EPA 560/6-77-003
CHEMICAL MARKET INPUT/OUTPUT ANALYSIS
OF SELECTED CHEMICAL SUBSTANCES
TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION
TASK II. BIPHENYL AND DIPHENYL OXIDE
October 1977
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
EPA 560/6-77-003 TR 76-599
FINAL REPORT
CHEMICAL MARKET INPUT/OUTPUT
ANALYSIS OF SELECTED CHEMICAL' SUBSTANCES TO ASSESS
SOURCES OF ENVIRONMENTAL CONTAMINATION
TASK II: BIPHENYL AND DIPHENYL OXIDE
William M. Meylan
Philip H. Howard
Contract No. 68-01-3224 - Task II
SRC No. L1273-07
October 1977
Project Officer - Thomas E. Kopp
Prepared for:
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Document is available to the public through the
National Technical Information Service, Springfield,
Virginia 22151.
-------
NOTICE
This report has been reviewed by the Office of Toxic Substances, EPA,
and approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
-------
Table of Contents Page
I. Introduction 1
II. Historical Development and Future Outlook 2
A. Historical Development 2
1. Biphenyl 2
2. Diphenyl Oxide 4
B. Future Outlook 6
1. Biphenyl 6
2. Diphenyl Oxide 7
III. Market Input/Output Data 9
A, Production 9
B,. Importation 12
C,, . Exportation 13
D,, Use Patterns 13
IV. General Manufacturing and Production Technology 16
A,. Biphenyl 16
1. Thermal Dehydrogenation of Benzene 16
a. Manufacture 16
b. Production Volumes 19
c. Economics , 20
d. Environmental Management 20
e. Alternative Biphenyl 20
2. By-Product From Dealkylation of Toluene 21
a. Chemistry 21
b. Process Description 22
c. Production Volumes 25
d. Environmental Management 25
e. Economics 25
3. By-Product From Partial Oxidation of Benzene 26
a. Process Description 26
B,. Diphenyl Oxide 26
iii
-------
Table of Contents (Cont'd) Page
1. By-Product From Chlorobenzene-Phenol Process 26
a. Manufacture 26
b. Production Volumes 30
c. Shipping 31
d. Economics 31
e. Environmental Management 32
2. Catalysis of Phenol 32
a. Production Volumes 33
b. Environmental Management 34
c. Economics 34
V. Use and Use Process Technology 35
A. Biphenyl 35
1. Dye Carrier 35
a. Manufacture 35
b. Dye Carrier Use 38
c. Environmental Management 40
d. Areas of Use 41
e. Economics 41
f. Alternative Products 41
g. Alternative Processes 43
2. Biphenyl Fungicide in Fruit Packaging 43
a. Manufacture 44
b. Production Volumes 44
c. Economics 45
d. Environmental Management 45
e. Alternatives . 45
3. Polychlorinated Biphenyl (PCB) 46
a. Manufacture 46
b. Production Volumes 46
c. Economics 46
4. Alkylated Biphenyl 47
a. Isopropylbiphenyl 47
(i) Manufacture 47
iv
-------
Table of Contents (Cont'd) Page
(ii) Production Volumes and Uses 47
(ill) Economics 48
b. Methylbiphenyl 48
c. Ethyl- and Butylbiphenyl 48
5. Eutectic Heat Transfer Fluid 48
6. Polybrominated Biphenyl (PBB) 48
a. Manufacture 49
b. Production Volumes . 49
c. Economics 49
d. Alternatives 49
B, Diphenyl Oxide 49
1. Eutectic Heat Transfer Fluid 49
a. Users 51
b. Production Volumes 51
c. Economics 52
d. Environmental Management 52
e. Use Alternatives 52
fib
2. Dowfax^ 53
a. Manufacture 53
b. Production Volumes 55
c. Economics 55
d. Environmental Management 55
e. Alternative Products 56
3. Diphenyl Oxide Dye Carriers 56
a. Volume of Use 56
b. Economics 57
c. Environmental Management 57
d. Alternative Products 58
4. Perfumes and Soaps 57
a. Manufacture 57
b. Volume of Use 58
c. Economics 58
d. Environmental Management 59
e. Alternative Products 59
-------
Table of Contents (Cont'd) Page
5. Butylated Monochlorodiphenyl Oxide 59
a. Manufacture 59
b. Production Volumes 60
c. Environmental Management 60
d. Economics 60
e. Alternatives 61
6. Deeabromodiphenyl Oxide 61
a. Manufacture 61
b. Production Volumes 62
c. Economics 62
d. Environmental Management 62
e. Alternatives 63
7. Minor Commercial Uses of Diphenyl Oxide 63
a. Chloromethyldiphenyl Oxide 63
b. Methoxymethyldiphenyl Oxide 64
c. Pesticides 65
VI. Sources of Biphenyl and Diphenyl Oxide Occurring in Nature 67
A. Biphenyl 67
1. Petroleum 67
2. Foods 68
B. Diphenyl Oxide 68
1. Plants 68
VII. Generation of Biphenyl and Diphenyl Oxide By-Products 70
A. Biphenyl 70
1. Dealkylation of Toluene 70
2. Naphthalene Feedstocks 70
3. Coal Tar 72
4. Automobile Exhaust 73
B. Diphenyl Oxide 73
1. Caprolactam - Nylon Production 73
2. Bituminous Coal Tar 74
vi
-------
Table of Contents (Cont'd) Page
VIII. Material Balance - Exposure to the Environment 75
A. Biphenyl 75
1. Dye Carrier 75
2. Fungicide^. 75
3. Dowtherm^A 77
4. Creosote Oils 77
5. Petroleum 78
6. Naphthalene Feedstock and Toluene Dealkylation 78
By-Product, Unrefined
7. Coal-Tar, Excluding Creosote Oils 78
8. Automobile Exhaust 78
B. Diphenyl Oxide 78
1. Dye Carrier 78
2. Perfumes/gand Soaps 80
3. DowthernTA 80
IX. Environmental Perspectives ' 81
A. Occupational Exposure to Man 81
B. Release to the Environment 82
1. Biphenyl 82
a. Effectiveness of Biphenyl Waste Treatment 82
b. Environmental Chlorination of Biphenyl 84
2. Diphenyl Oxide 88
a. Effectiveness of Waste Treatment 88
b. Biodegradation 88
c. Bioconcentration 89
X. Environmental Assessment 90
A.. Biphenyl 90
B. Diphenyl Oxide 91
Appendix A - Physical Properties 93
Appendix B - Material Safety Data Sheets 96
REFERENCES 103
vii
-------
List of Tables • Page
III-l. United States Biphenyl Producers 10
V-l. Textile Chemical Specialty Firms Who Make Biphenyl Dye 37
Carriers
VIII-1. Estimated Environmental Releases of Biphenyl 76
VII1-2. Estimated Environmental Releases of Diphenyl Oxide 79
IX-1. Chlorination of Biphenyl Utilizing Water Renovation 86
Conditions
viii
-------
List of Figures Page
III-l. Annual Biphenyl Production (SRC Estimation) 11
III-2. 1976 Annual Biphenyl Use in the United States ^
III-3. Domestic Diphenyl Oxide Use in 1975 15
IV-1. Biphenyl From Thermal Dehydrogenation of Benzene 18
IV-2. General Process for Hydrodealkylating Toluene to Benzene 23
IV-3. Diphenyl Oxide From Chlorobenzene - Phenol Process 28
V-l. Polyester Fiber to Garment Flow Diagram 36
V-2. Dyeing and Finishing of Polyester Fabrics 39
V-3. Process Manufacture of Dowfax^ Solutions 54
IX-1. Reduction of Concentration Owing to Biodegradation - 85
Analysis of Culture Cells and Water
ix
-------
I. Introduction
Occupational exposures to the compounds biphenyl and diphenyl oxide (phenyl
ether) have been regulated by the Occupational Safety and Health Administration.
The standards established by OSHA are directed at protecting workers who might
be exposed occupationally to air vapors or particulates of biphenyl or diphenyl
oxide. Until recently, however, little thought has been given to the amounts
of biphenyl or diphenyl oxide that are released to the environment, and thus
indirectly result in human exposure or environmental damage. Of additional
concern are reports which have suggested that various PCS (polychlorinated
biphenyl) isomers are formed when sewage, which contains biphenyl, is discharged
to waste treatment plants utilizing chlorine for disinfection and deodorization
(Carlson et al., 1975; Gaffney, 1974, 1976; Johnsen, 1975). Biphenyl and
diphenyl oxide have also been shown to bioconcentrate several hundred times in
fish and, therefore, small concentrates in water may result in significant con-
centrations in fish. This report considers environmental sources of biphenyl
and diphenyl oxide and estimations of the amounts which may be exposed to the
environment.
-------
II. Historical Development and Future Outlook
A. Historical Development
1. Biphenyl
Biphenyl (diphenyl; phenylbenzene), (C,HC)0, was first reported in
0 _> L
1862 by Fittig, who prepared it by the action of metallic sodium on bromobenzene.
Berthelot prepared biphenyl in 1867 by passing benzene vapors through a red hot
tube. In 1875, Blichner found biphenyl in high-boiling fractions from coal-tar
distillation (Poffenberger, 1950).
In 1927, Theodore Swann of the Federal Phosphorus Co. was asked
to supply biphenyl in commercial quantities for use as a heat transfer fluid in the
refining of lubricating oils. He set up a pilot plant for this purpose. Soon
after, the chlorination of biphenyl assumed commercial importance when the Swann
Corp. developed the "Aroclor" series of PCB's (polychlorinated biphenyls); how-
ever, Monsanto took over the PCB production in the early 1930's. About that
©
time, Dow Chemical Co. entered the commercial biphenyl field with Dowtherm A,
a eutectic mixture of biphenyl and diphenyl oxide for use in heat transfer.
Historically, the two principal manufacturers of biphenyl have been the Monsanto
Co. and the Dow Chemical Co. (Versar, 1976; Poffenberger, 1965).
The earliest commercial reactors were vessels holding a bath of
molten lead at 750°C, through which benzene vapors were bubbled (Scott, 1933;
Durgin and Jenkins, 1933). Later reactors used electrical resistance heaters to
raise the temperatures above 650°C. The major technical problem was the tendency
of benzene to decompose at very high temperatures to give carbon and heavy tar
deposits which clogged the heat exchange surfaces. Practically all of the patents
covering the manufacture of biphenyl have been proposed as solutions to this problem.
-------
Patents have also been issued which identify biphenyl as a major
by-product of phenol produced by the partial oxidation of benzene (Porter, 1946;
Dundee, 1964). Biphenyl appeared on the U.S. market in 1964 which was refined
from this process (Poffenberger, 1965). However, biphenyl currently produced by
this method has little commercial importance due to the limited capacity of
phenol production via partial oxidation of benzene.
In the late 1960's the commercial potential of recovering a bi-
phenyl by-product formed when toluene is hydrodealkylated to benzene was realized.
Today, the biphenyl obtained from the dealkylated toluene by-product is the most
important commercial source of biphenyl. This apparently occurred due to large
available quantities of the low-cost by-product and a sharp demand for biphenyl
dye carriers. Approximately 70% of the current annual biphenyl production of
85 million pounds is obtained by refining the dealkylated toluene by-product
(SRC estimation). The remaining 30% of the biphenyl production is produced by
Monsanto1s process of thermally reacting benzene vapors.
The earliest uses of biphenyl involved heat transfer agents and
synthesis to PCB's. During the late 1940's, biphenyl began to be used as a mild
fungicide when coated on individual fruit wrappers, although the patent describing
this use was dated somewhat earlier (Mispley and Barber, 1940). More recently,
biphenyl has been impregnated onto paper pads used in closed fruit packages.
These fungicidal uses still exist today, but at a level which has slowly decreased
due to better transportation and refrigeration systems.
In the 1960's, biphenyl found use as a dye carrier for disperse
dye applications to polyester fibers. The use of biphenyl dye carriers has
accelerated so greatly in the past six years that this use represents the largest
-------
single application of biphenyl at present, consuming nearly 60% of the annual
biphenyl production of 85 million pounds (SRC estimation). Large quantities of
biphenyl, nearly 21 million pounds annually, are still being used for PCB manu-
facture; however, present legislation to eliminate PCB production will eli-
minate this use of biphenyl. Several million pounds of biphenyl are annually
destined for heat transfer fluids. Since 1970, alkylated biphenyls have become
commercially important, especially isopropylbiphenyl. Approximately 10 million
pounds of isopropylbiphenyl are annually produced, at present, for applications
in carbonless paper.
Commercial production of flame retardant PBB's (polybrominated
biphenyls), which began in 1970, was thought to have been terminated in November,
1974, a year after PBB's were mistakenly added to cattle feed in Michigan
(Mumma and Wallace, 1975). However, decabromo- and octabromobiphenyl were
commercially produced in 1975 and 1976 for export purposes (Neufeld et^ al^., 1977).
In 1976, about 130 thousand pounds of biphenyl were consumed in the production of
these two PBB products.
2. Diphenyl Oxide
Dr. Herbert H. Dow carried out experiments with diphenyl oxide
(phenyl ether, diphenyl ether, phenoxybenzene, DPO) in 1925-1926, using it as
a heat transfer fluid in a steam power process. These experiments eventually
led to the development of Dowtherm"^ A, a eutectic heat transfer mixture of
fS\
73.5% diphenyl oxide and 26.5% biphenyl, in the early 1930's. DowthemT*'A
has been a widely-used heat transfer fluid since that time.
-------
The original American patents describing diphenyl oxide pro-
duction were assigned to the Dow Chemical-Co. The first patent (Hale, 1930)
described the production of diphenyl oxide as heating equimolar amounts of
chlorobenzene and aqueous base, such as Na~CO_ or NaOH, under pressure with
copper catalysts. The second patent (Hale and Britton, 1933) refers to the Dow
process of phenol production from chlorobenzene and aqueous base. In this
process, diphenyl oxide is formed as a by-product. Historically, nearly all
of the diphenyl oxide produced in the U.S. has been obtained from the by-product
from Dow's chlorobenzene-phenol process. However, Monsanto has recently entered
the commercial diphenyl oxide market. A new Monsanto unit, completed in late
1975, produces high-purity diphenyl oxide in a one step process which involves
reacting phenol in the presence of a catalyst.
The only commercially important early use of diphenyl oxide,
®
other than for Dowthemr A heat transfer fluid, was for applications with per-
fumes and soaps. Diphenyl oxide has a characteristic geranium odor. Use in
perfumes and soaps is still important, with roughly 100,000 pounds annually
consumed. Historically, most of diphenyl oxide produced has been used to
formulate Dowtherm A. Roughly two-thirds of the estimated 6 million pounds
®
of diphenyl oxide produced in 1975 was used in Dowthernr^ A (SRC estimation).
Other commercially important current uses of diphenyl oxide
®
include Dowfax^ (alkylated sulfonated derivatives) surface-active agents, deca-
bromodiphenyl oxide flame retardants, diphenyl oxide dye carriers, and butyl-
chlorodiphenyl oxide capacitor fluid. Dowfax^production started in the early
1960's and decabromodiphenyl oxide and diphenyl oxide dye carriers started in
the 1970's. Butylchlorodiphenyl oxide is discussed in Future Outlook - Diphenyl
Oxide.
-------
Several diphenyl oxide derivatives, chloromethyl diphenyl oxides,
and methoxymethyl diphenyl oxide, have minor commercial uses in polymer and
resin production.
B. Future Outlook'
1. Biphenyl
The sizeable increase in biphenyl production from 1970 to the
present is primarily due to the dye carrier use of biphenyl in polyester dyeing.
Future increases in production may, therefore, be aligned with increases in the poly-
ester market. Several industry spokesmen are projecting an 85% increase in the
polyester market by 1980 and a 170% increase by 1985. Biphenyl, however, is
only one of perhaps eight to ten commercially important dye carriers used in
polyester dyeing. After consulting with industry spokesmen, it is estimated
(SRC estimation) that biphenyl dye carriers make up approximately 25-30% of the
total dye carrier market at present. The total dye carrier market is expected
to increase by 47% by 1980. This 47% figure is smaller than the 85% polyester
growth figure because technological improvements in dyeing techniques should
decrease the amount of dye carrier which is required.
_If_ biphenyl maintains 25-30% of the dye carrier market, an addi-
tional 20-25 million pounds of biphenyl will be used for dyeing by 1980. Present
biphenyl consumption in dye carriers is estimated at 50 million Ibs. annually
(SRC estimation).
Increased biphenyl consumption is also projected for heat transfer
(S)
fluids and alkylated biphenyls. Dow has announced an expansion of their Dowthernr^ A
units, to be completed by 1978 (Anon., 1976 a). In early 1976, Monsanto began
commercial production of Therminol VP-1 heat transfer fluid, which will compete
-------
with Dow's Dowtherm^A. Therminol VP-1 and DowthemP A have identical chemical
compositions. Isopropylbiphenyl, used in carbonless paper, and methylbiphenyl,
used as a dye carrier, are also expected to increase output by 1980. A guess
would project that nearly 10 million additional pounds of biphenyl will b,e used
for heat transfer and alkylation by 1980 (SRC estimation).
The projected phase-out of PCB's which is required by section 6e
of the Toxic Substances Control Act (PL 94-469) would decrease the needed
biphenyl production by nearly 21 million pounds annually. However, alternatives
to PCB's may include another biphenyl derivative. Effects to the biphenyl
market by the PCB phase-out cannot be ascertained at this time.
2. Diphenyl Oxide
There will be large increases in the production of diphenyl oxide
by 1980. Until the end of 1975, the only commercial quantities of diphenyl oxide
were obtained from Dow's chlorobenzene-phenol process as a by-product. This
amounted to approximately 6 million pounds annually (SRC estimation). However,
at the end of 1975, Monsanto began commercial production of diphenyl oxide for
use in Therminol VP-1 heat transfer fluid. Also, Dow has announced a $37 million
expansion of their chlorobenzene complex to be completed in 1978. This will in-
clude expansion of diphenyl oxide production, primarily for use in butylchloro-
©
diphenyl oxide, but also for Dowthernf^A and decabromodiphenyl oxide (Anon., 1976 a)
An estimated $10 million of this expansion had been completed by April, 1976.
The primary reason for Dow's diphenyl oxide expansion appears to
be synthesis of butylchlorodiphenyl oxide. Dow is hoping that butylchlorodiphenyl
oxide will be widely accepted as a PCB replacement in capacitors. McGraw-Edison,
a capacitor manufacturer, has totally converted to the use of this Dow product in
-------
1976, making a reality of commercial production. Dow says it hopes to have
production capacity in excess of 5 million Ibs/year of butylchlorodiphenyl
oxide by the end of 1976 (Anon., 1976b). If this 5 million Ib figure proves
correct, then diphenyl oxide production in the U.S. will have doubled in a
year's time. The degree of diphenyl oxide expansion in the future may be
determined by industry's acceptance of butylchlorodiphenyl oxide as a PCB
substitute. It should be noted, however, that other companies are developing
and evaluating PCB substitutes different from butylchlorodiphenyl oxide.
-------
III. Market Input/Output Data
A. Production
Table III-l lists the domestic producers of refined biphenyl with their
respective production sites, years, and capacities. Also listed in Table III-l
are the petrochemical companies who commercially supply unrefined biphenyl feed
stock (by-product from toluene dealkylation) to biphenyl refiners. Annual bi-
phenyl production is shown in Figure III-l.
Two companies have stopped refined biphenyl production. First is Geneva
Industries of Houston, Texas, who sold their biphenyl refinery to Pilot Industries
in 1974. Second is Bethlehem Steel Corp. of Sparrows Point, Maryland, who termi-
nated biphenyl refining in 1974.
The Dow Chemical Co. and Monsanto Industrial Chemicals Co. are the only
domestic producers of diphenyl oxide. The Dow production site is located in
Midland, Michigan, while Monsanto's site is located at their Chocolate Bayou
facility in Alvin, Texas. Dow has been involved in the production of diphenyl
oxide since the early 1930's. Monsanto began commercial production at the end
of 1975.
Dow did not release their annual production volumes, as the information
is considered confidential (Otis, 1976). However, before the current diphenyl
oxide expansion, Dow obtained all of their diphenyl oxide as by-products from
their chlorobenzene-phenol process. Capacity of this phenol process has been
estimated at 48-70 million pounds annually (SRI, 1975 a, 1976). Since approxi-
mately 0.1 pound of diphenyl oxide is formed for every 1.0 pound of phenol
formed (Hahn, 1970), the annual diphenyl oxide output would be 4.8 to 7.0 million
pounds; and, therefore, 6 million pounds may be a good estimate of the annual
-------
Table III-l. United States Biphenyl Producers
Refined Biphenyl Producers - 1976
Producer . .
1.
2.
3.
4.
5.
6.
7.
8.
Chemol , Inc .
CPS Chemical Co., Div. of
Chemistry & Pollution
Sciences
Dow Chemical Co.
East Coast Chemical Co.
Monsanto Industrial Chemicals
Pilot Industries
Sun Oil of Penn. (Suntide)
Sybron Corp., Tanatex
Chemicals Div.
Production Site
Greensboro, NC
Old Bridge, NJ
Bay City, MI
Cedar Grove, NJ
Anniston, AL
Houston, XX
Corpus Christi, TX
Lyndhurst, NJ
Years Estimated Capacity (x 10 Ib/yr)
1972
1971
1974
1933
1974
1970
1971
- Present
"""
- Present
- Present
- Present
- Present
- Present
- Present
5
< 1
10 -
1-4
45
15 -
10 -
10
20
20
20
Biphenyl Feed Stock Producers - Commercially Available Product
1. Coastal States Gas Producing
Co.
2. Cosden Oil and Chemical Co.
3. Dow Chemical Co.
4. Gulf Oil Corp.
Corpus Christi, TX
Big Spring, TX
Bay City, MI
Philadelphia, PA
-------
«
r^
I
120-r
£
Q.
m
100 H
90-
80-|
70-|
60-|
50H
40H
30
84.6
PCB Production Cut—Back
Considers PCB Ban
O Data From United States International Trade
Commission,"Synthetic Organic Chemicals"
—I 1 1 1 1 1 1 1 1 1 1 I I I I I I
1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982
Year
Figure III-l. Annual Biphenyl Production (SRC Estimations)
-------
capacity. Of course, that figure is somewhat higher currently, depending upon
how much of the chlorobenzene expansion has been completed.
The production capacity of Monsanto's facility for diphenyl oxide is
considered proprietary and has, therefore, not been obtained. Monsanto produces
diphenyl oxide by reacting phenol with catalyst.
B. Importation
Prior to 1974, there is no record in the literature of any importation
of biphenyl or diphenyl oxide. However, the 1974 edition of "Imports of Benzenoid
Chemicals and Products" (United States International Trade Commission) lists the
following imports:
Biphenyl 10,758 pounds
Phenyl Ether (Diphenyl Oxide) 43,201 pounds
It should be noted that this reference source includes only surveys conducted
at the major ports of entry. The above quantities are relatively insignificant
when compared to the total biphenyl and diphenyl oxide consumption in the United
States; they represent less than 1% of the yearly consumption.
"Imports of Benzenoid Chemicals and Products" (1967-1974 editions)
also list imports of unspecified "textile assistants" ranging from 1.4 to 4.7
million pounds annually. The chemical ingredients of these textile assistants have
not been determined by SRC. It is possible that some of these textile assistants
are biphenyl dye carriers, although it would be surprising if more than one million
pounds of biphenyl are imported via this route.
It is also possible that quantities of biphenyl and diphenyl oxide are
@\
imported as heat transfer fluids with compositions identical to Dowthernr'A.
These heat transfer fluids, made overseas, are listed in Section V-B-1; quantities
which may be imported were not obtainable.
12
-------
C. Exportation
No figures revealing export quantities of biphenyl or diphenyl oxide
were available. After consulting with industry spokesmen, it is believed that
small quantities of biphenyl dye carriers are exported to Canada and Mexico.
Also, biphenyl fungicide pads are used for overseas shipments of fruit, but
this quantity is less than a million pounds. Overseas exportation, in bulk
quantities, appears to be virtually unknown.
D. Use Patterns
Figure III-2 and Figure III-3 diagram the 1976 uses of biphenyl and
1975 uses of diphenyl oxide, respectively. Quantities used in each application
are included where known or estimated.
13
-------
i
Biphenyl •
-*• Dye Carriers
-»• Heat Transfer
Derivatives
0.6-0.8
-»• Dowtherm ® A
-»• Therminol VP-I
21
•*-PCB's
9 Alkylated
Biphenyls
-*• Fruit Paper Fungicide
Methylbiphenyt
Ethylbiphenyl
Isopropylbiphenyl
Butylbiphenyl
Dye Carrier
Heat Transfer
Carbonless Paper
• Heat Transfer
Note:
All Figures Indicate Biphenyl Consumption x 10s Ibs.
and are SRC Estimations.
Figure III-2. 1976 Annual Biphenyl Use in the United States
-------
i
Diphenyl
Oxide
0.25
Dye Carrier
-*• Heat Transfer
Derivatives
0.1
Dowtherm ® A
Therminol VP —I
•*• Chloromethyldiphenyl oxide
—'•—^ Di(chloromethyl)diphenyl oxide
—'—»• Methoxymethyl diphenyl oxide
0.75
• Oecabromodiphenyl oxide •
-»• Butylchlorodiphenyl oxide
0.75
-*• Polymers, Foams
Polymers, Foams
-*• Dory' resins
•*• Fire retardant
Capacitor fluid
Dowfax ( Dodecyldiphenyloxidisulfonic acid, Disodium salt)
•*• Perfumes and Soaps
Surface—active agents
Note:
All Figures Indicate Diphenyl oxide Consumption x 106 Ibs.
and are SRC Estimations.
Figure III-3. Domestic Diphenyl Oxide Use in 1975
-------
IV. General Manufacturing and Production Technology
A. Biphenyl
1. Thermal Dehydrogenation of Benzene .
Monsanto Industrials Chemicals Co., located in Anniston, Alabama,
is the only current biphenyl producer to use the thermal dehydrogenation of
benzene process. Both Monsanto and Dow began using the process in the 1930's;
however, Dow termination their process in 1968 in favor of biphenyl production
from dealkylated toluene.
a. Manufacture
The chemistry involved in the thermal dehydrogenation of
benzene is shown in the following reaction:
(0.08%)
+ Higher
Polyphenyls
(2%)
+ H_ + Carbon
(4.9%)
At temperatures of 700-850°C, benzene reacts by a homogeneous gas-phase reaction
(in which a benzene molecule joins with another benzene molecule or with a poly-
phenyl molecule, liberating hydrogen and forming biphenyl or higher polyphenyls)
or by a heterogenous gas-solid phase reaction, giving carbon and hydrogen. Most
process development work has been directed to repressing the second reaction, which
is catalyzed by metals, particularly iron, copper, and nickel (Poffenberger, 1965).
16
-------
Figure IV-1 illustrates the typical process method of
biphenyl production from thermal dehydrogenation of benzene. The raw material
benzene and recycled benzene are vaporized and heated to about 600°C and then
injected into a thermal reactor at 1-2 atm. pressure. The reactor raises the
temperature to 700-850°C, the time of exposure to the higher temperatures being
on the order of one second. Under these conditions, a well-designed thermal
reactor yields a condensed product containing 12-15% by weight of biphenyl,
terphenyl, and polyphenyls corresponding to approximately 20% by weight of the
biphenyl, and the remainder as unreacted benzene. The yield of biphenyl, based
on benzene consumed, should be 80-85% of theory. The yield of biphenyl plus
terphenyl and other polyphenyls should be 90-95% of theory. At a 15% conversion
per pass, the yield of biphenyl is 0.80 Ib and that of terphenyl, etc. is 0.12 Ib
per pound of consumed benzene. The mechanical loss of benzene is 0.02-0.04 Ib
per pound of consumed benzene (Poffenberger, 1950, 1965).
The product from the reactor is condensed in a heat exchange
system and then distilled to drive off the benzene which is recycled. The
i
biphenyl-rich still residues are then vacuum distilled to separate the biphenyl
from the terphenyls, etc. Benzene in the noncondensable gas (mostly hydrogen)
vented from the heat exchange system is recovered either by compression or
activated charcoal adsorbers. All of the benzene is passed through the heat
exchangers to raise the benzene temperature and to cool the reactor products'
temperature (Sanders and Slocombe, 1955; Poffenberger, 1950, 1965).
Heat is generated in the thermal reactor by means of electrical
resistance elements. At temperatures above 650°C, benzene has a tendency to
decompose to give carbon and heavy tar deposits which coat heat exchange surfaces.
17
-------
Benzene
H2Gas
Compressor
or
Activated
Charcoal
00
Gas Vent f .
Benzene
Feed'
Distill
Column
Biphenyl.-Polyphenyl
12-15% Biphenyl
1 -5% Polyphenyls
80-85% Benzene
Thermal
Reactor
*> Biphenyl
8% o—Terphenyl
49%m-Terphenyl
23%p-Terphenyt
20% Triphenylene, Quaterphenyls, etc.
To
Terphenyl
Processing
(Adapted from Poffentaerger 1950.1965; Sanders and Slocomtae. 1955]
Figure IV-1. Biphenyl From Thermal Dehydrogenation of Benzene
-------
Metal surfaces made of iron, nickel, or copper catalyze this carbon formation;
therefore, metal surfaces are coated with carbide, nitride, or oxide to reduce
the catalytic effects (Prutton, 1940; Moose and Pritchard, 1934).
The following shipping information is available (Monsanto
Technical Bulletin 1C/FF-29):
Shipping Classification (U.S.)! Diphenyl (phenyl benzene)
Labelling: Product label
Standard Containers: 50 Ib net multiwall bags
260 Ib net fibre drums
Tank trucks
Tank cars
b. Production Volumes
Monsanto is the only domestic biphenyl producer currently
utilizing thermal dehydrogenation of benzene. Most of the biphenyl presently
made by Monsanto is captively used to produce PCB's (SRC estimation). Approxi-
mately 21 million pounds of biphenyl are required for the annual PCB production
of 40 million pounds. Additionally, slightly less than one million pounds of
biphenyl may be supplied by Monsanto for fungicidal purposes (SRC estimation).
Monsanto has also just begun production of a heat transfer fluid called Therminol
VP-1, which is an eutectic mixture of 26.5% biphenyl and 73.5% diphenyl oxide.
Several million pounds of biphenyl may be required for annual production of
Therminol VP-1.
The capacity of Monsanto's Anniston, Alabama biphenyl unit
is probably twice that of current utilization. In 1970, Monsanto produced 85
million Ibs of PCB's (Versar, 1976), which would require approximately 44 million
pounds of biphenyl. After 1970, Monsanto restricted PCB sales to closed system
uses; hence, production was cut approximately in half.
19
-------
c. Economics
The current (1976) selling price of Monsanto's biphenyl is
$0.36/lb; however, most is captively used in synthesis of PCB's.
To estimate the raw material cost to produce biphenyl via
thermal dehydrogenation of benzene, the yields previously described have been
assumed: 1 Ib of consumed benzene yields 0.80 Ib biphenyl and 0.12 Ib terphenyl,
etc. Also, the current selling price of benzene is $0.80/gallon or $0.11/lb.
Therefore, one pound of biphenyl consumes $0.136 worth of
benzene raw material. Additional costs must be added for equipment, labor,
insurance, transportation, etc.
d. Environmental Management
The only wastes from the process are the crude still pot
residues, which will be high molecular weight hydrocarbons, tars, and carbon.
It is very likely that a small amount of biphenyl will be present in these
residues; however, a chemical composition breakdown of the still pot residues
was not available. Also, the environmental fate of these residues was not
determined, but it is suspected that the residues are burned for fuel purposes
or used in coking operations. Due to the nature of the process, large amounts
of biphenyl cannot be released to the environment and any amounts which may be
released are very much smaller than amounts released by the dyeing industry.
e. Alternative Biphenyl
The advantage of Monsanto biphenyl is the purity, a very
high-grade product compared to biphenyl normally produced from dealkylation
of toluene. The disadvantage is price, $0.36/lb compared to $0.16-$0.25/lb
for dealkylated toluene biphenyl. Since the lower-grade biphenyl is suitable
for dye carrier application, Monsanto1s biphenyl is not very competitive for
this large quantity use.
20
-------
2. By-Product From Dealkylatlon of Toluene
The companies listed below are all currently refining biphenyl
from a by-product obtained when toluene is hydrodealkylated to benzene:
Chemol, Inc. Greensboro, NC
Dow Chemical Co. Bay City, MI
East Coast Chemical Co. Cedar Grove, NJ
Pilot Industries Houston, TX
Sun Oil of Penn. Corpus Christi, TX
Sybron Corp., Tanatex Chemical Div. Lyndhurst, NJ
Dow Chemical and Sun Oil generate their own by-product, while the
other companies listed above purchase the by-product feedstock from one of the
following petroleum companies: Coastal States Gas Producing Co. (Corpus Christi,
TX), Cosden Oil and Chemical Co. (Big Spring, TX) , Dow Chemical (Bay City, MI),
or Gulf Oil Corp. (Philadelphia, PA).
a. Chemistry
Hydrodealkylation involves the removal of one or more alkyl
groups from alkylbenzenes to produce high-grade benzene as the end product. The
reactions are carried out either thermally or catalytically in the presence of
excess hydrogen at elevated temperatures and pressures. When toluene is used
as the starting material, the. principal hydrodealkylation reaction leading to
the selective product formation of benzene is:
(1) . LL "*" H2 - + CH4 (Doelp, 1966)
The types of reactions contributing most to the nonselective product formation
are the following:
21
-------
(2)
(3)
H.,
(biphenyl)
(methylbiphenyl)
(4)
D.
+ 2H,
(fluorene)
Figure IV-2 illustrates the general process for hydrodealkylating
toluene to benzene. The various companies employ slightly different techniques
to accomplish the basic operations; however, the overall processes are quite
similar.
The toluene feed and hydrogen-rich gas are heated to an elevated
temperature and pumped into a tubular reactor of 400 - 1000 psig pressure and
811 - 1033°F temperature. The hydrogen-to-toluene mole ratio is 4-12. This
stoichiometric excess of hydrogen helps to suppress the non-selective reactions.
Contact time in the reactor averages 20-80 seconds (Doelp, 1966). Catalysts
are used in several processes.
22
-------
10
Toluene Feed
Hydrogen—rich Gas •
Fuel Gas
Reactor
Biphenyl
Products
94-97% Pure
Distill
Column
Benzene Product
Bottoms: Biphenyl 40-70%
Fluorenes
Methylbiphenyl
Toluene
Anthracene
Pyrene
Residues to
Fuels or Coking
Figure IV-2. General Process for Hydrodealkylating Toluene to Benzene
-------
The product from the reactor is condensed through heat ex-
changers and the fuel gas (hydrogen and methane) is vented off for fuel uses.
Benzene is separated from the non-selective products by fractional distillation.
The yield of benzene from toluene is greater than 95% of theoretical.
The bottoms residue from the benzene fractionator will vary
slightly from company to company. However, an average composition for this
residue would be (Earhart, 1976; Derrig, 1976; Doelp, 1966):
Biphenyl 50%
Toluene 15-20%
Fluorenes 10-15%
Methyl biphenyls 5%
Anthracene 3%
Pyrene 3%
Other Aromatic 9%
Hydrocarbons
The weight of the bottoms residue is approximately 2% of the weight of toluene
feed. Therefore, approximately one pound of biphenyl is formed for every 100
pounds of toluene which is dealkylated.
These bottoms from the benzene fractionator have two uses.
Economically, the best use is to refine the biphenyl or sell the bottoms to
biphenyl refiners (if the refined biphenyl can be sold). Otherwise, these
bottoms are usually added to fuel oils and burned as fuels.
The biphenyl is refined from the other hydrocarbons in the
benzene fractionator bottoms by distillation. A biphenyl product of 95-97%
purity is commonly obtained, which is quite suitable for use in dye carriers.
The residues from the biphenyl distillation are either added to fuels or used
in coking operations.
Bulk shipments of biphenyl to customers is done via railway
or truck tankers in a molten state (biphenyl melts at 69°C).
24
-------
c. Production Volumes
Estimated capacities of the biphenyl refiners are listed
in Table III-l, p. 10. Roughly 60 million pounds of refined biphenyl are currently
being obtained from dealkylated toluene (SRC estimation). Ten years ago, the
figure was very nearly zero. The sharp increase has come since 1970.
d. Environmental Management
The nature of this production method limits biphenyl release
to the environment to virtually nothing. More biphenyl is probably spilled
during loading of tankers than released in plant effluents (Earhart, 1976).
Appendix B contains Material Safety and Handling Sheets.
e. Economics
The biphenyl by-products from toluene dealkylation have
become available recently due to economic considerations concerning benzene.
The price of benzene has risen from $0.22/gallon in 1970 to nearly $0.80/gallon
in 1976. With the current price of toluene in the $0.55/gallon range, the
profit potential of obtaining benzene by simply dealkylating toluene can be
appreciated. Some of the dealkylation units idled or cut-back in 1970 are now
running nearer to capacity and new units are being installed. This increase in
dealkylation of toluene has resulted in a biphenyl by-product from which profits
can be realized. Therefore, the.biphenyl by-product has found use as fuel
additives or as a refined product.
The biphenyl by-product can be sold to biphenyl refiners for
$0.35 per gallon of which approximately 50% by weight is biphenyl (Derrig, 1976).
The biphenyl content of the by-product would, therefore, have a selling value
of about $0.085/lb. The refined biphenyl can be sold to dye carrier manufacturers
25
-------
for $0.16-$0.25/lb., depending upon the purity. This would indicate that re-
fined biphenyl obtained from dealkylation of toluene accounts for annual sales
of $10-15 million. The quoted prices for this biphenyl in 1973 was $0.03-$0.07
less per pound than current prices.
A number of petrochemical companies produce a biphenyl by-
product from dealkylating toluene, but do not refine the biphenyl and do not sell
it to refiners. They use it only as an additive to fuel oils. These companies
and the quantities of biphenyl put in fuel oils will be discussed in Section
VII-A-1.
3. By-Product From Partial Oxidation of Benzene
CPS Chemical Co. of Old Bridge, NJ is currently refining small
quantities of biphenyl from a by-product obtained when phenol is formed by
partial oxidation of benzene. Production volumes of this refined biphenyl are
much less than one million pounds annually.
a. Process Description
A vapor phase mixture of benzene and oxygen are passed
through a tubular reactor of 0.5 - 2.0 atm. pressure and 600-800°F. Of the
benzene which reacts, 43% yields phenol, 25% yields biphenyl, and the rest
yields gaseous products (Porter, 1946). The biphenyl is obtained by distillation.
This process for the production of phenol is so minor a
commercial method that it receives virtually no mention in the available
literature.
B. Diphenyl Oxide
1. By-Product From Chlorobenzene-Phenol Process
a. Manufacture
26
-------
The Dow Chemical Co., plant site located in Midland, MI,
produced diphenyl oxide as a by-product from their phenol production via ehloro-
benzene until the phenol operation was shut-down in 1975. This entire process
is illustrated in Figure IV-3.
Brine undergoes electrolysis to produce hydrogen gas,
chlorine gas, and caustic soda (NaOH). The chlorine is used to chlorinate
benzene to monochlorobenzene. A one mole ratio of monochlorobenzene and a 2-2 1/2
mole ratio of a 10-15% aqueous caustic soda solution are then introduced into a
high pressure pump along with a small percentage of diphenyl oxide. The di-
phenyl oxide is added to repress its own formation during the hydrolysis reaction.
It should be noted that the quantity of diphenyl oxide produced as by-product
can be partially controlled by the quantity of diphenyl oxide recycled to the
high pressure pump. It provides a degree of flexibility to a process designed
primarily for the production of phenol. Other materials added to the reactants
in comparatively small quantities are anticorrosion agents (amines), emulsifiers
(hydroxydiphenyl), and a catalyst (copper salts) (Faith et^ al., 1965).
The reactants are then pumped through a nickel-lined,
counter-current heat exchanger which raises the reactants' temperature to
275-300°C. The flow is injected into a continuous-flow tubular reactor of
4000-5000 psi pressure and heated to 400°C. Contact time is usually 15-20
minutes at the 400°C temperature. The selective and non-selective reactions
which occur in the reactor are the following:
Cl
i
(selective)
I s—\ 1
2NaOH
Na
H20
ONa
(non-selective)
+ NaCl
27
-------
NI
oo
Brine
Technical Grade
Diphenyl Oxide
Benzene-Phenol
Mixture
NaCI Layer (aq I
Figure IV-3. Diphenyl Oxide from Chlorobenzene - Phenol Process
-------
When leaving the reactor, the reaction products are passed
through the heat exchanger once again, to warm the incoming reactants and to
cool the reaction products. The reaction products are then allowed to settle
in a density separator. Two phases are obtained: (1) an aqueous sodium phenoxide
phase, and (2) an oil phase consisting principally of diphenyl oxide and un-
reacted monochlorobenzene. The oil is distilled to produce diphenyl oxide and
the monochlorobenzene is recycled to the reactor. The aqueous sodium phenoxide
layer is passed to a neutralizer and treated with hydrochloric acid prepared
from the HC1 gas by-product from the chlorinator. The neutralization reaction
which produces phenol is:
!)Na OH
Qj + HCl(aq) -> [Q
NaCl
The product from the neutralizer is density separated to
produce an aqueous NaCl layer and a phenol-rich layer. The phenol layer is
distilled to obtain USP grade phenol. The NaCl layer is extracted with benzene
to remove phenol content, and the NaCl solution is returned to the electrolytic
cell. The phenol-benzene mixture is distilled to obtain high-purity phenol
(Poffenberger, 1968; Faith et^ al., 1965).
The overall yield of phenol based on monochlorobenzene is
90-95% by weight. Conversion per pass through the reactor is 35-45% (Faith
et^ al^., 1965). Approximately 0.1 pound of diphenyl oxide is formed per pound
of phenol formed (Hahn, 1970), but additional diphenyl oxide will be produced if
it is not introduced into the high pressure pump to limit the non-selective
reaction. Small amounts of ortho and para-phenylphenol are formed as by-products
during the neutralization and are separated from the phenol-rich layer during
29
-------
distillation. Ortho-phenylphenol is used as a dye carrier and as an active
(R)
ingredient in Lysoi^ cleaner.
The diphenyl oxide obtained from the initial distillation
of the oil-layer from the reactor is a "technical" grade diphenyl oxide. This
technical grade can be purified to Dow1s "perfume" grade diphenyl oxide. Puri-
fication can be done by crystallization from solution in methyl alcohol (Britton
and Reed, 1933). The technical and perfume grades differ only slightly in odor,
the distinction being apparent only to individuals trained in screening by ol-
factory response. Dow also offers an "industrial" grade diphenyl oxide. This
industrial grade is intended for use as a dye carrier, and assays about 90%
diphenyl oxide (Dow Form No. 11028872). The additional 10% makeup is primarily
naphthalenes and methyl naphthalenes (also effective dye carriers).
b. Production Volumes
Production quantities of diphenyl oxide from the Dow facility
are considered confidential information (Otis, 1976), and cannot be obtained.
However, the now defunct (terminated in 1975) phenol capacity of Dow's chloro-
benzene process had been estimated at 48-70 million pounds annually (SRI, 1975,
1976). Since approximately 0.1 Ib of diphenyl oxide are formed per pound of
phenol formed, the annual diphenyl oxide capacity could have been 4.8-7.0 million
pounds. Therefore, up to 1975, the annual diphenyl oxide production from this
process is estimated at 6 million pounds.
The Dow chlorobenzene and diphenyl oxide facilities at
Midland, MI are currently undergoing revision and expansion to be completed in
1978. Ten million dollars of the total $37 million expenditure for this re-
vision and expansion have been completed to date (Anon., 1976 a). Estimates of
future diphenyl oxide capacities are not available.
30
-------
c. Shipping
The technical and industrial grades of diphenyl oxide are
shipped via tank cars and tank trucks in a molten state. Freezing point of the
molten diphenyl oxide is approximately 80°F, so only minimal heating from steam
coils is required to maintain a molten form. Size of the tankers can range from
4,000-10,000 gallon railway tankers to 5,000 gallon trucks. No extra-ordinary
precautions are required during shipping.
Technical grade diphenyl oxide can also be shipped in black
iron drums of 55 gallon capacity. Perfume grade diphenyl oxide is shipped in
55 gallon galvanized steel drums. These drums are equipped with dip pipes for
convenient removal of the diphenyl oxide in molten form. Drum warmers may be
required to obtain the molten state.
d. Economics
The following selling prices (1976) are for bulk shipments
of diphenyl oxide:
industrial grade $0.52/lb
technical grade $0.60/lb
perfume grade $0.85/lb
However, the large percentage of Dow's diphenyl oxide
production is captively used to make Dowthenn"'A, Dowfax*^ surfactants, butyl-
chlorodiphenyl oxide, and decabromodiphenyl oxide. Since the diphenyl oxide is
obtained as by-product, cost estimations are difficult.
In the expansion and revision of the chlorobenzene pro-
cesses now underway at the Dow Midland facility, phenol production via
chlorobenzene will be eliminated in favor of phenol production from cumene.
31
-------
This would indicate that diphenyl oxide will be prepared directly from chloro-
benzene and caustic soda. Dow held the original patent describing diphenyl
oxide manufacture by this direct route (Hale, 1930). The chemistry of this
reaction is:
Cl
o ff\] j. oxT nu Cu Catalyst^ /^\\ /^X
2 K)l + 2NaOH — ^-^((jAKCj) + 2NaC1
The current selling prices of chlorobenzene and sodium hydroxide are $0.29/lb and
$0.125/lb, respectively (Chemical Marketing Reporter, 1976). At a 90% yield,
one pound of formed diphenyl oxide would consume $0.49 of raw materials. Since
Dow makes the chlorobenzene and NaOH, cost would be considerably less than the
selling price.
e. Environmental Management
All diphenyl oxide-phenolic product losses in the sewer are
treated by the Dow Chemical, Michigan Division, Waste Treatment Plant (Otis, 1976).
Treatment efficiency for the diphenyl oxide in the Dow treatment plant is unknown.
2. Catalysis of Phenol
Monsanto Industrial Chemicals began producing diphenyl oxide at
their Chocolate Bayou complex in Alvin, Texas in late 1975. Monsanto did not'
reveal any details concerning their process except that the overall process
involves reacting phenol with catalysts.
The original description of producing diphenyl oxide by catalyzing
phenol is contained in a German patent (SchOllkopf, 1929). The patent describes
phenol as being heated to 350°C in an autoclave with activated fuller's earth to
32
-------
give a 15% yield of diphenyl oxide. The process presently being used by Monsanto
may be very similar. Undoubtedly, superior catalysts and techniques have been
developed to increase reaction yields and rates which make the process economi-
cal. A simple flow-diagram illustrating this process would be:
Phenol
Feedstock
Recycled Phenol
Water
High-Grade —
Diphenyl Oxide
Low-Grade
Diphenyl Oxide Bottoms
2 C,HCOH-
O D
The selective chemical reaction should be:
catalyst -s. ,„ „ N _
H20
The diphenyl oxide grade produced by Monsanto is 99.9% pure
(Monsanto Technical Sheet IC/FF-49).
a. Production Volumes
Monsanto has been producing diphenyl oxide only since late
33
-------
1975. Capacity or production volumes at the facility are not available as the
information is considered proprietary. The large percentage of production will
be used captively to make Therminol VP-1 (Pane, 1976), which is a heat transfer
(S)
fluid of identical composition to Dowtherm^ A. The unit which produces Therminol
VP-1 was placed on-stream in early 1976 (Garza, 1976).
b. Environmental Management
Wastes generated by Monsanto's diphenyl oxide process are
treated by the company's own waste treatment facility (Pane, 1976). The water
by-product produced during the process will be included in the wastes treated
by Monsanto. The efficiency of the treatment facility upon the diphenyl oxide
wastes is unknown.
c. Economics
The current selling price (1976) of Monsanto's diphenyl
oxide is $0.80/lb in bulk shipments.
Assume a 90% yield of diphenyl oxide from the phenol raw
material and a phenol price of $0.27/lb (Chemical Marketing Reporter, 1976).
Then 1 pound of formed diphenyl oxide consumes $0.332 worth of phenol.
-------
V. Use and Use Process Technology
A. Biphenyl
1. Dye Carrier
At the present time, nearly 60% of the refined biphenyl produced
in the U.S. is consumed in dyeing assistants called dye carriers. Polyester
/|^ fl^
fibers, such as Dacroir^ and Terylene , are difficult to dye because the polymers
themselves are practically inert to most forms of chemical attack. To enable
dyes to penetrate into these polyester fibers, the fibers must be treated with
compounds which cause the fibers to swell. These swelling compounds, or "carriers"
as they are usually called, are aromatic chemicals that improve the rate, color
intensity, and uniformity of dyeing when added to the dyebath.
a. Manufacture
The companies who produce biphenyl are generally not the
companies who formulate biphenyl into dye carrier products. Figure V-l illu-
strates the overall schematic for the virgin polyester fiber-to-finished garment
process. The companies who produce the dye carrier chemicals sell these chemi-
cals to textile chemical specialty firms. Twenty-four of the larger textile
chemical specialty firms who sell biphenyl products are identified in Table V-l.
The specialty firms receive the biphenyl chemical and add
approximately 10% surfactants, or emulsifiers, which will render the water-
insoluble biphenyl emulsifiable in the dyebath. Both nonionic and anionic
emulsifiers are used with biphenyl to create the aqueous emulsions. The non-
ionic emulsifiers (condensation products of alkylphenols with ethylene oxide)
are the most recommended types. However, a small amount of anionic emulsifier,
such as sodium salts of naphthalene sulfonic acid, formaldehyde condensation
35
-------
Largest:
Burlington
Deer ing—Mill Been
J. P. Stevens
Dye
and
Finish
Colored
Fabrics
Cut
and
Sew
Examples:
Farah
Levi
Etc.
Majors:
Dow
Finetex
Hooker
Monsanto
Pfizer
Standard Chlorine
Vetsi col
Chemical
CPS Chemical
Dow
East Coast Chemical
Monsanto
Pilot Industries
Sun Oil of Pennsylvania
Tanatex
Figure V-l.
Polyester Fiber to Garment Flow Diagram (adapted from Otis, 1976, and various
personal communications)
-------
Table V-l. Textile Chemical Specialty Firms Who Make Biphenyl Dye Carriers
Firm
Site
Basic Product Name
1. Arol Chemical Products Co.
2. Chemical Processing of Georgia
3. CNC Chemical Corp.
4. DePaul Chemical Co.
5. W.F. Fancourt
6. Finetex, Inc.
7. High Point Chemical Corp.
8. Independent Chemical Corp.
9. Jordan Chemical Co.
10. Lutex Chemical Corp.
11. Millmaster Oxyx, Refined Onyx
Div.
12. Piedmont Chemical Ind.
13. Raytex Chemical Corp.
14. Richmond Oil, Soap & Chemical
15. SAB Chemicals Co.
16. Sandoz Color & Chemical
17. A.E. Staley Mfg. Co.
18. Standard Chemical Products
19. Star Chemical Inc.
20. Sun Chemical Corp.
21. Tanatex Chemical Corp.
22. U.S. Oil Co.
23. Virkler Chemical Co.
24. Woonsocket Color & Chemical
Jersey City, NJ
Dalton, GA
Central Falls, RI
Long Island City, NY
Greensboro, NC
East Patterson, NJ
High Point, NC
Brooklyn, NY
Folcroft, PA
Chattanooga, TN
Lyndhurst, NJ
High Point, NC
Charlotte, NC
Philadelphia, PA
Jersey City, NJ
Hanover, NJ
Charlotte, NC
Charlotte, NC
Macon, GA
New York, NY
Lyndhurst, NJ
East Providence, RI
Charlotte, NC
Woonsocket, RI
Arosolve PC-7
Chemcryl COD
Chemkar 209
Carrier A
Depco Jet Carrier
296
Neoport BT
Accelerit BP
Carrier 100
Speco Carrier 23
Jocar LOG
Super-Lok 845
Decar BC
Carrier L-300
Raycar LBP
Rocar 4921-A
Sabcar #235
Dilatin FBL
Charlab LBPW
Standye Car 180
Carrier P-40
Sunkem 660
Carolid AL
Uscosist 810
Vircocarrier B
Woonco Dye Assist M
37
-------
products, sodium lignin sulfonate, and sulfonated turkey oil and other alkylaryl
sulfonates, may be present to maintain proper dyeing levels. The surfactants
added by each individual specialty firms are considered proprietary.
The biphenyl dye carrier product may also contain other
common dye carriers, especially methylbiphenyl and chlorinated solvents. Methyl-
biphenyl is a common by-product obtained at the same time that biphenyl is re-
fined from dealkylated toluene bottoms and has excellent dye carrier properties.
The chlorinated solvents may include trichlorobenzene and perchloroethylene.
b. Dye Carrier Use
The textile chemical specialty firms, in turn, sell the
biphenyl dye carrier products to the fabric producers and dyers, who are the
ones who actually use the biphenyl product. As many as four to five hundred
fabric dyers exist in the U.S. who use biphenyl as a dye carrier (estimate by
industry spokesmen). Therefore, no effort was made to identify all dyers. How-
ever, industry spokesmen indicated that three particular fabric producers repre-
sented a "sizable" portion of the polyester market. Those three are:
(1) Burlington Industries
(2) J.P. Stevens, Inc.
(3) Deering-Milliken & Co.
The corporate offices of all three are located in New York City, and all have
various plants situated throughout the United States. Burlington, for example,
has mills located in Greensboro, Kernersville, and Rhodhiss, North Carolina and
Roanoke, Virginia, in addition to 125 plants in the U.S.
Figure V-2 illustrates the general unit operations for
dyeing and finishing polyester fabrics. The following stepwise procedure is
recommended by Dow:
38
-------
CO
VO
Dye Carrier
Dyestuffs. Etc. '
Fabric
Biphenyl
Vapor Release
Dye
Bath
Release to
Waste Treatment
Wash
Biphenyl
Vapor Release
Vacuum
Drier
• Finished Fabric
Figure V-2. Dyeing and Finishing of Polyester Fabrics
-------
Step #1 Water 25,000 Ibs
#2 Heat to 120°F
#3 Polyester Fabric 1,000 Ibs
#4 Sequesterant 15 Ibs
#5 Lubricant 10 Ibs
#6 Anionic Dispersant 10 Ibs
#7 Acetic Acid 70% 15 Ibs
#8 Dye Carrier 40 Ibs
#9 Disperse Dyestuffs 20 Ibs
#10 Heat to 260°F
#11 Run for 45 minutes
#12 Cool to 160°F
#13 Emulsified Perchloroethylene 25 Ibs
#14 Wash
In general practice, the concentration of biphenyl varies
from 3-12% of the weight of fabric (Carter, 1976; Monsanto Technical Bulletin
1C/FF-29). After washing, the fabric is dried and "heat set" in a vacuum drier.
The dyebath liquor and wash water are released to waste treatment, which may be
in-plant or city-county facilities.
c. Environmental Management
The dyebath vessel can either be pressurized or unpressurized.
When dyeing at atmospheric pressure takes place, biphenyl vapors will be released
from the dyebath. OSHA regulations permit a TWA (time weight average) of 0.2 ppm
for biphenyl so dyers commonly use exhaust fans to vent biphenyl vapors to the
outside atmosphere. After the fabric has been washed, it will still contain
small amounts of biphenyl. The vacuum drier effectively removes this biphenyl,
and the vapors are again vented to the outside. Small crystals of biphenyl may
infrequently remain in the fabric after heat setting, but biphenyl1s tendency
to sublime under normal conditions leads to disappearance of these crystals.
At least 95% of the biphenyl added as dye carrier is re-
leased in the waste waters. Since the biphenyl is in an emulsified state, it
40
-------
is too difficult to separate from the water; otherwise, it could be reused.
It appears that most of the smaller dyers release their wastewaters directly
to city-county sewage treatment facilities while several of the larger mills
have on-site treatment (see Section IX-B-1).
d. Areas of Use
Nearly 22 million pounds per year of biphenyl dye carriers
are estimated to be used in dyeing of polyester carpets and draperies in
Georgia (Versar, 1976; Gaffney, 1976). This relatively small geographical
area accommodates 250 to 300 mills representing 65% of the world's carpet and
rug market.
A similar quantity of biphenyl may well be used in the
fabric mills of North Carolina. The textile mills of New England also use sig-
nificant amounts of biphenyl.
e. Economics
The biphenyl producers are currently selling 50-55 million
pounds of biphenyl to the textile chemical specialty firms at a $0.16-$0.22/lb
price. This would indicate annual sales of $8-12 million. The textile chemical
firms process the biphenyl into dye carrier products and sell the products to
the fabric dyers at a price which is often 100% and more, above the price which
they paid for the biphenyl.
f. Alternative Products
The following chemicals are all commercially used dye
carriers which can be used in place of biphenyl:
41
-------
(1) Butyl Benzoate -
Selling Price:
Manufacturers:
(2) o-Phenylphenol -
$0.30/lb (1976)
CPS Chemical Co., Cindet Chemicals, Finetex,
Velsicol, Pfizer, Tanatex
HO.
DMO
Selling Price:
Manufacturer :
(3) Trichlorobenzene -
Selling Price:
Manufacturers:
(4) Dichlorobenzene -
Selling Price:
Manufacturers:
(5) Methyl Salicylate -
Selling Price:
Manufacturers:
(6) Perchloroethylene -
$1.50/lb (1976)
Dow Chemical
$0.39/lb (1976)
Dow Chemical, Hooker, Standard Chlorine
ci
$0.31/lb (1976)
Allied, Dow, ICC Industries, Monsanto, PPG, Solvent
Chemical, Specialty Organics, Standard Chlorine
$1.00/lb (1976)
Dow, Monsanto, Tenneco
ci2c - cci2
Selling Price:
Manufacturers:
$0.165/lb (1976)
Diamond Shamrock, Dow, DuPont, Ethyl Corp., Occidental,
PPG, Stauffer, Vulcan
42
-------
(7) Methyl Naphthalenes -
Manufacturers: Crowley Hydrocarbon, Koppers, Marathon Oil
g. Alternative Processes
A commercial waterless dyeing process for textiles has been
developed by Martin Processing Inc., Martinsville, VA. The company claims that,
compared to conventional processes, it will eliminate water pollution, cut
energy consumption in half, and reduce capital investment 60%. The process
makes use of a combination of organic solvents maintained in a closed system
within the equipment. Solvents are continuously purified and recycled, and no
dyes are lost, the company says. According to Martin, which will market the
process early in 1977 through its Temple Machinery Co. Division, the process is
applicable to about half of the 14 billion yards of fabric piece dyed annually
in the U.S. (Anon., 1976 c).
2. Biphenyl Fungicide in Fruit Packaging
Biphenyl has been used for nearly 30 years as a mild fungicide
in citrus fruit wrappers and packaging. It would be impossible to ship citrus
fruit across the U.S. or overseas in cartons, without a blue mold preventive
like biphenyl. Years ago, "orange crates" of open lattice wood were used to let
air circulate through and reduce mold formation. However, this exposed the
fruit to the drying effects of air, external molds, water, dirt, etc. The
new sealed cartons prevent all these problems, but absolutely require a mold
retardant.
During the mid-19501s, the FDA investigated the toxicity of
biphenyl. The Institute of Paper Chemistry (IPC) was chosen to determine analysis
43
-------
methods and to investigate potential problems. As a result of the work by IPC,
biphenyl was given a clean "bill-of-health" by the FDA (Versar, 1976).
a. Manufacture
The two American producers of biphenyl-impregnated papers
are listed below:
(1) Crown Zellerbach Corp. San Francisco, CA
(2) Paper-Pak Corp. Orlando, FL
Biphenyl tissue wrappers are still manufactured as described
in the original patent (Mispley and Barber, 1940). The biphenyl is bonded to
the tissue paper by a solvent carrying the biphenyl; the solvent consisting of
liquid paraffin oil fortified with paraffin wax. The tissue paper will contain
about 1.75-2.97% of its weight as biphenyl and 7% to 9% of its weight as solvent.
Paper pads are impregnated in a similar fashion with 4 Ibs
of biphenyl per 1000 sq. ft. surface area (Cosner, 1976). Two pads are inserted
into each container of fruit, one on top and one on bottom. The tissues are
used to wrap each piece of fruit individually.
Efforts have been made to coat the insides of corrugated
paper boxes with a biphenyl paste, but this method has yielded inferior pro-
tection. The air permeability of corrugated boxes allows the biphenyl to
dissipate (sublime).
b. Production Volumes
Approximately 600,000 to 800,000 pounds of biphenyl are
consumed for fungicide papers per year at present (Cosner, 1976). Production
is seasonal, as would be expected from its use in fruit protection.
44
-------
Ten years ago, at least several million pounds of biphenyl
were annually consumed for fungicidal purposes. However, the advent of faster
domestic transportation has lowered the need considerably. Today, a sizeable
portion of the biphenyl papers produced are used for overseas shipments. Domestic
use is still important, though, for long-haul shipment and closed container
storage.
The amount of biphenyl used as a fungicide has been de-
creasing in recent years. Future projections indicate, at best, a stable
market; however, slight decreases can be expected.
c. Economics
A high-grade purity biphenyl is required for fungicidal
uses. The current selling price of Monsanto's high-grade biphenyl is $0.36/lb,
indicating biphenyl sales for fungicides of $0.21 to $0.28 million annually.
The sale of biphenyl papers may amount to several million dollars per year.
d. Environmental Management
The nature of this biphenyl use indicates that all of the
biphenyl so used will eventually be exposed to the environment. A large per-
centage of biphenyl papers will eventually be disposed in solid trash disposals
and/or incinerated.
e. Alternatives
One commercial alternative to biphenyl is £-phenylphenol
(o-hydroxybiphenyl). Ortho-phenyIpheno1 can be obtained as a by-product during
Dow's phenol production from chlorobenzene, the same process from which diphenyl
oxide was recovered. The o-phenylphenol is converted to the sodium salt which
is used to control molds and rots of citrus and other fruits and for the
45
-------
disinfection of domestic and agricultural buildings, warehouses, and refrigerated
stores. Price is slightly higher than biphenyl, but its wider-range of protection
CD
is a definite advantage. It is an active ingredient in certain Lysol^cleaners.
3. Polychlorinated Biphenyl (PCB)
PCB production and use has been thoroughly studied in a previous
EPA report (Versar, 1976), so only a brief review will be given here. This use
of biphenyl has been stopped by Monsanto and no manufacturer is allowed to
produce PCB's two years after the effective date (January 1, 1977) of the Toxic
Substances Control Act (Section 6e, PL94-469).
a. Manufacture
Monsanto, the sole domestic manufacturer of PCB's, manufactured
this chemical in their Sauget, Illinois plant. The PCB manufacturing operation
is conducted in two steps. First, biphenyl is chlorinated with anhydrous chlorine
in the presence of ferric chloride to produce crude PCB's and then the crude PCB's
are distilled to obtain the finished product.
Until recently Monsanto made four different PCB products;
Aroclor 1221, 1242, 1016, and 1254. The difference is in chlorine content which
ranges from 21% in Aroclor 1221 to 54% in Aroclor 1254.
b. Production Volumes
Monsanto produced 40.4 million .pounds of PCB's in 1974 and
8.5 million pounds in the first quarter of 1975 (Versar, 1976). The average
chlorine content is roughly 48% when all PCB products are lumped together.
Therefore, approximately 21 million pounds of biphenyl are consumed annually
to produce PCB's.
c. Economics
Current selling price (1976) of PCB products averages about
$6 per gallon (11.36 Ibs/gallon). Total annual sales would therefore be nearly
$11.1 million.
46
-------
4. Alkylated Biphenyl
a. Isopropylbiphenyl
Commercially, isopropylbiphenyl is the most important of
the alkylated biphenyls. Tanatex Chemical Division in Lyndhurst, NJ is the
largest domestic producer of isopropylbiphenyl (Cohen, 1976); Pilot Industries
of Houston, TX also manufactures the chemical (Barrow, 1976).
(i) Manufacture
Isopropylbiphenyl is manufactured by a Freidel-Crafts
reaction of biphenyl with propylene, the chemistry being:
DHO
-2
Primarily, the monoisopropyl derivative is formed,
but small amounts of the diisopropyl derivative will also exist.
(ii) Production Volumes and Uses
Currently, about 10 million pounds of isopropyl-
biphenyl are annually produced (SRC estimation). Nearly all of the production
is used in carbonless paper (Cohen, 1976). Manufacture started about 1971 and
has accelerated to the present volume. In 1971, Monsanto terminated PCB's
sales for carbonless paper, and isopropylbiphenyl has been used as a substitute
for PCB in this application.
Isopropylbiphenyl may find future applications in heat
transfer and capacitor fluids. It may be a component in Monsanto's proprietary
dielectric fluid trade named "MCS-1238" (Versar, 1976). Monsanto has been testing
"MCS-1238" as a possible PCB replacement.
47
-------
(iii) Economics
The 1976 selling price of isopropylbiphenyl is
$0.56/lb, which would indicate annual sales of $5.6 million to the carbonless
paper industry.
b. Methylbiphenyl
Methylbiphenyl is obtained as a by-product when toluene is
hydrodealkylated to benzene. It commonly exists as an impurity in the grade
of biphenyl sold for dye carrier use; however, methylbiphenyl alone exhibits
excellent dye carrier properties. Small quantities of methylbiphenyl are iso-
lated and sold by Pilot Industries of Houston, TX, but commercial-scale pro-
duction has yet to occur (Barrow, 1976).
Since methylbiphenyl has such good dye carrier properties,
it is conceivable that efforts to synthesize it may have commercial importance
in future years.
c. Ethyl- and Butylbiphenyl
Ethyl- and butylbiphenyl are produced by Freidel-Crafts
reaction of biphenyl with ethylene and butylene, respectively. Pilot Industries
produces small quantities for applications in heat transfer, but they are not
commercially important yet (Barrow, 1976).
5. Eutectic Heat Transfer Fluid
See Section V-B-1.
6. Polybrominated Biphenyl (PBB)
PBB production and use has been studied in previous EPA reports
(Mumma and Wallace, 1975; Neufeld eit al., 1977), so only brief review will be
given here.
-------
a. Manufacture
Commercial production of PBB's was thought to have been ter-
minated in 1974 (Mumma and Wallace, 1975), the commercial producers being
Michigan Chemical Corp. of St. Louis, MI, and White Chemical Corp. of Bayonne,
NJ. The suspected termination was precipitated when, in 1973, PBB's were
inadvertently fed to dairy cows with harmful effects. However, decabromo- and
octabromobiphenyl were commercially produced in 1975 and 1976 for export purposes
by White Chemical (Bayonne, NJ) and by Fine Organics (Sayreville, NJ) (Neufeld
et al., 1977).
The manufacturing process of PBB's is considered proprietary,
but patent literature (Moore et al., 1974; Mitchell, 1973) describes production
via bromination of biphenyl by bromine chloride or liquid bromine.
PBB's were used exclusively as flame retardants for plastics,
and are currently exported for this purpose.
b. Production Volumes
Michigan Chemical produced a total of about 11.2 million
pounds of PBB's during the period of 1970 to 1975, and White Chemical produced
about 100,000 pounds of PBB's from 1970 to 1973. In 1976, 805 thousand pounds
of PBB's were produced (Neufeld et^ al., 1977). The total production of PBB's
from 1970 to 1976 was 13.334 million pounds.
c. Economics
The 1975 selling price of the major PBB product (Firemaster
BP-6) was $0.75/lb. Combining this with the largest production year, 1974 (4.8
million pounds), reveals 1974 sales of nearly $3.6 million.
d. Alternatives
One viable alternative is decabromodiphenyl oxide (see
Section V-B-6 for this discussion).
49
-------
B. Diphenyl Oxide
1. Eutectic Heat Transfer Fluid
The major current use of diphenyl oxide is for manufacture of a
eutectic heat transfer mixture composed of 73.5% diphenyl oxide and 26.5%
biphenyl. This mixture has been marketed by Dow Chemical Co. as Dowthemr^A
since the early 1930's. Dow produces Dowtherm^ A in Midland, Michigan. Mon-
santo Industrial Chemicals, in Alvin, Texas, began producing an identical mixture
called Therminol VP-1 in early 1976. Dow and Monsanto are the only domestic
producers; however, all of the known world producers of this particular mixture
are listed below:
Producer Country Product
Dow Chemical USA DowthemP'A
Monsanto USA Therminol VP-1
Imperial Chemical Great Britain Thermex
Nippon Steel Chemical Japan Therm S-300
Bayer West Germany Diphyl
Progil France Gilotherm
The biphenyl-diphenyl oxide eutectic mixture is used as both a
heating and cooling heat transfer media. It is used in liquid phase at tem-
peratures from 60°F to 750°F, and in the vapor phase at temperatures from 495°F
to 750°F. It is non-corrosive, so carbon steel is usually selected for equipment
in which it will be used. Physical properties of the mixture are listed on the
Material Safety Data Sheets for Dowthernr' A in Appendix B.
The eutectic mixture is stable except at the upper temperature
levels. The first decomposition effect of elevated temperatures is a polymeri-
zation to materials of higher molecular weight, but these polymers remain in
solution in the liquid and do not affect operation as long as their concentray
tion does not exceed 10%. At 750°F, the decomposition rate varies between 0.8%
and 3.0% per 100 hours (Danziger, 1966). Dow has an analysis and purification
service and can reprocess deteriorated Dowtherm if polymerization is not too
advanced. Charles E. Sech - Consulting Associates (in Michigan) sells a purification
50
-------
system to individual users of DowthernP^A, which is nothing more than a single-
plate distillation column. The impurities from the distillation are usually
added to fuel oils because their heating value, as well as that of Dowtherm,
is quite high (Sech, 1976).
a. Users
The eutectic mixture has numerous applications in synthetic
fiber production and finishing, petroleum refining, and plastics manufacturing.
(g)
About 2500 new installations, utilizing Dowtherm A, were made in the U.S. from
1955-1965 alone (Danziger, 1966). It is virtually impossible to identify all
users of the product as the use is so wide-spread.
b. Production Volumes
SRC estimates that approximately two-thirds of Dow's 1975
diphenyl oxide production (SRC estimation - 6 million pounds) was used to form-
(S)
ulate DowthernP^ A. This would correspond to a 1975 production of slightly less
than 5.5 million pounds of Dowtherm. Biphenyl use accounted for roughly
1.5 million pounds.
Dow is currently expanding their facilities which produce
diphenyl oxide and Dowtherm^ A. Estimates of future capacities are not available.
The capacity of Monsanto's new Therminol VP-1 unit is also
not available. Due to the large available sources of the eutectic mixture
overseas, the U.S. production is consumed domestically. It would seem unlikely
that Monsanto's production in the near future would be larger than Dow's current
production.
World-wide consumption of the eutectic mixture exceeded
1 million gallons (8.83 million Ibs) in 1962 (Davies, 1963).
51
-------
c. Economics
(6)
The following selling prices (1976) are for Dowtherm^A:
5 gallon pail $0.84/lb
55 gallon drum $0.79/lb
4000 gallon tankers $0.66/lb
The 1975 sales of Dowtherm^A would roughly be $4 million
considering a 5.5 million pound production.
d. Environmental Management
Occupational exposure to vapors of the eutectic mixture
have been regulated by OSHA standards.
Manufacture involves only mixing of liquid diphenyl oxide
and biphenyl. It seems unlikely that any quantity would be released to the
environment during manufacture except by accidental spill or leak. Dow1s
"Material Safety Data Sheet" for Dowthernr^A calls for incineration of spilled
materials (see Appendix B).
Users of the mixture can have contaminated quantities re-
processed by Dow or use old quantities as a burning fuel.
e. Use Alternatives
One of the major alternatives to Dowtherm^A is petroleum-
derived oils. Numerous oils are included in this category and collectively,
these petroleum-derived oils are probably the most widely used heat transfer
media at temperature levels above that of moderate-pressure steam (up to 550°F).
These oils are obtained as high-boiling fractions from petroleum. Several com-
mercial products are listed below:
(1) Mobiltherm 600 Mobil Oil Co.
(2) Caloria 43 Exxon Corp.
(3) Security 205 Gulf Oil Corp.
(4) Tellus 7Z Shell Oil Co.
52
-------
Dowthernr^A has advantage over petroleum oils due to a higher
©
film temperature which can be sustained before degradation occurs. DowthernT^ A
is useable at temperatures up to 750°F,'while the petroleum oils have a limit
of 600°F. In addition, Dowtherm^ A maintains a cleaner operating surface during
(S)
normal use. The disadvantages of Dowthenn^ A include a price differential in
favor of the petroleum oils, and the extra cost of heat-tracing pipes as Dowtherm
freezes at 54°F.
/6N
2. Dowfax^
flb
Dowfax^ is the tradename for dodecyldiphenyl oxide disulfonic
/o\
acid, disodium salt manufactured by Dow Chemical in Midland, Michigan. Dowfax^
surfactants are anionic wetting agents of the sulfonate type which are used in
latex production, agricultural formulations, cleaning compounds, dye assists,
detergents, and in textile fiber production (Dow Products & Services Catalog).
a. Manufacture
A flow diagram illustrating the manufacture of Dowfax^ is
shown in Figure V-3.
Diphenyl oxide is alkylated with either n-dodecyl chloride
or 1-dodecene to dodecyldiphenyl oxide. The dodecyldiphenyl oxide is dissolved
in an organic solvent, and sulfonation is carried out with S0_. The chemical
reaction is:
SO H)
-------
1 — Dodecene
or •
n — Dodecyl Chloride
Diphenyl
Oxide
Alkylation
Reactor
SO,
Organic
Solvent
Reactor
Recycled Organic Solvent
Density
Separation
Dowfax® Solutions
Evaporator
Neutral izer
NaOH
[Adapted From Valenta and Stienhauer, 1964 ]
Figure V-3. Process Manufacture of Dowfax^Solutions
-------
The solution is allowed to density separate and the upper layer of organic sol-
vent is decanted. An aqueous NaOH solution is now added to the bottom layer to
neutralize the dodecyldiphenyl oxide disulfonic acid to the disodium salt. Evap-
oration of the solution to dryness gives a buff to white powder of dodecyldiphenyl
oxide disulfonic acid, disodium salt (Valenta and Steinhauer, 1964; Branson, 1977).
Several Dowfax^ products are available from Dow:
(1) Dowfa^ 2A1 Surfactant Solution
(2) Dowf ax«v 3B2 Solution
(3) Dowfax^ 2AO
(1) and (2) above are sodium salt solutions containing 45%
active ingredient of mono and di alkyldiphenyl oxide disulfonate, where the alkyl
group is C1„ and C-n, respectively. (3) Is the acid form (not neutralized with
NaOH).
b. Production Volumes
Production volumes were not available from Dow; however,
SRC estimates that Dow captively consumes about 0.75 million pounds annually of
diphenyl oxide to synthesis Dowfax surfactants. This would mean an annual
production of roughly 2.3 million pounds of Dowfax*^ surfactants. Dow introduced
this product in the early 1960's. Projections for future growth were not obtained.
c. Economics
/e\
The selling price (1976) of Dowfax^ 2A1 Surfactant Solution
is $0.47/lb; therefore, the selling price of the dry powder dodecyldiphenyl oxide
disulfonic acid, disodium salt would be approximately $1.00/lb. This would indicate
annual sales of $2.3 million.
d. Environmental Management
It is doubtful if significant quantities of diphenyl oxide
(E)
are released to the environment via manufacture of Dowfax^ Sewer wastes
55
-------
containing diphenyl oxide are treated by Dow's Michigan Division Waste Treatment
Plant (Otis, 1976). Treatment efficiency of the plant with respect to diphenyl
oxide is unknown.
e. Alternative Products
There are numerous surfactants commercially available on
the American market. Many are organic derivatives of high molecular weight
©
alkyl sulfates or sulfonates. Dowfax can be included in the group of surface-
active agents having ester or ether linkages. Other chemicals included in this
group are:
(1) Sulfosuccinic acid esters
(2) Coconut oil acids, 2-sulfoethyl ester, sodium salt
(3) Dodecyl sulfoacetate, sodium salt
(A) Herring oil, sulfonated, sodium salt
(5) Isooctylphenol, ethoxylated and sulfonated, sodium salt
(6) ri-Octylphenol, ethoxylated and sulfonated, sodium salt
Selling prices on the above vary from $0.55 - $1.00/lb.
3. Diphenyl Oxide Dye Carriers
Diphenyl oxide dye carriers were made commercially available in
the U.S. in 1973. Dow Chemical supplies the "industrial" grade diphenyl oxide
to the textile specialty chemical firms as described for biphenyl dye carriers
(see Section V-A-1). This industrial grade assays 90% diphenyl oxide and the
remainder as methylnaphthalenes and naphthalenes (Dow Form No. 110-288-72).
Diphenyl oxide is used the same as biphenyl as a dye carrier.
The textile chemical specialty firm which apparently handles
most of the diphenyl oxide dye carriers is Chemical Processing of Georgia in
Dalton, Georgia.
a. Volume of Use
Company spokesmen for Chemical Processing of Georgia estimate
56
-------
diphenyl oxide dye carrier use at much less than one million per year currently.
No great increase is expected in the near future.
SRC estimates the current use of diphenyl oxide in dye carriers
at roughly 0.25 million pounds per year.
b. Economics
Recent selling price (1976) for Dow "industrial grade
diphenyl oxide is $0.52/lb, up from $0.32/lb in 1973. After the chemical
specialty firms add emulsifiers and proprietary ingredients, the cost to the
textile dyers may be 100-200% greater. This would make the total sales of
diphenyl oxide dye carriers in the neighborhood of $0.35 million per year.
c. Environmental Management
Same as for bipheriyl. See Section V-A-1.
d. Alternative Products
Same as for biphenyl. See Section V-A-1.
4. Perfumes and Soaps
Due to its characteristic geranium odor, diphenyl oxide has been
used in perfume formulations since the early 1930's.
a. Manufacture
The major manufacturers of diphenyl oxide perfumes are:
(1) Givaudan Corp. Clifton, NJ
(2) Florasynth, Inc. New York, NY
Actual compositions of perfume products are considered
proprietary; however, the concentration of diphenyl oxide in the final products
is listed below (Opdyke, 1974):
57
-------
Concentrations in %
Soap Detergent Creams, Lotions Perfume
Usual 0.05 0.005 0.05 0.15
Maximum 0.20 0.03 0.10 0.40
The largest user of diphenyl oxide in soaps and detergents
has been suggested to be Proctor & Gamble Company, corporate offices in Cin-
cinnati, Ohio.
Before compounding the "perfume" grade diphenyl oxide into
perfumes, it is common to increase the purity by chemical means (Mahinka, 1976).
Crystallization is probably the most common method.
b. Volume of Use
Recent estimates of diphenyl oxide use in fragrances in the
U.S. amounts to about 100,000 Ibs/yr (Opdyke, 1974). This figure is down from
200,000 Ibs/yr in 1965 (Cantrill, 1968). The 100,000 Ibs/yr figure is expected
to remain stable in the near future.
Nearly one-half of the diphenyl oxide currently used in
fragrance products is imported. In 1974, 43,201 pounds of diphenyl oxide were
imported for this use (United States International Trade Commission, "Imports
*
of Benzenoid Chemicals and Products 1974"). Before 1974, there is no record of
any imports.
c. Economics
The selling price (1976) for "perfume" grade diphenyl oxide
is $0.85/lb, which is up from $0.51/lb in 1965. After formulation into fragrance
products, the price will be many times greater.
58
-------
d. Environmental Management
The nature of fragrance products indicates that all 100,000
Ibs/yr use will be exposed to man and the environment. It should be noted that
biological data (Opdyke, 1974) suggest no adverse effects due to human use of di-
phenyl oxide in perfumes and soaps.
e. Alternative Products
Perfume formulators (Mahinka, 1976; Graham, 1976) cite many
aromatic ethers which are useable in perfumes. The only reason diphenyl oxide
is chosen in certain instances is its relatively low cost compared to alternatives.
5. Butylated Monochlorodiphenyl Oxide
Butylated monochlorodiphenyl oxide has recently been marketed by
Dow Chemical in Midland, Michigan, under the tradename "XFS-4169L". Dow hopes
that this product will be a viable alternative to PCB's used in capacitors.
In September 1975, Dow began manufacturing XFS-4169L in pilot-quantities for
use by McGraw-Edison and other U.S. capacitor producers (Anon., 1976 b) and
is in the process of expanding capacity.
a. Manufacture
Specific details of manufacture were not available from
Dow, but production is probably accomplished by monochlorination of diphenyl
oxide followed by butylation. Monochlorination of diphenyl oxide is described
in a Dow patent (Hennis, 1974). According to the patent, diphenyl oxide, con-
taining 0.005 moles of 98% H-SO, as catalyst, is chlorinated to yield the
following products: 8% ^-chlorodiphenyl oxide, 67% p_-chlorodiphenyl oxide, 10%
dichlorodiphenyl oxide, and 15% unreacted diphenyl oxide.
59
-------
The monochlorodiphenyl oxide can be butylated by Freidel-
Crafts reaction (Aid- catalyst) with butene or butyl chloride. The general
formula for XFS-4169L is (Branson, 1975):
b. Production Volumes
Until 1976, only pilot-quantities of XFS-4169L were being
produced, but Dow assured the electrical industry that it would have a capacity
rate of one million pounds per year during the first quarter of 1976 (Branson,
1975). Dow now says (Anon., 1976 b) that it hopes to have production capacity
in excess of 5 million Ibs/yr by the end of 1976. Five million pounds of
butylated monochlorodiphenyl oxide would consume roughly 3 million pounds of
diphenyl oxide. The diphenyl oxide and chlorobenzene expansion presently under
construction at Dow is designed to produce the additional capacity of required
diphenyl oxide.
c. Environmental Management
Sewer wastes containing diphenyl oxide are treated by Dow
Michigan Division Waste Treatment Plant (Otis, 1976); however, significant
quantities of diphenyl oxide should not be released from the XFS-4169L process
as unreacted diphenyl oxide can be recycled for chlorination. Specific environ-
mental management techniques concerning the chlorodiphenyl oxides were not
obtained from Dow.
d. Economics
1976 selling prices of XFS-4169L range from $21.50 to
$30 per gallon depending upon volume; least expensive for 55 gallon drums, most
60
-------
expensive for 5 gallon pails. Large scale production figures to lower the
selling price to $12 per gallon ($1.40/lb). If 5 million pounds per year are
sold, this would represent sales of $7 million.
e. Alternatives
Butylated monochlorodiphenyl oxide was developed to be an
alternative to the toxic and persistent PCB's, which sell for $6-$7 per gallon.
However, because of environmental contamination resulting from their use, PCB's
will no longer be produced in the future. Many corporations are presently in-
volved in research and testing of new compounds to replace PCB's. Some of the
primary possibilities have been summarized in a previous EPA - Office of Toxic
Substances Report (Versar, 1976); they are listed below:
(1) Dioctyl Phthalate
(2) Diisononyl Phthalate
(3) Isopropyl Dichlorobiphenyl
(4) Silicones
(5) Diaryl Sulfone
6. Decabromodiphenyl Oxide
Decabromodiphenyl oxide (decabromodiphenyl ether, decabromo-
phenoxylbenzene) is used as a flame retardant in certain types of flame re-
sistant polystyrene, polypropylene, polybutylene, terephthalate, ABS resins,
and other plastic materials (Levek and Williams, 1975).
a. Manufacture
The four domestic producers of decabromodiphenyl oxide are:
Producer Site Tradename
(1) Dow Chemical Co. Midland, MI FR-300-BA
(2) Great Lakes Chemical Corp. El Dorado, AR Great Lakes DE-83
(3) Hexcel Corp., Sayreville, NJ
Fine Organics, subsid.
(4) White Chemical Corp. Bayonne, NJ
61
-------
Details concerning actual manufacturing methods are con-
sidered proprietary and are not available. A survey of patent literature re-
vealed no information concerning decabromodiphenyl oxide production. A Dow
patent (Moore et al., 1974) describes bromination of biphenyl with bromine
chloride. Decabromobiphenyl is obtained by adding a stoichiometric excess of
bromine chloride, under pressure in a closed vessel, to biphenyl in the presence
of an Aid- catalyst. Decabromodiphenyl oxide could conceiveably be prepared
by a similar method. The bromine content in decabromodiphenyl oxide is nearly
83% by weight (Tabor, 1973).
b. Production Volumes
SRC estimates that roughly 0.5 million pounds of diphenyl
oxide are presently consumed per year to produce decabromodiphenyl oxide. This
would correspond to an annual decabromodiphenyl oxide production of 2.8 million
pounds. Commercial production of decabromodiphenyl oxide began in 1972.
Company spokesmen are projecting increases in production
during the next several years; an exact percentage was not available.
c. Economics
Decabromodiphenyl oxide (Dow's FR-300-BA) is currently
selling (1976) for $1.80/lb, which is up from $1.08/lb in 1973. Annual sales
could amount to nearly $5 million.
d. Environmental Management
Wastes from decabromodiphenyl oxide production units should
contain only small amounts of diphenyl oxide. The total diphenyl oxide which
may be exposed by these units is probably insignificant when compared to other
diphenyl oxide uses. Effectiveness of diphenyl oxide waste treatment is dis-
cussed in Section IX-B-2.
62
-------
e. Alternatives
Several years ago, polybrominated biphenyls (PBB's) were
an important commercial flame retardant. Decabromodiphenyl oxide was developed
to compete with PBB's for various applications, but decabromodiphenyl oxide cost
nearly twice as much as PBB's. However, domestic PBB production was terminated
in November 1974, after dairy cattle were mistakenly fed a PBB product (Mumma
and Wallace, 1975). PBB's are still produced for export (Neufeld et^ al., 1977).
One of the new flame retardants, with applications similar
to decabromodiphenyl oxide, is Citrex BC-26, sold by Cities Service Company in
Rockville, Conn. (Mumma and Wallace, 1975). Citrex BC-26 is a halogenated
organic containing 29% bromine and 40% chlorine with a price comparable to
decabromodiphenyl oxide.
Other comparable flame retardants include (Tabor, 1973):
(1) Tetrabromobisphenol-A $0.57/lb
(2) Pentabromochlorocyclohexane $1.10/lb
(3) Dibromoneopentyl Glycol $0.55/lb
(4) Tris (2,3-dibromopropyl)phosphate $0.65/lb
7. Minor Commercial Uses of Diphenyl Oxide
a. Chloromethyldiphenyl Oxide
Chloromethyldiphenyl oxide and di(chloromethyl)diphenyl
oxide are produced in small quantities and are used to make thermosetting foams
and resins.
The production technology was developed by Dow Chemical
(Doedens and Rosenbrock, 1961), but the only U.S. producer of Chloromethyl-
diphenyl oxide and di(chloromethyl)diphenyl oxide is Stauffer Chemical in
Edison, NJ (Insera, 1976). Stauffer has produced these chemicals since 1971.
63
-------
Diphenyl oxide reacts with formaldehyde and hydrochloric
acid to produce a variety of chloromethylated compounds. The degree of chlor-
ination determines the distribution of isomers. Chloromethylation to 25.2%
chlorine, for example, would produce the following isomer distribution (Dow Form
No. 110-288-72):
HCHO + HC1
(0.25%)
(2.35%)
CH2C1 CH2C1
(10.5%)
CH0C1 CH.C1
2 i L
Pure materials can be recovered by use of solvent extraction and distillation
(Doedens and Cordts, 1961).
The total combined production of chloromethyl and di(chloro-
methyl)diphenyl oxide amounts to much less than 100,000 pounds per year (Insera,
1976). Initial hopes for large-scale production have failed to materialize and
significant growth in the future is not forecast.
b. Methoxymethyldiphenyl Oxide
Methoxymethyldiphenyl oxide is also produced by Stauffer
Chemical in Edison, NJ. Production volumes are less than those for chloro-
methyldiphenyl oxide (Insera, 1976).
64
-------
Diphenyl oxide and formaldehyde are used as the starting
materials to produce methoxymethyldiphenyl oxide. Various isomers are formed,
as shown for chloromethyldiphenyl oxide. The mono-para and mono-ortho isomers
shown below make-up the bulk of production.
CH2OCH3
Methoxymethyldiphenyl oxide is used to manufacture Westing-
house's Doryl resins (Cogley, 1976). Doryl resins are used in high temperature
varnish applications for electrical insulators.
c. Pesticides
Diphenyl oxide has been identified in a pesticide plant's
raw effluent (Webb et al. , 1973) via gas chromatography - mass spectrometry. A
survey of patent literature revealed that Ciba-Geigy Corporation holds patents
v
describing insecticide production from diphenyl oxide. However, the Ciba-Geigy
pesticide production facilities (in Mclntosh, Alabama) failed to respond to in-
quiries asking about diphenyl oxide use, perhaps due to proprietary considerations.
The following synthesis is an example of diphenyl oxide use
in insecticides detailed in a Ciba-Geigy patent (Franke and Traber, 1972) :
(1)
+ HCl
HCHO-HC1
65
-------
(3)
Ciba-Geigy has marketed the following pesticides with a
diphenyl oxide moiety:
(Chloroxuron)
(Fluorodifen)
It is doubtful that the above pesticides are synthesized
with diphenyl oxide as a raw material, but diphenyl oxide may be generated in
by-product amounts large enough to detect via gas chromatograph - mass spectro-
meter. This may account for the identification of diphenyl oxide in pesticide
effluents, but this is only speculation. We have not been able to determine if
diphenyl oxide is definitely used as a raw material for pesticide production,
and this possibility still exists.
66
-------
VI. Sources of Biphenyl and Diphenyl Oxide Occurring in Nature
A. Biphenyl
1. Petroleum
Aromatic compounds of almost every known type have been found
in petroleum. Biphenyl and its three mono-methyl derivatives have been identi-
fied and isolated from crude petroleum (Hunt and O'Neal, 1967).
Biphenyl, which boils at 255°C, was isolated in the dinuclear
aromatic portion of petroleum boiling in the range 255° to 275°C. Mair and
Mayer (1964) have estimated that biphenyl makes up 0.008% by volume of crude
9
petroleum. In 1973, 3.1 x 10 barrels of crude oil were produced in the United
States (SRI, 1975 b). This translates to approximately 1.3 x 10 gallons of
crude oil of which an estimated 0.008% by volume was biphenyl. Converting to
weight measurement, an estimated 80 million pounds of biphenyl were present as
a naturally occurring constituent of the petroleum domestically produced in
1973. In addition, nearly 5 x 10 gallons of crude petroleum were imported in
1973 (SRI, 1975 b), which may have contained an estimated 30 million pounds of
biphenyl. Note that the combined total of biphenyl content in domestically
produced and imported crude oil, 110 million pounds, is slightly higher than the
amount of biphenyl which is refined annually, 85 million pounds (SRC estimation).
The biphenyl which is present in petroleum appears to be used in fuels because
it is not refined; 0.008% is much too small to recover.
It has been estimated that the total oil influx into the ocean
from routine discharges from tankers, accidents in port and on the high seas
in exploration and production, in storage, in pipeline breaks, from spent lubri-
cants, from incompletely burned fuels, and from untreated industrial and domestic
67
-------
sewage is between 11 - 12,000 million pounds per year (Blumer et^ al., 1971).
Assuming 0.008% by volume biphenyl content, simple calculation suggests that
approximately 1,000 pounds of biphenyl are annually released into the environ-
ment with spilled oil.
Methylbiphenyls amount to an estimated volume %, relative to
crude petroleum, of approximately 0.0404% (Mair and Mayer, 1964; Yew and Mair,
1966). This amounts to five times the volume of plain biphenyl.
2. Foods
Stevens e± al. (1966) identified biphenyl in the volatile con-
stituents of grapes by use of a capillary gas chromatograph attached to a mass
spectrometer. Biphenyl had previously been identified in orange volatiles by
Schultz £t ajL. (1964); however, Schultz et_ al^. attributed the biphenyl's presence
to packaging materials which were impregnated with fungistat biphenyl. The grapes
used by Stevens in his investigation were handled in bulk, and fungistat biphenyl
could not have come from packaging. It would seem possible, therefore, that
biphenyl may be a naturally occurring constituent of grape volatiles.
Kinlin et_ al. (1972) identified biphenyl in the volatile consti-
tuents of roasted filbert nuts while Walradt et_ al. (1971) found biphenyl in
peanut volatiles. Stoll £t al. (1967) identified biphenyl as one of 202 consti-
tuents present in coffee concentrate.
The amounts of biphenyl which may occur in foods are very small
and it is very doubtful if any significant quantities of biphenyl are exposed
to the environment via this route.
B. Diphenyl Oxide
1. Plants
In addition to biphenyl, Stevens et^ al. (1966) identified diphenyl
68
-------
oxide in the volatile constituents of grapes. Kimland et al. (1972) identified
diphenyl oxide as one of many compounds present in Greek tobacco.
The amounts of diphenyl oxide which may be released to the environ-
ment from plants are probably very small.
69
-------
VII. Generation of Biphenyl and Diphenyl Oxide By-Products
Section IV (General Manufacturing and Production Technology) discussed the
processes by which biphenyl and diphenyl oxide by-products are obtained and
refined commercially. This section examines biphenyl and diphenyl oxide gener-
ation in processes in which they are not refined or intended to be refined.
A. Biphenyl
1. Dealkylation of Toluene
The commercial producers of refined biphenyl, from the dealkylated
toluene by-product, are identified in Section III (Production) and Section IV-A-1,
along with the petrochemical company sources of the by-product. The companies
listed below also produce benzene by dealkylating toluene; however, they do not
refine the biphenyl stream or sell it to refiners.
Company Site
1. Ashland Oil Co. . Cutlettsburg, KY
2. Crown Central Petroleum Corp. Houston, TX
3. Enjay Chemical Co. (Exxon) Baytown, TX
4. Leonard, Inc. Mount Pleasant, MI
5. Monsanto Alvin, TX
6. Shell Oil Co. Odessa, TX
7. Signal Oil & Gas Co. Houston, TX
8. South Hampton Co. Stilsbee, TX
9. Sunray-DX Tulsa, OK
The biphenyl streams generated by the above companies are added
to fuels, usually fuel oils. The amount of biphenyl added to fuels via toluene
dealkylation totals nearly 20-25 million pounds annually (SRC estimation).
2. Naphthalene Feedstocks
Most of the naphthalene produced by petroleum operators is
petroleum-derived. Naphthalene and/or naphthalene precursors occur in
*Hahn, 1970, p. 411-412
70
-------
significant quantities in the following petroleum-derived streams (Erskine, 1970),
and the streams are used as naphthalene feedstock to produce a purified naphtha-
lene.
(1) Petroleum streams are catalytically reformed with the intention
of producing high-octane motor and aviation gasoline, and it is
possible to operate the reformer to yield heavy "bottoms" that
contain a high portion of methylnaphthalenes and naphthalenes.
Biphenyl is found as a by-product in the "bottoms".
(2) Catalytic cracking is used to convert heavy petroleum fractions
into lighter gasoline components, and one of the products of
cracking contains naphthalene precursors. Biphenyl is also
formed during cracking.
The typical composition of naphthalene feedstocks obtained from catalytic re-
formates and cracking are (Doelp, 1966):
Catalytic Catalytic
Reformates (Wt %) Cracking (Wt %)
biphenyl & acenaphthenes 6% 6%
alkylnaphthalenes 55% 35%
alkylbenzenes 20% 25%
other aromatics 19% 34%
Naphthalene is obtained by hydrodealkylating the alkylnaphthalenes
by the same method as previously described for hydrodealkylating toluene to ben-
zene (Section IV-A-2). Once again, the biphenyl by-product which is produced
will probably be added to fuels.
71
-------
3. Coal Tar
Biphenyl was first identified in the high-boiling fractions from
coal tar distillation in 1875 by Bvichner (Poffenberger, 1950). Coal tar amounts
to about 3% by weight of the coal which is processed. Along with many other
hydrocarbons, biphenyl is part of the high-boiling fractions, distilling in the
range 250°-300°C; however, no chemicals are separated commercially from this
range. A fraction distilling mainly in the range 240°-270°C is employed at
coking installations as wash oil for scrubbing benzole from coal gas, but most
of the oils in this range are used in creosote blends (McNeil, 1969). These
creosote oils are used for coating wood as a preservative, usually on railroad
ties and telephone poles. Due to the nature of this use, any biphenyl content
of the creosote oil will be exposed to the environment from weathering effects,
which may leach or vaporize the biphenyl from the treated wood.
Approximately 160 million gallons of creosote oil are consumed
annually (SRI, 1974). Dolansky (1974), in an analysis of creosote oil, determined
that 60% of the oil was composed of a hydrocarbon fraction and that 1.35% of the
hydrocarbon fraction was biphenyl. Applying Dolansky's figures to the U.S.
consumption of 160 million gallons of creosote oil annually reveals that
approximately 10 million pounds of biphenyl are contained in this consumption.
It is probably reasonable to assume that the bulk of this biphenyl will be ex-
posed to the environment.
In 1974, 677 million gallons of coal tar were produced domesti-
cally (United States International Trade Commission). Excluding that portion
of the coal tar distilled to creosote oils, the coal tar probably contained from
several to 10 million pounds of biphenyl which apparently ended up in fuels or
coking operations, but this is not known for certainty.
72
-------
4. Automobile Exhaust
It is likely that biphenyl is a component of the exhaust gas
emitted by an automobile engine; however, there is no proof in the literature
to support this supposition. Schofield (1974) lists the various hydrocarbon
components identified in auto emissions, which he obtained from the General
Motors Research Laboratories. The hydrocarbon list contains 1.11% by volume
of unidentified aromatics, and it may be possible that biphenyl is included
in these unidentified aromatics. Schofield does identify the presence of ben-
zene at a volume concentration of 2.15%, and at the elevated temperatures of
an automobile engine it is possible that the benzene could react chemically
to form biphenyl. Section IV-A-1 describes Monsanto's commercial production
of biphenyl by passing benzene vapors through a thermal reactor.
The total emissions of hydrocarbons from transportation sources
was estimated to be 29,400 million pounds in 1971 (Council on Environmental
Quality, 1973). If even a fraction of a percent of these emissions is biphenyl,
sizeable quantities could be released directly to the environment.
B. Diphenyl Oxide
1. Caprolactam - Nylon Production
Over 90% of the caprolactam produced in the U.S. is used to manu-
facture Nylon 6. The following data suggest that diphenyl oxide is formed as
a by-product during the production of caprolactum or its precursors: (1) Phenyl
ether (diphenyl oxide) has been identified in a settling pond of a nylon plant
in concentrations of 0.05 mg/1 (Webb at al., 1973); and (2) diphenyl oxide has
been isolated as an impurity in technical caprolactam in concentrations of
10 ppm (Kolar and Klacel, 1962).
73
-------
Caprolactam is commercially synthesized from processes based on
cyclohexanone. It is difficult to predict any diphenyl oxide by-product for-
mation during these processes. However, cyclohexanone is prepared, in one
commercial process, by catalytic hydrogenation of phenol. Phenol can be
catalyzed to produce diphenyl oxide, as shown by Monsanto's commercial method.
It may, therefore, be possible that diphenyl oxide is formed in small amounts
during the manufacture of cyclohexanone via phenol.
2. Bituminous Coal Tar
Diphenyl oxide has been identified as one of 133 individual
compounds present in bituminous coal tar (Karr et^ al., 1967). The fate of
diphenyl oxide which may be present in coal tar is unknown.
74
-------
VIII. Material Balance - Exposure to the Environment
This section attempts to define quantitatively the amounts of biphenyl and
diphenyl oxide released to the environment by man. Only uses which are releasing
or could potentially release substantial amounts of biphenyl and diphenyl oxide
to the environment are discussed. The following areas are not discussed because
quantities which may be released are insignificant by comparison: production of
refined biphenyl and diphenyl oxide and chemical synthesis (PCB's, alkylated
j^
biphenyls, Dowfax , butylated mpnochlorodiphenyl oxide, decabromodiphenyl oxide,
chloromethyldiphenyl oxide, or pesticides).
A. Biphenyl
Table VIII-1 lists the estimated environmental releases of biphenyl.
Explanations of the high-low estimates are given below.
1. Dye Carrier
Virtually all of the biphenyl used in dye carriers is released
from the dyeing plants, either in air emissions or in waste waters. Industry
spokesmen estimate that less than 5% of the biphenyl is exhausted as vapor,
so the large bulk is released in the waste waters. A discussion involving the
environmental fate of this water-released biphenyl is presented in Section IX-
B-l. The high estimate given in Table VIII-1 was obtained by arbitrarily assuming
that only 50% of the released biphenyl was effectively treated or treated at
all; the low estimate was obtained by assuming all of the biphenyl was treated
with a 95% efficiency. ,.'
2. Fungicide
As described in Section V-A-2, the biphenyl used as fungicide is
bound by solvents to either tissue paper or to paper pads. The biphenyl will
75
-------
Table VIII-1. Estimated Environmental Releases of Biphenyl
Use* or
Dye Carrier
Fungicide
/B\
Dowthernf0'^ A
Creosote Oils
Petroleum
Naphthalene Feedstocks
and Toluene Dealkylation
By-Product, Unrefined
Coal Tar, excluding
Creosote Oil Fractions
Automobile Exhaust
Current Annual
Use, Production
Content (X106 Ibs)
50
0.6-0.8
1.5
10
110
30-40
3-10
-
Quantities of Biphenyl
Current Annual
Environmental Release
Estimates (X106 Ibs)
High Low
25 3
0.6-0.8 0.3-0.4
small* -
10 10
small* -
small* -
unknown -
unknown unknown
(SRC Estimations)
Estimated 1966-1975
Use, Production, or
Content (X106 Ibs)
250-300
20-30
10-15
100
1000
200-300
30-100
-
Estimated 1966-1975
Environmental Release
(X106 Ibs)
High Low
125-150 15-18
20-30 10-15
small* -
100 100
0.01
small* -
unknown
unknown unknown
* See discussions in this section
-------
eventually dissipate from the papers as air emissions, due to biphenyl's
volatility, if left open to the atmosphere. The high estimate given in
Table VIII-1 was obtained by assuming all of the biphenyl was allowed to
dissipate; the low estimate by assumming one-half of the papers were des-
troyed by incineration, thereby destroying the biphenyl.
®
3. Dowthernr A
/m
It would seem unlikely that large amounts of Dowtherra^ A are
released to the environment because decomposed or impure Dowtherm can be used
for fuel purposes or purified via distillation.
(5)
There is no set "working-life" for Dowtherm^ A (Anderson, 1976).
As long as decomposition does not occur, the fluid can be used for many years
(decomposition is dependent upon working temperature). In actual practice,
the impurities are periodically removed from the system and the system is
simply "topped-off" with fresh Dowtherm.
Because Dowtherm^ A can last for years, the quantities in
current use must be quite high. SRC estimates that 5.5 million pounds of
Dowtherm^ A were produced in 1975. It is possible that 30-40 million pounds
or more are currently being used. An attempt to produce an exact figure for
current use was unsuccessful.
4. Creosote Oils
As explained in Section VII-A-3, due to the nature of the use
of creosote oils, any biphenyl content will be exposed to the environment
through use. Due to biphenyl's volatility, this biphenyl will be exposed
to the air as vapor emissions or may be leached by water from the treated wood.
77
-------
5. Petroleum
It would seem unlikely that any large quantities of the very
low percentage of biphenyl present in petroleum will be exposed to the environ-
ment. In Section VI-A-1, it was estimated that approximately 1000 pounds of
biphenyl are exposed to the environment annually from oil spills. For the ten-
year period between 1966-1975, a figure of 10,000 pounds was assumed for release
determination.
6. Naphthalene Feedstock and Toluene Dealkylation By-Product,
Unrefined
As for petroleum, it would seem unlikely that any large quan-
tities of biphenyl present in these sources will be exposed to the environ-
ment. The biphenyl from these sources will probably be added to fuel oils
which are burned. The biphenyl that is burned for fuel should be destroyed
and, therefore, not released to the environment.
7. Coal-Tar, Excluding Creosote Oils
As explained in Section VII-A-3, the eventual fate of this
product is not certain; therefore, no estimate is made.
8. Automobile Exhaust
See discussion of Section VII-A-4.
B. Diphenyl Oxide
Table VIII-2 lists the estimated environmental releases of diphenyl
oxide. Explanations of estimates are given below.
1. Dye Carrier
All of the diphenyl oxide used in dye carriers is released from
the dyeing plants, either in air emissions or in waste waters as previously
78
-------
Table VIII-2. Estimated Environmental Releases of Diphenyl Oxide
vo
Quantities of Diphenyl Oxide (SRC Estimation)
Current Annual
Use*
Dye Carrier
Perfume and Soap
(8)
Dowtherm^ A
Current Annual
Use (X106 Ibs)
0.25
0.10
4.0
Environment
Estimates
High
0.13
0.10
small*
:al Release
(X106lbs)
Low
.013
0.05
-
Estimated 1966-1975
Environmental Release
Estimated 1966-1975 (X1°6 lbs)
Use (X106 Ibs) High Low
1.0 0.5 0.05
1.0-2.0 1.0-2.0 0.5-1.0
30-40 small*
* See discussion in this section
-------
described for biphenyl dye carriers. The high estimate given in Table VIII-2
was obtained by assuming that only 50% of the released diphenyl oxide was
effectively treated or treated at all; the low estimate was obtained by
assuming all of the diphenyl oxide was treated with a 95% efficiency.
2. Perfumes and Soaps
It can be assumed that all of the diphenyl oxide used in per-
fumes and soaps will be released to the environment. The high estimate given
in Table VIII-2 assumes no treatment at waste water facilities to degrade
diphenyl oxide content; the low estimate assumes that 50% of the released
diphenyl oxide is treated effectively.
/g\
3. Dowthernr^ A
See discussion in Section VIII-A-3.
80
-------
IX. Environmental Perspectives
A. Occupational Exposure to Man
The following OSHA standards have been established for exposure to
biphenyl and diphenyl oxide in air:
3
Biphenyl 0.2 ppm (approximately 1 mg/m ) (time weighted average)
Diphenyl Oxide 1.0 ppm (time weighted average)
There are no OSHA recommendations to control direct contact of biphenyl or di-
phenyl oxide in solid or liquid form; possible skin absorption of these sub-
stances is apparently not considered to have measureable health significance.
The following toxicity data are available for the two chemicals
(Christensen and Luginbyhl, 1975; Opdyke, 1974; Haas e£ al., 1975; Branson, 1977)
3
Biphenyl: inhalation - human *TD : 4400 yg/m
oral - rat LD^°: 3280 mg/kg
oral - rabbit LDsn: 240° m8/k§
skin - rabbit U> ": 2500 mg/kg
fish - fathead minnow TL (96 hrs): 1.5 mg/1
- fathead minnow LC™ (96 hrs): 5.3 mg/1
Diphenyl
Oxide: oral - rat LDSO: 337° m8/k§
skin - rabbit LD^JJ: > 5000 mg/kg
fish - fathead minnow LC^ (96 hrs): 5.5 mg/1
*Key to Abbreviations
TD - lowest published toxic dose
LD^° - lethal dose 50 percent kill
TL - tolerance median
LC,.- - lethal concentration 50 percent kill
81
-------
B. Release to the Environment
1. Biphenyl
Most of the biphenyl released to the environment by man is re-
leased by the textile dyeing industry. The larger dyers (Burlington, for ex-
ample) operate mills which have their own waste treatment facilities to process
wastes while most other dyers apparently release wastes to city or county
facilities.
a. Effectiveness of Biphenyl Waste Treatment
The exact effectiveness of treatment of biphenyl wastes by
each treatment plant cannot be ascertained because the individual treatment
plants do not monitor biphenyl levels. Instead, they monitor BOD and/or COD
levels.
To provide an example of COD levels before and after treatment,
SRC contacted the largest Burlington Industries' mill, which is located in
Greensboro, NC. Burlington operates their own waste treatment facility at this
mill. Mr. Joe Ameen, Sanitary Engineer for the mill, reports that COD normally
measures 1200-1500 mg/1 on the influent stream to waste treatment while the
effluent normally measures 200-300 mg/1. The effluent is discharged into a
river. In addition to biphenyl, the influent stream contains other dye carriers,
such as trichlorobenzene, butyl benzoate, etc., dyestuffs, emulsifiers, and all
other factory wastes. Mr. Ameen also reports that in community waste treatment
plants operated by Burlington in other cities, a 15% or more addition of community
solid wastes to the Burlington wastes reduces COD levels of the effluent to 50-
100 mg/1.
Dr. Peter Gaffney of the Biology Department of Georgia
State University has been studying biphenyl problems in water at municipal
82
-------
waste treatments for several years. He states (Gaffney, 1976) that biphenyl is
effectively processed by the treatment plants; however, his concern has been
directed at potential PCB formation during chlorine pre-treatments.. This PCS
formation is discussed in more detail in Section IX-B-l-c.
Biphenyl has been detected in river water by Webb et al.
(1973) and Kites (1973). Kites identified biphenyl, trichlorobenzene, and
butyl benzoate in the waters of the Merrimack River at 0.1-0.5 ppb concentra-
tion. Kites attributes the presence of these organics to upstream textile
factories.
Also, W.C. Tichner of the Environmental Resources Center
of Georgia Institute of Technology has been studying the problem of biphenyl
effluents from polyester carpet manufacturing in Georgia. Tincher has measured
biphenyl concentrations in streams at the point of effluent discharge to several
miles downstream. He has found that the biphenyl concentration drops quite
rapidly after effluent discharge. He attributes this phenomenon to the vola-
tility of biphenyl (Tincher, 1976). It is worth noting that rather than complete
biphenyl degradation, at waste treatment plants, or complete volatilization occurr-
ing, various degradation intermediates may be present (usually not determined)
such as, phenylphenol (Gaffney, 1977 a). There has apparently been no work done
showing the kinetics of biphenyl degradation completely to carbon dioxide and
water; this would be desireable.
In 1974, the Sun Oil Co. commissioned Dr. J. Ferguson of
Johns Hopkins University to experimentally determine biodegradation rates for
biphenyl and other common dye carriers. To determine aerobic biodegradation
83
-------
rates, typical treatment cultures were obtained and pre-conditioned to the dye
carriers. All cultures received an initial dye concentration of 50 ppm. Ex-
tractions of the culture and the water system were made at various times and
analyzed.
Figure IX-1 shows how long the microorganisms took to reduce
the concentration of the dye carrier containing 95% biphenyl and of the other
dye carriers (Haas et al., 1975). The biphenyl was totally biodegraded in about
48 hours.
b. Environmental Chlorination of Biphenyl
Dr. Peter Gaffney first reported finding PCB's in a sewage
treatment plant's trickling filter bed in 1974 (Gaffney, 1974). He suggested
that the PCB's were generated as a result of a high biphenyl influx from a tex-
tile mill coupled with a waste water pre-chlorination for odor control and dis-
infection. It was determined later, however, that commercial PCB's were entering
this waste treatment facility. In laboratory tests, Gaffney found that PCB's
were formed when 10 mg/1 of biphenyl were added to dionized water held at 20°C,
and then 1 mg/1 of chlorine was added and the reactants kept in contact for one
hour (Versar, 1976).
Carlson &t^ al. (1975) conducted a detailed laboratory
analysis to determine chlorine incorporation into biphenyl and other aromatic
compounds under conditions utilized for water renovation. Table IX-1 is a
summary of PCB and chlorobiphenyl formation under the various aqueous conditions
used (Carlson et al., 1975). the results shown in Table IX-1 confirm the
possibility of chlorine incorporation into the biphenyl nucleus under a variety
of conditions.
84
-------
100
1,2,4-Trichlorobenzene
and Perchloroethykene
o
I
o
u
3-Methyl-Methyl Sal icy late
40-
20-
Elapsed Time ( Hours)
Figure IX-1.
Reduction of Concentration Owing to Biodegradation - Analysis of
Culture Cells and Water (Haas et al. , 1975)
85
-------
Table IX-1. Chlorination of Biphenyl Utilizing Water Renovation Conditions
(Carlson et al., 1975)
oo
Chlorine
Source
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
Ca(OCl)2
C12
NaOCl
C12
NaOCl
ci2a
NaOCl
pH
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.5
2.1
2.8
4.9
10.4
2.2
7.0
Chlorine,
ppm
100
100
100
100
10
20
35
50
100
10.9
295
266
830
1350
2950
Reaction
Time, hr
24
48
72
120
120
120
120
120
120
0.25
0.25
0.25
0.25
0.25
0.25
Reaction,
0.4
1.0
1.7
2.5
0.004
0.02
0.04
0.15
0.27
2.2
9.3
0.1
0.6
16
5.2
2-
15
32 •
56
69
0.1
0.44
1.4
4.0
8.8
120
450
5-10
40
180
280
Ppb of Chlorinated Product
3-, 4- 2,2' 2,3'-2,4' 4,4'-
10
27
47
82
0.12
0.51
1.2
4.9
7.4
10 20
190 10 130 40
80 80 370 500
110 80 30
Saturated biphenyl solution found experimentally to be 6.0 mg/1.
Higher chlorinated isomers also present.
-------
Dr. Gaffney has conducted an investigation to determine if
chlorobiphenyls can be produced in wastewater treatment plants because of the
use of chlorine with municipal wastes containing biphenyl (Gaffney, 1977 b).
The results indicated that various chlorobiphenyl isomers are produced during
final chlorination. The chlorobiphenyl isomers predominately formed are the
2-chloro, 2,2'-dichloro, and 2,4'-dichloro isomers. A relatively small amount
of trichlorobiphenyl was also detected. It should be noted that the term PCB
should be reserved for only those biphenyl molecules having three or more
chlorine atoms attached. Laboratory chlorination of influent and effluent from
a municipal waste treatment facility also results in the formation of these and
other chloro-organic substances (Gaffney, 1977 b).
Dr. Richard Johnsen has also conducted laboratory studies
of biphenyl chlorination under conditions which may exist at waste treatment
plants (Johnsen, 1975). Biphenyl in water (5 ppm) was added to chlorinated water
given chlorine concentrations of 8, 83, and 830 ppm. Under ambient conditions
and after aging for 24 hours and 1 week, the samples were analyzed, along with
suitable controls, by gas chromatography. The results were somewhat surprising;
i
when chromatographs of biphenyl reacted with Cl^-water (83 ppm and 830 ppm) for
1 day are superimposed over a chromatograph of Arochlor 1221 (a commercial PCB),
striking overlaps are observable, although peak heights are not the same. This
preliminary work by Dr. Johnsen is being continued.
Dr. E.L. Kothny has suggested an interesting source of PCB
and other chlorinated organics found in the environment (Kothny, 1976). He has
proposed that the chlorine released from sea salt particles might chlorinate
organics such as biphenyl found in the atmosphere. There is, however, no evi-
dence to support this contention at present.
87
-------
2. Diphenyl Oxide
The information and data given below have been acquired from the
Dow Chemical Co. (Otis, 1976).
a. Effectiveness of Waste Treatment
"Generally, organic chemicals with a BOD- (5 day biochemical
oxygen demand) value in excess of 60 percent of the stoichiometrically required
amount of oxygen are readily degraded in conventional waste treatment facilities.
Under favorable waste treatment conditions, concentrations of diphenyl oxide in
waste streams have been reduced up to 95%. This magnitude of reduction is typi-
cal of that encountered with municipal wastes. Analytical methods are available
for measuring the concentrations of diphenyl oxide in waters and waste streams.
In the event of a gross discharge of diphenyl oxide into a river, techniques are
available that can predict the downstream concentrations of diphenyl oxide based
on some known rates and routes of removal from the river. These routes include
microbial degradation (by a variety of aquatic microorganisms), absorption on
suspended solids, and volatility from water" (Dow Technical Data Sheet - XAS-
1075L).
b. Biodegradation
"The most desirable environmental property of diphenyl oxide
is its ability to biodegrade into carbon dioxide and water in the presence of
naturally occurring microorganisms. This observation is supported by a variety
of tests including the standard biochemical oxygen demand (BOD) test, an oxygen
probe test, and tests which measure the chemical disappearance from soil and
river sediments. A postulated mechanism of diphenyl oxide conversion to carbon
dioxide and water under the influence of aerobic microorganisms is believed to
88
-------
involve some catechol-like intermediates. However, positive proof for this
mechanism has proven difficult because of the transient existence of the inter-
mediate compounds" (Dow Technical Data Sheet - XAS-1075L).
c. Bioconcentration
"Detection of chemical residues in fish has been the key
environmental alert for DDT and PCB's. Consequently, the potential of diphenyl
oxide to bioconcentrate was determined.* Bioconcentration is a measure of the
relative distribution of a test chemical between fish tissue and exposure water.
Diphenyl oxide has been found to bioconcentrate to only a limited extent, quite
unlike DDT or PCB's. When placed in fresh water, the fish were found to eliminate
diphenyl oxide rapidly, 50% each day compared to 50% each 30 days for an isomer
of PCB's. These results show that hazardous or persistent concentrations of
diphenyl oxide in fish are unlikely to occur" (Dow Technical Data Sheet - XAS-
1075L).
The potential for biphenyl to bioconcentrate was also deter-
mined by Dow Chemical. Neely et^ a!L., (1974) determined the bioconcentration as
the ratio of the uptake rate of the exposure chemical to the clearance rate.
For biphenyl, the bioconcentration was found to be 438+48 while for diphenyl
oxide the bioconcentration was 196+39.
*Results published by Neely e^t al., (1974). The log bioconcentration factor
was experimentally determined as 2.29 (therefore, bioconcentration factor = 196)
89
-------
X. Environmental Assessment
A. Biphenyl
Biphenyl is being released to the environment in quantities which may
total 60 million pounds annually and perhaps even higher (SRC estimate). The
largest known source of biphenyl release is from biphenyl's use as a dye carrier
in the dyeing industry. Approximately 50 million pounds of biphenyl are annually
used for dyeing applications (SRC estimate). This biphenyl is usually released
in the wastewaters from the dyeing factories to either municipal treatment
facilities or to on-site treatment facilities. Common forms of waste treatment
appear to be successful in the processing of biphenyl wastes (Gaffney, 1976).
Laboratory experiments have shown that typical cultures from water renovation
facilities are able- to reduce biphenyl concentrations to nearly zero in only 48
hours (Haas et^ al., 1975). However, since biphenyl is not monitored at treat-
ment facilities, the efficiency of general treatment cannot be determined with
certainty. Also, the method of treatment may be a significant factor in the
amount of biphenyl converted by biodegradation. Tihcher (1976) has found that
the concentration of biphenyl released to streams rapidly falls below 1 ppm
after release, due to biphenyl's volatility. This suggests that methods which
allow biphenyl wastes to be exposed to the atmosphere for periods of time during
treatment may allow quantities of biphenyl to be released into the air by volatil-
ization.
A major concern of biphenyl release to waste treatment plants from the
dyeing industry is the evidence which indicates that biphenyl-containing sewage
may be chlorinated to PCB or chlorobiphenyl isomers during pre-chlorination
processes for disinfection and deodorization (Gaffney, 1974, 1976, 1977b;
90
-------
Carlsen, 1975; Johnsen, 1975). Laboratory experiments which have mimicked
treatment facility methods have found that the biphenyl nucleus can be chlor-
inated with four, or usually less, chlorine atoms. Commercially prepared PCB's
have a much greater degree of chlorination and have certainly less biodegrada-
bility than the PCB and chlorobiphenyl isomers which may be generated at waste
treatment plants. Although sufficient research has yet to be done for conclusive
results, the present indications suggest that chlorination of biphenyl-containing
sewage deserves a great deal of consideration and perhaps restriction.
Another major source of biphenyl release to the environment is from
creosote oils which are used to preserve wood, especially railroad ties and
telephone poles. Biphenyl is present in creosote oils because it is one of the
constituents in the high-boiling fractions of coal tar from which these creosote
oils are derived. It is likely that nearly 10 million pounds of biphenyl are
annually released to the atmosphere by biphenyl1s volatilization or to water by
leaching from creosote oils (SRC estimate).
An uncertain but potentially significant source of biphenyl exposure
to the atmosphere is automobile exhaust. It is possible that biphenyl is one of
the many hydrocarbons present in auto emissions; however, there is no available
monitoring data to confirm this supposition. Even if biphenyl is present in
only a very small fraction of a percent, the annual quantity emitted could be
very large due to the enormous amounts of hydrocarbons emitted by autos.
B. Diphenyl Oxide
Diphenyl oxide is being released to the environment in quantities which
may total 0.25 million pounds annually (SRC estimation). The two major sources
91
-------
of diphenyl oxide release are soap and perfume use and dye carrier use. Man
has been exposed to diphenyl oxide as an ingredient in some soaps and perfumes
since the early 1930's. Laboratory and practical experience have suggested
no adverse effects from diphenyl oxide use via perfumes and soaps. The Council
of Europe (1970) included diphenyl oxide in the list of temporarily admissible
artificial flavouring substances (Opdyke, 1974); however, spokesmen for Dow
Chemical (Branson, 1977) indicate that flavouring should mean odor and not
food additive. They question the use of diphenyl oxide as a food additive
without more data.
Industrial effluents from plants using diphenyl oxide as a dye carrier
can apparently be effectively treated in conventional waste treatment facilities
(Dow Technical Literature - XAS-4169L) when such treatment is used.
92
-------
Appendix A
Physical Properties
93
-------
Biphenyl (Monsanto Tech. Bull. 1C/FF-29)
Melting point, °C
Boiling point at 760 mm Hg, °C
10.5 mm Hg, °C
Specific gravity, 20°/4°C
77°/4°C
69
'255
118
Vapor pressure 0.0097 mm Hg at 25°C**
Lbs./gallon at 77°C
Refractive index, n
77
D
Viscosity at 70°C, Saybolt Sec.
100°C, Saybolt Sec.
1.04
0.99
8.23
1.588
31.2
28.8
Surface tension at 129,2°C, dynes/cm 39.5
Flash point, closed cup, °C
Open cup, °C
Latent heat of fusion, Btu/lb.
Specific heat, Btu/lB/°F
Odor
Appearance
Molecular Weight
Empirical Formula
Structural Formula
113
124
53.1
0.43
Pleasant, peculiar
Colorless to pale yellow crystallized solid or flakes
154.20
C6H5C6H5
Solubilities - Grams biphenyl per 100 cc of solvent
Solvents Solubility
Water
bons Mineral Spirits
Gasoline (Texaco)
Kerosene
Benzene
Xylene
Turpentine
Toluene
16.9
24.1
17.5
81.5
56.9
24.2
62.0
0.00018*
0.00075 at 25°C**
26
26
27
27
27
24
18
* 95% Biphenyl dye carrier (Haas et al., 1975)
** Branson (1977)
94
-------
Diphenyl Oxide (Dow Form No. 110-288-72)
DIPHENYL OXIDE GRADE
Technical Perfume Industrial
Molecular Weight
Boiling Point °C 760 mmHg
Specific Gravity 25/25°C
Pound per gallon, 25 °C
Refractive Index, 25 °C
Freeze Point °C
Flash Point °F COC
Fire Point °F
Auto Ignition Point °F
Latent Heat of Vaporization
Cal/mole at B.P.
Approximate Solubility g/lOOg
Solvent at 25 °C
Acetone
Ether
Benzene
Methanol
Water
Carbon tetra chloride
n-Heptane
170.2
257°
1.070
8.92
1.578
26°
239°
258°
1144°
11,800
00
00
oo
oo
20.8 ppm
00
00
170.2
257°
1.070
8.92
1.579
27°
239°
258°
1144°
11,800
OO
00
00
oo
21 ppm
00
00
_
255°
1.065-1.075
8,92
-
15°
235°
255°
-
-
00
00
00
oo
21 ppm
oo
00
Solubility of DPO in water at 25°C 20.8 ppm
Solubility of water in DPO at 25°C ........... 0.071%
Solubility of water in DPO at 30°C 0.077%
BOILING POINTS OF DIPHENYL OXIDE
Boiling Point MM Hg
257. 9°C
181. 3°C
147. 1°C
121. 0°C
77.0°C
760
100
30
10
1
Vapor pressure 0.019 mm Hg at 258C*
*Branson (1977)
95
-------
Diphenyl Oxide (Dow Form No. 110-288-72)
DIPHENYL OXIDE GRADE
Technical Perfume Industrial
Molecular Weight
Boiling Point °C 760 mmHg
Specific Gravity 25/25°C
Pound per gallon, 25 °C
Refractive Index, 25°C
Freeze Point °C
Flash Point °F COC
Fire Point °F
Auto Ignition Point °F
Latent Heat of Vaporization
Cal/mole at B.P.
Approximate Solubility g/lOOg
Solvent at 25°C
Acetone
Ether
Benzene
Methanol
Water
Carbon tetra chloride
n-Heptane
170.2
257°
1.070
8.92
1.578
26°
239°
258°
1144°
11,800
00
00
00
00
20.8 ppm
oo
00
170.2
257°
1.070
8.92
1.579
27°
239°
258°
1144°
11,800
00
00
00
00
21 ppm
00
00
— .
255°
1.065-1.075
8.92
-
15°
235°
255°
-
-
00
00
00
00
21 ppm
00
00
Solubility of DPO in water at 25°C 20.8 ppm
Solubility of water in DPO at 25°C 0.071%
Solubility of water in DPO at 30°C 0.077%
BOILING POINTS OF DIPHENYL OXIDE
Boiling Point MM Hg
257. 9°C
181. 3°C
147. 1°C
121. 0°C
77.0°C
760
100
30
10
1
Vapor pressure 0.019 mm Hg at 25°C*
*Branson (1977)
95
-------
Appendix B
Material Safety Data Sheets
96
-------
MATERIAL SAFETY DATA SHEET
(APPROVED BY THE U.S. DEPARTMENT OF LASOR AS • "essantiolly similar" to form OSHA-20)
Act af 1970 0-.1 iboll 131 b. j»j lor :
Section I NAME & PRODUCT
MA:; ji; iC V-iPER'S N AVL CITY. STATE. Z.P CODE
DOW CHEMICAL U.S.A. MIDLAND, MICHIGAN 48640
L^A't T •• S P O r* M WRlTTCN
February 19. 1973
E V. £ R C E f J C v '
517-
PREPARED S> iSignoture) N ^^ > , ^^S"
> HO *1 t
636-
j^1
NO. • Z4 HOURS
4400
Diphenyl Oxide, Technical
Diphenyl Ether
Section 2 INGREDIENTS
Diphenyl oxide
(Not a specification value)
%
95
TLV
1 P!
Section 3 PHYSICAL DATA
BOILING POINT ?F.)
VAPOR PRESSURE (mmHgol 20°c)
VAPOR DENSITY (oir = 1)
4QR
__-
___
SOLUBILITY IN WATER
SPECIFIC GRAVITY (H20= 1)
r, VOLATILE BY VOLUME
Insoluble
1.070 ft ?7M°r.
— - _
APPEARANCE _ . Colorless liciuid
Section 4 FIRE AND EXPLOSION HAZARD DATA
> . A 5 H = O 1 N T
205 'f
IANO METHOD OSEDI
EXTINGUISHING
MEDIA •-
fx
WATER
FOG
Cleveland
IXjFOAM
Open Cup
r— -i ALCOHOL
|X | FOAM
r L, AMMA B LE
L.F.L. (j
fx
co?
L'MITS
.8
ra
(STP IN AIRp
DRY
CHEMICAL
|u. F. L.
OTHER
_Q _
1.5
SKEf.AL FIRE FIGHTING PnOTECTION EQUIPMENT AND HAZARDS
None.
Section 5 REACTIVITY DATA
STABILITY
(NORMAL CONDITIONS)
X STABLE
INCOMPAT.
IBILITY
UNSTABLE
MA TfiftlA L5 TO A
LjWATER
0
THEP
CONDITIONS TO AVOID
/OIO
n___ _ n v 1 nt 7 IMf* '
ACID BASE I (CORROSIVE MATERIAL
None.
HAZARDOUS
POLYMERIZ-
ATION
X
MAY
OCCUR
WILL NOT
OCCUR
CONDITIONS TS AVOID
Section 6 SPILL OR LEAK PROCEDURES
Small spills - absorb in sweeping compound.
Large spills - call Dow emergency number for instructions
' ;S A . ME THOD
Burn or bury in accordance with local ordinances.
97
-------
Mfl
Diphenyl Oxide, Technical
ATERiAL SAFETY DATA SHEET (CO,T.,
DOW CHEMICAL U.S.A.
MIDLAND, MICHIGAN 43640
Section 7 HEALTH HAZARD DATA
tow single dose oral; LDgo 4000 mg/kg for both rats and guinea pigs. Estinat
ng from these data, the lethal dose for a 100 pound person may be in the
range of 3/4 cupful.
E > L C 3 :« T A C i'
|Mild to moderate irritation; unlikely to cause injury.
[Occasional contact - no adverse effects expected.
Mild to moderate irritation upon repeated, prolonged contact.
I
I
:1SO" = TCN No LD determined because of lack of indication of
Not readily absorbed - problem from absorption. '
LV: 1 ppm - based on odor control. No problem at room temperature.
Disagreeable odor, possible liver injury at high concentration.
1
-'
f\
1
t
a
•
.
EYE
'
FLUSH
fliTH
FLOWING
WATER
EYES & SKIN: Flush with plenty of water; get medical atten-
tion if irritation develops. Remove contaminated clothing
and free of chemical before reuse.
INHALATION: If discomfort develops from breathing vapors, get
patient to fresh air.
INGESTION: No known antidote; treat symptomatically.
•
NEVER GIVE
FLUIDS OR
INOUCE
VOMITING
IS UNCONS-
CIOUS OR
HAVING
CONVULSIONS
Section 8 SPECIAL PROTECTION INFORMATION
t: -i T ,. A i • ON
Sufficient to control to TLV.
"' i~A"f 5 KT~3'!~"3 TcTcTio'f T' i. p"e cTTx"ty p« <
When disagreeable odors occur, full-face mask and canister for organic vapors,
T .f: :_OTHING
Clean clothing.
I
,
! \:>3r NOR^A'-'-vlylsArErY cL»ssir«i
f RO'I ECTlO" 3
(The iilcrnotion herein ij given in good foith, bjt no wo.-ront>, eipreited or implied, it mode)
-------
MATERIAL SAFETY DATA SHEET
(APr^O'/iD 3f Th= U.S. DEPARTMENT Or I.A30R Ai - "sssMLL NOT
X L o-cus
C 5N •> r :CNi T3 A ,' J, r
•
Sectijn 6 5P1LL OS LcAX PROC£OUSi=3
Scoop up and salvage if possible.
Observe Federal, Stats and Local laws
for disposal instructions.
Contact The Dow Chemical Corr.oanv
99
-------
I
I
3iphenyl, High Purity
•1ATERIAL SAFETY DATA SHEET {CONT,
DO'V CH-.vdC
M.3LASD, -I t;-ii
Sect.on '' HEALTH H^ZARO CUT
!Low single dose oral toxicity. LD5o rats is .greater than 4000 mg/kg.
Estimating front thesa data, the lethal dose for a 100 Ib. person .-.ay b
4-5 ounces.
§' - - "4C:
Up to slight irritation but no corneal injury.
Shore single exposure not likely to cause significant irritation. Prolonged
or repeated exposure may cause slight irritation.
I
Not likely to be absorbed in toxic amounts.
I
T!_V: 0.2__p_?m or 1 mg/m3 (1974)
Respiratory irritation.
SYZS:. Flush with plenty of vater for 5 minutes and get T.edicaL .,.,,,,=
help
if ill effects occur. SKIM: Wash with scii
Remove grossly contaminated cio:.hing a-.l wash befTr.i r-2Lij=
NHALATION: If ill effects occur, ^^
gat medical help. INGESTION: Not likely a problen
amounts are swallowed, see above, promptly ir.duca vomiting
and get medical help.*
•
Co.ntrol dusts or mists to TLV.
Respiratory protection required in absence of proper environ
If recuirod, use an approved dust respirator.
Clean body covering clothing.
no •-,-.••<
_, :'^. Vo."k"N?LE* p Eye _f our. tain and v a shir.': facilibiss n-ar v;o:rk area.
„.__—._.„ _^.--_ -.___._.__,.______.._..._.._.
Practice reasonable care and cleanliness to avoid gross :;;kin and aye contact.
Avoid breathing vapors and dusts if generated.
*NOT2 TO PHYSICIAN: No specific antidote known. Traatrr.eni: depends on the
sound judgment of the physician and the individual reactions of the pacier.-.
100
-------
MATERIAL SAFETY DATA SHEET
(APPROVED SY THE U.S. DEPARTMENT OF LABOR AS.. "cssentiolly similor" to form OSMA-20)
(,< 1970 end »he
Section 1 NAME & PRODUCT
•A •..,-- „" • ..'• t .-••« <: AMfc
CHEMICAL JS
C i I 'i 'J 7 i T £ Z ; P C O O E
MIDLAND. MICHIGAN 48640
. H f T£ M
1974
'Signofure)
E'-C <• "HO'IE MC. ;j
517 - 636 - 4400
T K« ., :_ t N - *.'. £
DOWTHERM® A heat transfer fluid
Section 2 INGREDIENTS
Diphenyl oxide
Diphenyl
73.5
26.5
jlppm
(Not specification values)
Section 3 PHYSICAL DATA
BOILING POINT (°F.)
VAPOR PPFSSURf: (inmHejot 20*c)
VAPOR DENSITY (air = I)
6"
>i
SOLUBILITY IN WATER
SPECIFIC GRAVITY jH2o-D 1.050-1.075 & 25/25
n VOLATILE BY VOLUME
iquM»_a.r
Section 4 FIRE AND EXPLOSION HAZARD DATA
LASH "^I'Jl trO METHOD USCD.
255T Cleveland Open Cup
L LIMITS .3 T P IH AIR1
0.5% (500°F) |u.,.L. 6.2% (500°F)
EXTIMCUISHINO
MEDIA «•
I WATER
i—|ALCOH<
| [FOAM
:o2
C r; ,.M. !'•=. r r IC-1 r INC PHOT CC flON fcQ'JIPMENT AND MA; AMOS
__„ OTHER
-.DRY i 1
JCHEMICAL I | _
Self-contained breathing apparatus may be needed in enclosed spaces
Section 5 REACTIVITY DATA
STABILITY
:NO«.VAL CONDITIONS)
P"77"1
UNSTABLE
COKTMTIONC TO AVOID
IHCOMPAT.
I8ILITY
None
LJ''A1ER LJACID LJBASE CORROSIVE [_X.
OXIDIZING
MATERIAL
.•. *:o•.!'•>: t: •( 13:1 vriornjc fs
HAZARDOUS
POLYMERIZ-
ATION
X
MAY
OCCUR
'WILL NOT
OCCUR
CuMUiriONS TO AVOID
Section 6 SPILL OR LEAK PROCEDURES
'.. •••* ' •'• f L 'J .'- C A', i M A ~! !" d i A -. ' -j~>i FT.' ^Af (TT7 OH &*• ' i '7e (. ' '
Soak up with absorbant material.
Incineration in approved equipment.
101
-------
i
DOWTHERM® A
1ATERIAL SAFETY DATA SHEET ,CONT,
DOW CHEMICAL U.S.A.
MIDLAND. MICHIGAN 4864G
Section 7 HEALTH HAZARD DATA
tow'single dose oral toxicity. LD5P rats is in the range of 2000 to 4000 mg/kg.
Estimating from these data, the lethal dose for a 100 Ib. person may be 2
™o 4 fluid ounces.
I
p to mild irritation but no corneal injury.
f:
lort single exposure not likely to cause significant irritation. Prolonged
or repeated exposure may cause up to mild irritation.
i
i
TIk~ely to be absorbed in toxic~ amounts. Very low in
route.
LV: JLpPjn (1973)
>'•".:"; '•"?•'£~* !:
I
I r I-10T NOPM»Ll.Y|v Ifti^STV CL4SSKS I Is A F E 1 V O L 4SS E i I JC-KVICM
I.ECTIONJ L—J.'if-CE1S««¥ |A_|/
-------
REFERENCES
Ameen, J. (1976), Personal Communication, Sanitary Engineer, Burlington Industries,
Greensboro, N.C., May 1976.
American Conference of Governmental Industrial Hygienists (1974), "Documentation
of the Threshold Limit Values".
Anderson, L. (1976), Personal Communication, Dow Chemical Co., Midland, MI,
May 1976.
Anon. (1976 a), "Journal of Commerce," April 22, 1976, p. 5.
Anon. (1976 b), "The Search Is On for PCB Substitutes," Chemical Week, Feb. 25,
1976, p. 34-35.
Anon. (1976 c), "Concentrates," Chemical & Engineering News, May 3, 1976, p. 21.
Barrow, W. (1976), Personal Communication, Pilot Industries, Houston, TX,
March 1976.
Blumer, M., Sanders, H.L., Grassle, J.F. and Hampson, G.R. (1971), "A Small Oil
Spill," Environment _13(2):2.
Branson, D. (1975), "Dow XFS-4169L: An Environmentally Acceptable Capacitor
Fluid," Nat. Conf. on Polychlorinated Biphenyls (Nov. 19-21, 1975,
Chicago, IL), EPA Contract No. 68-01-2928.
Branson, D. (1977), Personal Communication with T.E. Kopp (Project Officer),
April 25.
Britton, E.G. and Reed, W.R. (1933), U.S. Patent No. 1,899,257, assigned to
Dow Chemical Co, Feb. 28, 1933.
Cantrill, J.E. (1968), "Phenolic Ethers," Kirk-Othmer Encycl. Chem. Technpl.,
2nd Edition, 15:165-175.
Carlson, R.M., Carlson, R.E., Kopperman, H.L. and Caple, R. (1975), "Facile
Incorporation of Chlorine Into Aromatic Systems During Aqueous Chlori-
nation Processes," Environ. Sci. Technol. j>(7):674-5.
Carter, C. (1976), Personal Communication, Chemical Processing of Georgia,
Dalton, GA, May 1976.
Chemical Marketing Reporter (1976), "Current Prices of Chemicals and Related
Materials," pp. 34-45, May 10.
Christensen, H.E. and Luginbyhl, T.T. (1975), Registry of Toxic Effects of
Chemical Substances^ 1975 Edition, U.S. Dept. of Health, Education, and
Welfare, U.S. Government Printing Office, Washington, D.C.
Cogley, R. (1976), Personal Communication, Westinghouse Corp, Manor, PA, May 1976.
103
-------
Cohen, S. (1976), Personal Communication, Tanatex Chemical Division, Lyndhurst,
NJ, March 1976.
Conover, C. and Huff, A.E. (1939), U.S. Patent No. 2,143,509, Jan. 10, assigned
to Monsanto Co.
Cosner, C. (1976), Personal Communication, Paper«Pak Corp., Orlando, FL, May 1976.
Council on Environmental Quality (1973), Environmental Quality - The Fourth Annual
Report of the Council on Environmental Quality, P266, Government Printing
Office, Washington, B.C.
Danziger, W.J. (1966), "Heat-Transfer Media," Kirk-Othmer Encycl. Chem. Technol.,
2nd Edition, J.0:846-851.
Davies, D.J.I. (1963), Chemical & Process Engineering ^4:473-476.
Derrig, M. (1976), Personal Communication, Gulf Oil Corp., Houston, TX, May 1976.
Doedens, J.D. and Rosenbrock, E.H. (1961), U.S. Patent No. 3,004,072, assigned
to Dow Chemical Corp.
Doelp, L.C. (1966), "Hydrodealkylation," Kirk-Othmer Encycl. Chem. Technol., 2nd
Edition, 11:453-461.
Doedens, J.D. and Cordts, H.P. (1961), "Diphenyl Ether Derivatives in Conden-
sation Polymers," Indust. and Eng. Chem. 5^3;59.
Dolansky, V. (1974), Sb. Vys. Chem. Technol. Praze, Technol. Pally 1974, D30,
329-34, Chem. Abstract J53:150092j.
Dundee, B. (1964), U.S. Patent No. 3,133,122.
Durgin, C.B. and Jenkins, R.L. (1933), U.S. Patent No. 1,894,266, January 17,
assigned to Monsanto Co.
Earhart, H.W. (1976), Personal Communication, Manager-Special Aromatic Products,
Sun Oil Co., Corpus Christi, TX, April-May 1976.
Environmental Protection Agency (1975), "National Conference on Polychlorinated
Biphenyls," (Nov. 19-21, 1975, Chicago, IL) EPA-560/6-75-004, Contract No.
68-01-2928.
Erskine, M.G. (1970), "Naphthalene," in Chemical Economics Handbook. Stanford
Research Institute, Menlo Park, CA.
Faith, W.L., Keyes, D.B. and Clark, R.L. (1965), Industrial Chemicals. 3rd
Edition, John Wiley & Sons Inc., New York, pp. 130-1, 585-88.
104
-------
Franke, A. and Traber, W. (1972), German Offen. 2,223,380, assigned to Ciba-
Geigy, Nov. 30.
Gaffney, P. (1974), "Letters - PCB's: Another Source?," Science 183;367-70.
Gaffney, P. (1976), Personal Communication, Georgia State University, Atlanta, GA,
June 1976.
Gaffney, P. (1977a), Personal Communication with T. Kopp (Project Officer), March.
Gaffney, P. (1977b), "Chlorobiphenyls and PCB's: Formation During Chlorination,"
Journal WPCF, March 1977, p. 401-404.
Garza, N. (1976), "Who's Building in HPI-USA," Hydrocarbon Processing, March,
p. 43.
Graham, W. (1976), Personal Communication, Florasynth, Inc., New York, NY,
April 1976.
Haas, J.M., Earhart, H.W. and Todd, A.S. (1975), "Environmental Guide to Dye
Carrier Selection," American Dyestuff Reporter, March 1975,
Hahn, A.V.G. (1970), The Petrochemical Industry, McGraw-Hill, pp. 411-12, 475.
Hale, W.J. (1930), U.S. Patent No. 1,744,961, Jan. 28, assigned to Dow Chemical Co.
Hale, W.J. and Britton, J.W. (1933), U.S. Patent No. 1,882,824, Oct. 18, assigned
to Dow Chemical Co.
Hennis, H.E. (1974), U.S. Patent No. 3,793,377, Feb. 19, assigned to Dow Chemical Co.
Kites, R.A. (1973), "Analysis of Trace Organic Compounds in New England Rivers,"
J. Chromatogr. Sci. 11(11);570-4.
Hunt, R.H. and O'Neal, M.J. (1967), "Petroleum (Composition)," Kirk-Othmer Encycl.
Chem. Technol., 2nd Edition, 14;849.
Insera, W. (1976), Personal Communication, Stauffer Chemical Co., Edison, NJ,
May 1976.
Johnsen, R. (1975), "Chlorination of Waters for Disinfection - A Study of the
Production of Undesirable Chlorinated Products," National Conf. on Poly-
chlorinated Biphenyls (Nov. 19-21, Chicago, IL), EPA Contract No. 68-01-2928.
Karr, C., Jr., Estep, P.A., LoChang, T. and Camberiati, J.R. (1967), U.S. Bureau
of Mines Bulletin No. 637, p. 198.
Kimland, B., Aasen, A.J. and Enzell, C.R. (1972), Acta Chem. Scand, 26(6):
2177-84. —
Kinlin, T., Muralidhara, R., Pittet, A., Sanderson, A. and Walradt, J. (1972),
"Volatile Components of Roasted Filberts," J. Agr. Food Chem. 20:1021-8.
105
-------
Kolar, B. and Klacel, Z. (1962), Chemicky Prumysl 12:326-332.
Kothny, E. (1976), "Letters - Living with PCB's," Chem. Eng. News, Jan. 19, p. 5.
Levek, R.P. and Williams, D.O. (1975), "Flame Retardants," Modern Plastics
Encyclopedia, _52(10A) :203.
Mahinkia, M. (1976), Personal Communication, Givaudan Corp, Clifton, NJ, April 1976,
Mair, B.J. and Mayer, T.J. (1964), "Composition of Dinuclear Aromatics, C^ to
C^, in the Light Gas Oil Fraction of Petroleum," Anal. Chem. 36; 35 1-362.
McNeil, D. (1969), "Tar and Pitch." Kirk-Othmer Encycl. Chem. Technol. . 2nd Ed.,
19:675.
Mispley, R.G. and Barber, W.R. (1940), U.S. Patent No. 2,173,453, assigned to
Crown-Zellerbach Corp., Sept. 19.
Mitchell, L.C. (1973), "Process for Production of Polybrominated Aromatics," U.S.
Patent No. 3,763,248, Oct. 2, assigned to Ethyl Corp.
Moore, D.E., Mills, J.F. and Schneider, J.A. (1974), "Bromination with Bromine
Chloride Under Pressure," U.S. Patent No. 3,845,146, Oct. 29, assigned to
Dow Chemical Co.
Moose, J.E. and Pritchard, W.N. (1934), U.S. Patent No. 1,968,154, July 31,
assigned to Monsanto Co.
Mumma, C.E. and Wallace, D.D. (1975), "Pollution Potential of Polybrominated
Biphenyls," Midwest Research Institute - EPA Contract No. 68-01-2105,
Office of Toxic Substances, June 1975.
Neeley, W. , Branson, D. and Blau, G. (1974), "Partition Coefficient to Measure
Bioconcentration Potential of Organic Chemicals in Fish," Environ. Sci.
Technol. .8(13) : 1113-1115.
Neufeld, M.L., Sittenfield, M. , and Wo Ik, K.F. (1976), "Market Input/Out Studies -
Task IV - Polybrominated Biphenyls," EPA Contract No. 68-01-1996, Office of
Toxic Substances, August 1977.
Opdyke, J. (1974), "Fragrance Raw Materials Monograph," Food and Cosmetics
Toxicology 12;707.
Otis, C.E. (1976), Personal Communication, Manager of Environmental Affairs,
Dow Chemical Co., Midland, MI, March-May.
Pane, T. (1976), Personal Communication, Monsanto Industrial Chemicals,
Alvin, TX, May 1976.
Poffenberger, N. (1950), "Diphenyl and Terphenyl," Kirk-Othmer Encycl. Chem.
Technol. , 1st Edition, ^:145-147.
106
-------
Poffenberger, N. (1965), "Diphenyl and Terphenyls," Kirk-Othmer Encycl. Chem.
Technol. , 2nd Edition, 7^:191-193.
Poffenberger, N. (1968), "Phenol-Hydrolysis of Monochlorobenzene with Aqueous
NaOH," Kirk-Othmer Encycl. Chem. Technol., 2nd Edition, 1.5:153-155.
Porter, F. (1946), U.S. Patent No. 2,392,875, Jan. 15, assigned to Solvay
Process Co.
Prutton, C.F. (1940), U.S. Patent No. 2,208,517, July 17, assigned to Dow Chemical
Co.
Saunders, J.H. and Slocombe, R.J. (1955), U.S. Patent No. 2,702,307, Feb. 15,
assigned to Monsanto Co.
Schofield, K. (1974), "Problems With Flame lonization Detectors in Automotive
Exhaust Hydrocarbon Measurement," Environ. Sci. Technol., JJ(9):826-834.
Schailkopf, K. (1929), German Patent No. 530,736, May 25.
Schultz, T.H., Teranishi, R., McFadden, W.H., Kilpatrick, P.W. and Corse, J.
(1964), "Volatiles from Oranges. II. Constituents of the Juice Identified
by Mass Spectra," J. Food Sci., 29_:79Q-95.
Scott, T.J. (1933), U.S. Patent No. 1,894,283, Jan. 17, assigned to Monsanto Co.
SRI (1974), "Creosote Oil-Salient Statistics," Chemical Economics Handbook,
Stanford Research Institute, Menlo Park, CA.
SRI (1975 a), 1975 Directory of Chemical Producers, Stanford Research Institute,
Menlo Park, CA.
SRI (1975 b), "Petroleum and Natural Gas," Chemical Economics Handbook, Stanford
Research Institute, Menlo Park, CA.
SRI (1976), 1976 Directory of Chemical Producers, Stanford Research Institute,
Menlo Park, CA.
Stevens, K.L., Bomben, J., Lee, A. and McFadden, W.H. (1966), "Volatiles from
Grapes. Muscat of Alexandria," J. Agr. Food Chem., 14;249-252.
Stoll, M., Winter, F., Gautschi, F., Flament, I. and Willhalm, B. (1967),
Helv. Chim. Acta _50(2) :628-94.
Tabor, T.E. (1973), "Bromine-Containing Fire Retardants," Symposium on Textile
Flammability, j.:143-152.
Tincher, W.C. (1976), Personal Communication, Environmental Resources Center,
Georgia Institute of Technology, Atlanta, GA, June.
107
-------
Todd, A.S. (1976), Personal Communication, Between A.S. Todd, Stewart-Todd
Associates, Wayne, PA, and H.E. Stokinger, Chariman-Threshold Limits
Committee, Cincinnati, OH, March 2.
U.S. International Trade Commission (1973-74), Synthetic Organic Chemicals,
United States Production and Sales, Washington, D.C.
U.S. International Trade Commission (1967-1974), Imports of Benzenoid Chemicals
and Products, Washington, D.C.
Valenta, J.C. and Steinhauer, A.F. (1964), U.S. Patent No. 3,127,441, March 31,
assigned to Dow Chemical Co.
Versar (1976), "PCB's In the United States, Industrial Use and Environmental
Distribution," Contract No. 68-01-3259 (Task I) for the U.S. EPA Office
of Toxic Substances, Feb. 25 (Final Report).
Walradt, J., Pittet, A., Kinlin, T., Muralidhura, R. and Sanderson, A. (1971),
"Volatile Components of Roasted Peanuts," J. Agr. Food Chem., 19;972-9.
Webb, R.G., Garrison, A.W., Keith, L.H. and McGuire, J.M. (1973), Current Practice
in GC-MS Analysis of Organics in Water, U.S. Nat. Tech. Inform. Serv.,
Springfield, VA, PB-224-947.
Williams, W.H. (1933), U.S. Patent No. 1,925,784, Sept. 5, assigned to Dow
Chemical Co.
Williams, W.H. (1934), U.S. Patent No. 1,978,069, Oct. 23, assigned to Dow
Chemical Co.
Yew, F.F. and Mair, B.J. (1966), "Isolation and Identification of C]j to C17
Alkylnaphthalenes, Alkylbiphenyls, and Alkylbenzofurans from 275°C to
305°C. Dinuclear Aromatic Fraction of Petroleum," Anal. Chem. 38:231-237.
108
-------
TECHNICAL REPORT DATA
(Please read Imiiructions on llic reverse before completing)
I. REPORT NO.
EPA 560/6-77-003
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANDSUBTITLE
Chemical Market Input/Output Analysis of Selected
Chemical Substances to Assess Sources of Environmental
Contamination: Task II. Biphenyl and Diphenyl Oxide
5. REPORT DATE
October 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
William M. Meylan
Philip H. Howard
8. PERFORMING ORGANIZATION REPORT NO
TR 76-599
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Center for Chemical Hazard Assessment
Syracuse Research Corporation
Merrill Lane
Syracuse, New York 13210
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-3224 - Task II
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report considers the sources of environmental contamination from
biphenyl and diphenyl oxide. Biphenyl is manufactured in commercial quantities
for use in dye carriers, heat transfer fluids, derivatives such as PCB's and
alkylated biphenyls, and fruit fungicides. Diphenyl oxide is manufactured in
commercial quantities for use in dye carriers, heat transfer fluids, derivatives
such as butylchlorodiphenyl oxide, decabromodiphenyl oxide, surfactants, and
perfumes and soaps. Thus, this report concentrates on the commercial production
and use of biphenyl and diphenyl oxide. Standards established by the Occupational
Safety and Health Administration have controlled the occupational exposure to
biphenyl and diphenyl oxide; however, large quantities of these chemicals are
released to the external environment, particularly to waste treatment facilities
which may utilize chlorine disinfection, Laboratory studies indicate that the
biphenyl nucleus can undergo chlorination to various chlorobiphenyl isomers during
treatment chlorine disinfection.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN tNDED TERMS C. COSATI Field/Group
18. DISTRIBUTION STATEMENT
Document is available to the public through
the National Technical Information Service,
Springfield, Virginia 22151.
19. SECURITY CLASS (This Report)
21. NO. OF PAf.bS
117
20. SECURITY CLASS (This (ingf)
22. PRICI-
EPA Form 2220-1 (9-73)
109
------- |