely complex
and costly, and therefore proper methods of assurance are seldom followed.
Secondly, there has been little research in the area of long term effec-
tiveness of this form of disposal and thirdly, deepwell injection really
represents a form of relatively unaccessable long-term storage for most
organic materials, as opposed to conversion to a nonhazardous material.
Currently utilized deep well disposal methods are described by Jones. ^'^
A general description of the technique is given in Volume III.
Option No.3 - Combustion. Submerged combustion is a direct combustion
method used by the petrochemical industry. A specially designed burner has
been used successfully for total or partial evaporation of waste streams
and for concentrating dissolved solids. A detailed description of the
Fredrich Uhde Combustion Process and the Fluor Submerged Combustion Process
has been provided by Jones. The concentrated effluent from this process
may then be treated as a concentrated waste as discussed in the section on
Concentrated Acrolein of this report. In principal, this means of dilute
waste treatment should be adequate.
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Due to its extreme chemical reactivity, toxicity, flammability, and
the processing difficulties associated with those characteristics, it is
anticipated that disposal systems to handle both dilute and concentrated
acrolein wastes will be required at National Disposal Sites located near
manufacturers and users. The dilute acrolein wastes that will require
treatment include spent cleaning solutions for acrolein containers and
any other on-site generated waste water containing acrolein. The concen-
trated acrolein wastes that will require treatment include any surplus,
contaminated, or degraded material.
The processes recommended for the treatment of dilute acrolein wastes
at National Disposal Sites are:
Process Order of Preference
Biological
Submerged
Combustion
First Choice
Second Choice
Remarks
In principal, this method appears
adequate when followed by proper
disposal of the concentrated effluent.
Method currently used; effectiveness
currently under study; requires
neutralization prior to lagooning.
The process for treatment of concentrated acrolein wastes at National
Disposal Sites are:
Process Order of Preference
Recycle
Incineration
First Choice
Second Choice
Remarks
Major producer has indicated
willingness to accept concentrated
acrolein waste.
Demonstrated technology; applicable
to most organic wastes.
56
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7. REFERENCES
0314. Jones, H. R. Environmental control in the organic and petrochemical
industries. New Jersey, Noyes Data Corporation, 1971.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1317. Carbide and Carbon Chemicals Company. Acrolein. New York, 1955.
24 p.
1318. Personal communication. E. D. Suthard, Union Carbide Corporation, to
W. P. Kendrick, TRW Systems, Mar. 22, 1972.
1321. Union Carbide Chemicals Corporation. Acrolein and derivatives.
Bulletin F-40-1188, 1957. 38 p.
1418. Personal communication: D. L. MacPeek, Union Carbide Corporation, to
W. P. Kendrick, TRW Systems, Mar. 27, 1972.
1431. Personal communication. E. D. Suthard, Union Carbide Corporation, to
W. P. Kendrick, TRW Systems, Mar. 28, 1972.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
1434. Kirk-Othmer encyclopedia of polymer science and technology. 12 v.
New York, Wiley-Interscience Publishers, 1964-1970.
1451. Gilbert, E. E., and J. J. Donleavy. The polycondensation of acrolein.
Journal of the American Chemical Society. 60(2):1,911-14, Aug. 1938.
57
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
C,H,,0
H. H. Name ACROLEIN (8) 3 4
Structural Formula
IUC Name 2-propenal
Common Names Acrolein. propenol; acrylic aldehyde
2
mice 66 ppm for 6 hrs.
CH0:CHCHO
TLV 0.001 ppm (0.0025)/24 hrs.
Molecular Wt. 56.06v1^ Melting Pt. -87.7 C^ Boiling Pt. 52.5
Density (Condensed) 0.841 G> 20 /4 C^ Density (gas) 1.44
@
air ^
Vapor Pressure (recommended 55 C and 20 Q) ^ 20 -j
760 mm @ 52.5 C^ 215 mm @ 20 678.5 mm @ ' 50
Flash Point Autoignition Temp. 532 f'1'
F1 ammabi 1 ity Limits in Air (wt %) 'Lower Upper
Explosive Limits in Air (vol.X) Lower 2.8 Upper_
Solubility
Cold Water 20.8% (wt) at 20 C Hot Water 24-0% (wt-) Ethanol Soluble
Others: Soluble in ether
Acid, Base Properties Approx. Neutral
Highly Reactive with Highly flammable; subject to explosive polymerization
Compatible with Acetic acid (as inhibitor); Hydroquinone as inhibitor
Shipped in Iron, Steel, Copper, Metal
ICC Classification 28,29 Coast Guard Classification Flammable^1'
Comments Jdfa^ ' ^^e^ Chemical Co.; Union Carbide Corp. Chemical & Plastics
References (1) 0766
58
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PROFILE REPORT
Dimethyl Sulfate (160)
— T 0
1. GENERAL
Dimethyl sulfate is an extremely toxic, colorless, oily liquid. This
material is particularly hazardous because it has no characteristic odor or
other warning property and symptoms of exposure to the vapors or liquid often
do not appear for several hours after the event
lyzed by water to form corrosive sulfuric acid.
do not appear for several hours after the event. It is readily hydro-
The principal domestic manufacturer of dimethyl sulfate is E. I. du Pont
de Nemours, Inc., who probably produce it from dimethyl ether and sulfur
1492
trioxide. It is used as a reagent for the introduction of methyl groups
(methylating agent) in the manufacture of many organic chemicals.
The physical/chemical properties of dimethyl sulfate are summarized in
the attached worksheet.
2. TOXICOLOGY "92.0766 .
The use of dimethyl sulfate as a war gas is testimony for the hazardous
nature of this compound. The most dangerous property of this material is its
virtual lack of warning characteristics (e.g., odor, irritation) and the
delayed appearance of symptoms which may permit unnoticed exposure to lethal
quantities.
The liquid produces severe blistering and necrosis of the skin. Suffir
cient skin absorption can occur to give serious poisoning. Dimethyl sulfate
vapors, after a latent period of several hours, cause severe inflammation and
necrosis of eyes, mouth and respiratory tract resulting in pulmonary damage.
Systemic effects may include prostration, convulsions, delirium, paralysis,
coma and delayed damage to kidneys, liver and heart. Death may occur in
three or four days in cases of heavy exposure.
59
-------
•5
A Threshold Limit Value (TLV) (skin) of 1 ppm or 5 mg/M has been
1493
recommended for man. Dimethyl sulfate is also extremely toxic to
1492
other species. The ID™ (oral) in rats has been reported to be 440
mg/kg and the fatal concentration for cats and monkeys is in the range
of 25 to 200 ppm of the vapor in the air.
3. OTHER HAZARDS
Dimethyl sulfate hydrolyzes in the presence of water to form sulfuric
acid and methanol. A concentrated solution of sulfuric acid is extremely
corrosive to many materials and will react exothermically with bases.
Explosive reactions have been reported for mixtures of dimethyl
sulfate with ammonium hydroxide and with sodium azide.
Dimethyl sulfate will burn at temperatures above its flash point, but
under normal handling conditions there is little danger of fire. '
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Detailed procedures for the safe handling, storage and transportation
140-3
of dimethyl sulfate may be found in the MCA Safety Data Sheet SD-19.
The governing principle for the safe handling of dimethyl sulfate is the
scrupulous avoidance of any contact with liquid or vapor. The effectiveness
1493
of the methods and equipment designed for this purpose will depend
primarily on the effectiveness of employee education in their use.
Dimethyl sulfate is shipped in glass bottles and steel containers
as large as tank cars. It is classified by the Department of
Transportation and U. S. Coast Guard as a corrosive liquid, requiring
a white label. It is considered unacceptable for shipment by air
on passenger flights and is limited to one liter containers on all-cargo
flights.
-------
Disposal Reuse
Dimethyl sulfate may be purified by distillation at reduced pressure;
distillation at normal atmospheric pressure results in decomposition.
The dangers inherent to the handling of a material with the insidious char-
acteristics of dimethyl sulfate militate against the purification for reuse
of large quantities of the material by any but the most experienced
personnel.
An adequate process for the disposal of dimethyl sulfate must include,
as the first step, dilution with water to less than one percent concentra-
1493
tion. Dilution reduces the danger of accumulation of toxic quantities
and hydrolyzes the dimethyl sulfate to sulfuric acid and methanol. The
diluted solution should then be neutralized with base to reduce its corrosive
nature.
Recommended provisional limits for dimethyl sulfate in the environment
are as follows:
Basis for
Contaminant and Environment Provisional Limit Recommendation
Dimethyl Sulfate in 0.01 ppm or 0.05 0.01 TLV
Air mg/M3
Dimethyl Sulfate in 0.25 ppm (mg/1) Stokinger
Water and Soil . and Woodward
Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The preferred processing options for the disposal of dimethyl
sulate wastes are briefly described in the following subsections together
with judgements as to their adequacy.
61
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Option No. 1 - Incineration
The Manufacturing Chemists Association (MCA) recommends that dimethyl
sulfate be disposed of by incineration in properly designed and operated
1493
chemical waste incinerators. The MCA also recommends that the waste
be diluted and neutralized before disposal, whenever conditions permit.
Incineration of dilute ( 1%), neutralized dimethyl sulfate waste is
recommended as the best method for disposal of the material. The incineration
must be performed by trained and experienced personnel using equipment
properly designed to handle hazardous materials and equipped with efficient
oxides of sulfur scrubbing devices. These incinerators should expose the
waste material to a minimum temperature of 1,800 F for at least 1.5 seconds.
These conditions may be easily met through the use of afterburners.
Disposal of concentrated dimethyl sulfate wastes by direct incineration is
judged to be less acceptable for all but very small (laboratory) quantities
of material. The danger of exposure to vaporized, but unburned dimethyl
sulfate is significantly greater when the material is disposed of in
concentrated form and, therefore, requires the employment of specially
trained personnel operating properly designed and maintained equipment.
Option No. 2 - Waste Water Treatment
The use of biological waste water treatments methods for the disposal
of dimethyl sulfate are acceptable only for very dilute, neutralized waste
streams. These procedures are less satisfactory than-proper incineration
because of the danger of exposure to incompletely hydrolyzed dimethyl
sulfate.
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Dimethyl sulfate is judged to be a candidate waste stream constituent
for disposal at National Disposal Sites. The high toxicity and insidious
nature of this material will require careful handling by trained and
experienced personnel using well designed and maintained equipment.
Assurance that the criteria for the safe disposal of dimethyl sulfate
are met can best be dbtained at a facility specializing in the handling
of such difficult materials.
It is recommended, for the reasons outlined in Section 5, that
incineration of dilute, neutralized dimethyl sulfate wastes be,the disposal
method used at National Disposal Sites.
€3
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Book Corporation, .1968. 1,251 p.
1492. Merck and Company. The Merck index of chemicals and drugs. 7th ed.
Rahway, New Jersey, 1960. 1,643 p.
1493. Manufacturing Chemists Association. Properties and essential info-
rmation for safe handling and use of dimethyl sulfate. Safety
data sheet SD-19. Washington, 1966. 14 p.
1569. National Fire Protection Association. Manual of hazardous chemical
reactions. 4th ed. NFPA No. 491M. Boston, 1971. 308 p.
1570. Weast, R. C., ed. Handbook of chemistry and physics. 50th ed.
Cleveland, The Chemical Rubber Company, 1969. 2,100 p.
1571. Schnell Publishing Co. 1971-72 OPD chemical buyers guide. 59th ed.
New York, 1971. 1,584 p.
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dimethyl Sulfate (160)
IUC Name Sulfuric acid. Dimethyl ester
Common Names '^Methyl Sulfate. QMS
Structural Formula
(CH30)2 S02
Molecular Wt. 126.13
Melting Pt. -31.75 C
Density (Condensed) 1.3283
@ 20C/20C Density (gas) 4.35
Boiling Pt.188.5 C (d)
G(Air=l) _____
Vapor Pressure (recommended 55 C and 20 C)
15mm
076 C
(2)
Flash
(cc)
"C (oc)
Autplgnition Temp.
Lower
Lower
Upper_
Upper_
115.6
Flammabillty Limits in Air (wt %")
Explosive Limits in Air (wt. J)
Solubility^
Cold Water2.8 g/IOOml @ 18 C Hot Water Hydrolysis
Others: ether, dioxane. acetone, aromatic hydrocarbons
Acid, Base Properties Neutral when anhydrous, hvdrolyses rapidly in water to yield HrS
Ethanol soluble
Highly Reactive with Ammonium hydroxide.^ Sodium Azide/4^ Oxidizing
Compatible with Glass, stainless steel (in the absence of moisture)
Shipped iff ^Glass bottles, steel drums and tank cars
(5\Corrosive liquid
IT 'White label
ICC Classification Corrosive Liquid, white label Coast Guard Class1f1cat1oi
Comnents ?ATA classification: corrosive liquid, white label, not acceptable (passenger),
1 liter (cargo).t5' Source: DuPont
T5T
References (1) (1493)
(2) (1570)
(3) (1492)
(4) (1569)
(5) (0766)
(6) (1571)
65
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PROFILE REPORT
Pentachlorophenol (322)
1. GENERAL
Pentachlorophenol is a broad-spectrum biotoxicant available
commercially in the form of flakes and needle crystals. Because of its
high toxicity, it is also available in a prilled form and oiled grade to
1433
greatly reduce dust associated with the flakes and needles. The pure
material melts at 191 C and decomposes at 310 C.0766
Pentachlorophenol can be manufactured by the direct chlorination of
phenol and polychlorophenols. One commercial process uses a mixture
of phenol, £-chlorophenol,2,6-dichlorophenol, and 2,4,6-trichlorophenol as
the starting materials. Chlorination is carried out in the absence of
solvents and catalyst until tetrachlorination is achieved; at that point a
Lewis acid catalyst such as FeClg, A1C13, SbCK, etc., is added to
facilitate the incorporation of the fifth chlorine group. The progress of
the reaction is monitored by determining the freezing point of the product.
When the proper freezing point is achieved, the chlorination is stopped,
and the material is flaked and packaged. Pentachlorophenol is also
1433
manufactured by the hydrolysis of hexachlorobenzene with 5 to 15 percent
sodium hydroxide in methanol at 130 to 140 C. The hexachlorobenzene is
easily prepared by the liquid-phase, iron-catalyzed chlorination of benzene.
The textile industry uses pentachlorophenol to preserve rope, binder
twine, burlap, cable covering and rubberized canvas belting. It is also
utilized by the wood and construction industries to impart termite
resistance to wood and to control mold growth on lumber products and
building surfaces. The pentachlorophenol is generally incorporated in the
treating of materials such as whitewash or paints, or mixed with oil for
spray application. It also finds use in the leather industry to impart
:e to
1277
1512
temporary mold resistance to upper leather for shoes, and as a
fungicide and herbicide.
S7
-------
Domestic production of pentachlorophenol was reported as 47.2 million
pounds while the quantity sold was 45.8 million pounds for the year 1970,
the remainder being for captive use. Manufacturers of pentachlorophenol
are Dow Chemical Company, Monsanto Company, Reinhold Chemicals Inc., Sanford
1718
Chemical Company,.and Vulcan Materials Company.
2. TOXICOLOGY1512
Pentachlorophenol is capable of producing severe irritation and
corneal damage upon contact with the eye. A single short exposure to the
skin may cause some reddening, while repeated or prolonged contact may
cause severe irritation or burns. This material is readily absorbed through
the skin in toxic amounts, particularly from solutions, and is highly
toxic if swalloed. Dust concentrations which are hazardous are very irritating
to the nose and throat. The material is not likely to cause sensitization
nor should there be any problem from ingestion incidental to correct
industrial handling.
The Threshold, Limit Value (TLV) and maximum allowable concentration
is 0.5 mg/M3. LD,-n for rats is 125-210 mg/Kg orally and 150-350 mg/Kg
1977 ou
dermal. l£//
3. OTHER HAZARDS
Although pentachlorophenol has no fire or flash point, it is dangerous
when heated to decomposition. Decomposition takes place at 310 C with the
emission of highly toxic fumes of chlorides.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation1512
Safety glasses with side shields, or their equivalent, should be worn
when this material or its solutions are handled. Where the likelihood of
appreciable exposure to dust or strong solutions cannot be avoided, workers
68
-------
should wear appropriate protective devices, including underwear with full
length arms and legs, coveralls, or other outer garments covering the whole
body, cloth gloves, cap, and a dust respirator bearing the approval of the
U. S. Bureau of Mines for use with toxic dusts. Impervious sleeves with
elastic bands at either end, to fit over long gauntlet gloves, may be useful
for protecting the arms and wrists. For extensive manual operation it may
be necessary to utilize protective rubber gloves.
Disposal/Reuse
A definition of acceptable criteria for the disposal of pentachloro-
phenol must also take into account acceptable criteria for the release of
hydrogen chloride and hydrochloric acid to the environment, since current
practice in pentachlorophenol disposal involves some processes that reduce
pentachlorophenol to these materials.
Any method of safe disposal of this material must insure that the
concentration of pentachlorophenol, hydrogen chloride and hydrochloric
acid in the environment does not exceed the following recommended
provisional limits:
Contaminant and
Environment
Pentachlorophenol
released to the
atmosphere
Hydrogen chloride
released to the
atmosphere
Hydrochloric acid
released to the
atmosphere
Provisional Limits
0.005 mg/M-'
0.05 ppm (0.07 mg/MJ)
0.05 ppm (0.07 mg/M^)
Basis ot
Recommendation
0.01 TLV
0.01 TLV
0.01 TLV
Pentachlorophenol
in water
0.25 ppm (mg/1)
Stoklnger and
Woodward
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Little information is available from literature and industrial sources
pertaining to the disposal of pentachlorophenol waste streams. However,
pentachlorophenol is chemically and structurally similar to other
chlorophenoxy compounds such as 2S4-D (2,4-dichlorophenoxy acetic acid),
2,4,5-T (2,4,5-trichlorophenoxy acetic acid), and MCPA (2-methyl-4-
chlorophenoxy acetic acid), and it is therefore assumed that processes
applicable to those wastes are applicable to pentachlorophenol wastes.
The various processes for treating concentrated and dilute chlorophenoxy
waste streams are discussed in detail in the Profile Report covering
2,4-D (135). The salient points of those discussions are presented in
the following sections of this report.
Dilute Pentachlorophenol Wastes
Option No. 1 - Adsorption with Powdered Activated Carbon. The
addition of powdered activated carbon to dilute aqueous waste streams
followed by stirring and filtration has proven to be an adequate method
of low concentration chlorophenoxy compound removal. Studies have shown
that compounds such as 2,4-D and probably pentachlorophenol can be
removed with as high as 99 percent efficiency under certain processing
conditions (carbon dosage of 320 ing/liter, a pH of 6, and one hour contact
time as in the case of a 10 ppm 2,4-D waste stream). The carbon adsorbent
may then be collected for disposal or the pentachlorophenol may be removed
in rotary hearth incinerators equipped with hydrogen chloride scrubbers.
The activated carbon may then be recycled.
Option No. 2 - Adsorption with Granular Activated-Carbon Beds. This
method of treatment has been successfully utilized to treat wastewater
containing 2,4-D and 2,4,5-T with removal efficiencies as high as
99 percent. The concentrated chlorophenoxy compounds are removed from
the carbon adsorbent through controlled oxidation in rotary hearth
70
-------
incinerators with subsequent effluent scrubbing to remove chlorides.
Because the technology is proven and since it is a well established
chemical engineering unit operation, adsorption with granular activated-
carbon beds should be considered as one of the more satisfactory methods
for treating dilute pentachlorophenol wastes.
Option No. 3 - Biological Degradation. Biological degradation of
dilute waste streams containing dichlorophenol has been utilized. One
such process started with pretreatment of the waste stream by first
sending it through a crushed limestone filled neutralization ditch and an
in-plant equalization pond, and a final pH adjustment to 7.2 by automatic
addition of slaked lime slurry in a continuous stirred pit. The
wastewater, containing 2 to 4.2 mg/liter phenoxy acids, was then treated
in an aerated lagoon and stabilization pond system before discharge to a
receiving stream. Although the removal of chlorophenoxy acids by the
lagoon and pond system ranged from only 49 to 80 percent, the stabilization
pond effluent with typically 1.1 mg/liter chlorophenoxy acids was considered
to be good quality. This would indicate that streams containing
pentachlorophenol (instead of dichlorophenol) could possibly be biologically
treated, however more work needs to be done in this area to establish
proper processing parameters.
Option No. 4 - Ion Exchange. The use of ion exchange columns to
remove chlorophenoxy compounds such as the sodium salt of 2,4-D from
water has been examined. It was determined that when chlorophenoxy
compounds are neutralized to their sodium salts, that ion exchange can
remove concentrations as high as 120 mg/liter completely using strongly
basic anion resins. It would appear that ion exchange is an adequate
method for treating dilute pentachlorophenol wastes.
Concentrated Pentachlorophenol Wastes
Option No. 1 - Incineration. The complete and controlled high
temperature oxidation coupled with adequate scrubbing and ash disposal
facilities offers the greatest immediate potential for the safe disposal
71
-------
of concentrated pentachlorophenol. The research on incineration of
pestcides conducted by Kennedy et al at Mississippi State University has
led to the conclusion that chlorophenols approach complete oxidation
when combusted at temperatures in the 600 C to 900 C range with hydrogen
chloride being the only pollutant liberated. If proper aqueous or caustic
scrubbing systems are utilized, efficient abatement of the hydrogen chloride
can be achieved. Therefore, properly designed and operated incination is
considered the best present and near future method for the disposal of
concentrated pentachlorophenol.
Option No. 2 - Deep-Well. Although pentachlorophenol is only sparingly
soluble in water, its persistence and stability in water and the potential
contamination of ground water make deep-well at best a questionable method
for disposal. The method is not recommended by the National Working Group
on Pesticides, and should not be considered.
The disposal of pentachlorophenol wastes as well as other chlorophenoxy
wastes in open pits, lagoons, unapproved landfill sites, by application to
the soil surface, and by on site burning or deep sea burial are not
recommended practices because of the obvious potential contributions to
air and water pollution.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is anticipated that disposal systems to handle both dilute and
concentrated pentachlorophenol and similar compounds will be required at
National Disposal Sites located near manufacturers, users, and especially
agriculture centers in the near future. The dilute pentachlorophenol
wastes that will require treatment include spent cleaning solutions from
pentachlorophenol containers and any other contaminated wastewater. The
concentrated pentachlorophenol wastes that will require treatment include
any surplus, contaminated or fully degraded material.
72
-------
The processes recommended for the treatment of dilute pentachlorophenol
wastes at National Disposal Sites are:
Process Order of Preference Remarks
Activated-
Carbon Beds
Ion Exchange
Biological
First Choice
Second Choice
Third Choice
Proven technology on commercial
scale; also adequate for removal
of the sodium salt of penta-
chlorophenol and most other
types of pesticides from
wastewater.
Demonstrated technology; requires
preliminary conversion to the
sodium salt.
Demonstrated technology on
closely related compounds;
requires treatment in aerated
lagoons and stabilization ponds.
The processes for the treatment of concentrated pentachlorophenol
wastes at National Disposal Sites are:
Process Order of Preference Remarks
Incineration
First Choice
Demonstrated technology;
applicable to the disposal of
most organic wastes; possibility
of recovering chlorine in the
form of usable hydrogen chloride.
73
-------
7. REFERENCES
0766. Sax, N. Irvine. Dangerous properties of industrial materials.
Reinhold Publishing Corporation, New York, 1957. 1,467 p.
1277. Bailey, J. B. and J. E. Swift. Pesticide information and safety
manual. Berkeley, University of California, Division of
Agricultural Science, 1968. 147 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22v and suppl,
New York, Interscience Publishers, 1963.
1492. Merck and Company. The Merck index of chemicals and drugs. Rahway,
New Jersey, 1960. 1,043 p.
1512. Dow Chemical Company. Antimicrobial agents. Technical Bulletin 1-6.
Midland 1969. 5 p.
1570. The Chemical Rubber Company. Handbook of chemistry and physics.
47th ed., Cleveland, 1962. 2,100 p.
1718. U. S. Tariff Commission. Synthetic organic chemicals; United States
production and sales, 1970. T. C. Publication 479. Washington
D. C., U. S. Government Printing Office. 1971. 262 p.
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Pentachloroohenol
IUC Name Pentachlorophenol
Common Names Pentachlorophenol. genta Santophen 20.
Dowicide 7
Structural Formula
Molecular Wt. 266.35
(1)
Melting Pt. 190 c
2
(1)
Density (Condensed) 1.978 @ 22/4 C* Density (gas)_
Vapor Pressure (recommended 55 C and 20 0
5.5 @ 160 6?) 50 9 220
(1)
Boiling Pt._jUfl_C_Uficp)
S5Q
3QQ
Flash Point None
Autolgnltlon Temp._
Flammabillty Limits in A1r (wt %) Lower_ _
Fire point - none (3)
Explosive Limits in Air (wt. X)
Lower
Upper.
Upper_
(1)
Solubility
Cold Water Almost insoluble''' Hot Water
Others: Freely soluble in ethe/^ soluble 1n benzene
Acid, Base Properties Acidic. pK. = 4.86
Ethanol Freely
.(1)
Highly Reactive with_
Compatible with_
Shipped in Multiwall paper bags . fiber
ICC Classification
Comments LD,... orally in rats* ISO mn
Coast Guard Classification,
MAr• flrftyn- n c TI/M nf gir
References (1) 1492
(2) 1570
(3)
(4) 1433
75
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-h
3. Recipient's Accession No.
4. Title and Subtitle Recommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume VIII, National
Disposal Site Candidate Waste Stream Constituent Profile
Reports - Miscellaneous Inorganic and Organic Compounds.
5- Report Date
Issuing date - Aug. 1973
6.
7. Authors) R. $. Ottinger, J. L. Blumenthal, D. F. Dal Porto,
G. I. Gruber. M. J. Santv. and C. C. Shin
8. Performing Organization Kept.
No'21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089
12. Sponsoring Organization Name arid Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Fi nal
14.
15. Supplementary Notes
Volume VIII of 16 volumes.
16. Abstracts
This volume contains summary information and evaluation of waste management methods in
the form of Profile Reports for miscellaneous inorganic and organic compounds. These
Profile Reports were prepared for either a particular hazardous waste stream constituent
or a group of related constituents. Each Profile Report contains a discussion of the
general characteristics of the waste stream constituents, their toxicology and other
associated hazards, the definition of adequate management for the waste material, an
evaluation of the current waste management practices with regard to their adequacy, and
recommendation as to the most appropriate processing methods available and whether the
waste material should be considered as a candidate for National Disposal, Industrial
Disposal, or Municipal Disposal.
17. Key Words and Document Analysis. 17a. Descriptors
Inorganic Compounds
Organic Compounds
National Disposal Site Candidate
Antimony Pentafluoride
Antimony Trifluoride
Chlorine ;
Contaminated Electrolyte
Fluorine
Nickel Carbonyl
17b. Identifiers/Open-Ended Terms
Perchloric Acid
Acrolein'
Dimethyl Sulfate
Pentachlorophenol
Hazardous Wastes
I7c. COSATI Field/Group 06F; 06T; 07B; 07C; 07E; 13B; 13H; 19A; 19B
18. Availability Statement
Release to public,
- 76 -
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
82
22. Price
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