United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-79-019d
May 1979
Research and Development
Source Assessment:
Manufacture of Acetone
and Phenol from Cumene
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-019d
May 1979
Source Assessment: Manufacture
of Acetone and Phenol from Cumene
by
J. L Delaney and T. W. Hughes
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
Contract No. 68-02-1874
Program Element No. 1AB015; ROAP 21AXM-071
EPA Project Officer: Bruce A. Tichenor
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Industrial Environmental Research Laboratory (IERL) of the
U.S. Environmental Protection Agency (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air Act,
the Federal Water Pollution Control Act, and solid waste legis-
lation. If control technology is unavailable, inadequate, or
uneconomical, then financial support is provided for the develop-
ment of the needed control techniques for industrial and extrac-
tive process industries. Approaches considered include: process
modifications, feedstock modifications, add-on control devices,
and complete process substitution. The scale of the control
technology programs ranges from bench- to full-scale demonstra-
tion plants.
The Chemical Processes Branch of the Industrial Processes
Division of IERL has the responsibility to develop control tech-
nology for a large number of operations (more than 500) in the
chemical industries. As in any technical program, the first
question to answer is, "Where are the unsolved problems?" This
is a determination which should not be made on superficial infor-
mation; consequently, each of the industries is being evaluated
in detail to determine if there is, in EPA's judgment, sufficient
environmental risk associated with the process to require
emissions reduction. This report contains the data necessary to
make that decision for the air emissions from the manufacture of
acetone and phenol from cumene.
Monsanto Research Corporation has contracted with EPA to investi-
gate the environmental impact of various industries which repre-
sent sources of pollution in accordance with EPA's responsibility
as outlined above. Dr. Robert C. Binning serves as Program
Manager in this overall program entitled "Source Assessment,"
which includes the investigation of sources in each of four cate-
gories: combustion, organic materials, inorganic materials, and
open sources. Dr. Dale A. Denny of the Industrial Processes
Division at Research Triangle Park serves as EPA Project Officer.
In this study of the manufacture of acetone and phenol from
cumene, Mr. Edward J. Wooldridge, Dr. I. Atly Jefcoat and
Dr. Bruce Tichenor served as EPA Task Leaders.
111
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ABSTRACT
This report describes a study of atmospheric emissions resulting
from the manufacture of acetone and phenol from cumene.
The air emissions from such manufacture consist only of hydro-
carbons. The potential environmental effect of these emissions
is evaluated by estimating the source severity, defined as a
ratio of the maximum time-averaged ground level concentration of
a pollutant to an acceptable concentration. The source severi-
ties of total nonmethane hydrocarbons for a representative
source having 136 x 103 metric tons of annual phenol capacity
are: 3.5 for the cumene peroxidation vent, 0.58 for the com-
bined cleavage section vents, 0.96 for the combined product
purification section vents, 0.13 for the combined storage tank
vents, 1.2 for the combined product transport loading vents, and
0.58 for fugitive sources.
Source severities greater than 0.05 for chemical substances are:
0.43 for benzene from the cumene peroxidation vent, 0.23 and
0.066 for cumene from the cumene peroxidation vent and the
cleavage section vents combined, 0.13 for the heavy ends storage
tank emission (assumed to be phenol), 0.17 for phenol from the
phenol storage tanks, and 1.3 for phenol from the product loading
vents combined.
Industry contributions to atmospheric hydrocarbon emissions from
stationary sources are estimated to be: 0.023% for the nation,
0.0049% for California, 0.013% for Illinois, 0.050% for Kansas,
0.034% for Louisiana, 0.034% for New Jersey, 0.049% for Ohio,
0.084% for Pennsylvania, and 0.081% for Texas.
A variety of hydrocarbon emission control methods are used de-
pending on the emission and emission point.
The two process technologies in use in the United States for
oxidizing cumene to cumene hydroperoxide and for cleavage of
the cumene hydroperoxide to acetone and phenol are discussed
and compared. These technologies are those of Allied Chemical
Corp. and Hercules, Inc. Economic and production trends in the
phenol industry and in the industries that use phenol acetone,
and the other byproducts are discussed and analyzed.
IV
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This report was submitted in partial fulfillment of Contract
No. 68-02-1874 by Monsanto Research Corporation under the spon-
sorship of the U.S. Environmental Protection Agency. The study
described in this report covers the period February 1976 to April
1978.
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CONTENTS
Preface iii
Abstract iv
Figures ix
Tables x
Abbreviations and Symbols xii
1. Introduction 1
2. Summary 3
3. Source Description 9
Process description 10
Plant material balance 33
Geographic distribution 33
4. Emissions 42
Selected pollutants 42
Locations and descriptions 45
Definition of a representative source 55
Source severity 55
Industry contribution to total atmospheric
emissions 59
Affected population 72
Growth factor 76
5. Control Technology 77
Installed emissions control technology 77
Future considerations 90
6. Growth and Nature of the Industry 92
Process technology 93
Emerging technology 99
Industry production trends 99
Outlook 103
References 108
Appendices
A. Storage tankage calculations 116
B. Specifications 122
C. Sampling procedures and equipment 123
D. Analytical procedures 128
E. Sampling and analysis methods for formaldehyde
and aldehydes 133
vii
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CONTENTS (continued)
Appendices (continued)
F. Average emission factors uncontrolled and controlled
from the peroxidation vent at a plant manufac-
turing acetone and phenol from cumene 138
G. Average emission factors for the cleavage section
vents (combined) at a plant manufacturing acetone
and phenol from cumene, 1976 and 1977 141
H. Reported emissions information 143
I. Derivation of source severity equations 150
J. Simulated source severity distributions 164
K. Affected population calculations 174
L. Plume rise calculations 179
Glossary 184
Conversion Factors and Metric Prefixes 186
Vlll
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FIGURES
Number
1 Chemistry of the main reactions in the cumene
peroxidation process 12
2 Main side reactions of the cumene peroxidation process 13
3 Phenol from cumene products, byproducts, and
intermediates 14
4 Process flow diagram for the Allied Chemical process
technology 16
5 Process flow diagram for the Hercules process
technology 18
6 Cumene peroxidation section of the Allied process . . 21
7 Upper explosive limits for the cumene-air system as
a function of temperature and pressure 22
8 Cleavage section of the Allied process 23
9 Product purification section of the Allied process. . 25
10 Cumene peroxidation section of the Hercules process . 26
11 Cleavage section of the Hercules process 27
12 Product purification section of the Hercules process. 29
13 Simplified process flow diagram for the manufacture
of acetone and phenol from cumene 34
14 Locations of plants manufacturing phenol from cumene,
and cumene 40
15 Simulated source severity distribution for total
nonmethane hydrocarbons emitted from the cumene
peroxidation vent 70
16 Simulated source severity distribution for total
nonmethane hydrocarbons emitted from the product
purification vents, combined 71
17 Variation of cumene concentration with temperature
and pressure 84
18 Condensation used as emission control on the cumene
peroxidation vent 85
19 Vent gas scrubber-cooler 88
20 Chemical relationship between major synthetic phenol
processes 94
21 Phenol uses and markets 101
22 Uses and markets for acetone and derivatives 104
23 Markets and uses for acetophenone, cumene hydro-
peroxide, and ot-methylstyrene 105
24 Capacity and production trends for phenol projected
to 1978 106
25 Historical and projected trends in cumene-based
phenol production and capacity 106
ix
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TABLES
Number gage
1 1975 Production and 1977 Capacity for Phenol and
Acetone 3
2 Average Emission Factors for the Manufacture of Acetone
and Phenol From Cumene by Emission Source, 1977. . . 6
3 Source Severities of Atmospheric Emissions From a
Representative Source Manufacturing Acetone and
Phenol From Cumene, 1977 7
4 Estimated Industry Contribution to Atmospheric Emis-
sions of Hydrocarbons, 1977 8
5 Properties of Major Products, Byproducts and Feed of
the Cumene Peroxidation Process 11
6 Tankage Requirements for a Representative Source
Manufacturing Acetone and Phenol From Cumene .... 31
7 Estimated Material Balance for a Representative Source
Manufacturing Acetone and Phenol From Cumene .... 35
8 Phenol Producers 37
9 Acetone Producers 38
10 Plants Manufacturing Acetone and Phenol From Cumene. . 40
11 Cumene Producers 41
12 Suspected Emissions From Acetone and Phenol Manu-
facture From Cumene Prior to Sampling 43
13 Characteristics of Emissions Identified During
Sampling or Reported From Acetone and Phenol Plants
Using Cumene Peroxidation 44
14 Emission Sources by Process Type at a Plant Manu-
facturing Acetone and Phenol from Cumene 46
15 Emission Sources at a Representative Plant Manufac-
turing Acetone and Phenol From Cumene 47
16 Variation of t With Degrees of Freedom for the 95%
Confidence Level 47
17 Average Emission Factors, Uncontrolled and Controlled,
From the Peroxidation Vent at a Plant Manufacturing
Acetone and Phenol From Cumene, 1977 49
18 Average Emission Factors for the Cleavage Section
Vents Combined at a Plant Manufacturing Acetone and
Phenol From Cumene, 1976 and 1977 51
19 Average Emission Factors for the Product Purification
Section Vents Combined at a Plant Manufacturing
Acetone and Phenol From Cumene, 1976 52
20 Calculated Emission Factors for Storage Tank Vents at
a Plant Manufacturing Acetone and Phenol From
Cumene 54
x
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TABLES (continued)
Number Page
21 Reported Emission Factors for Product Transport
Loading Vents Combined at a Plant Manufacturing
Acetone and Phenol From Cumene, 1975 and 1978. ... 54
22 Plant Parameters Used in Determining the Representa-
tive Source for a Plant Manufacturing Acetone and
Phenol From Cumene 56
23 Emission Control Technologies Used at Representative
Plant 57
24 Average Emission Factors for Phenol and Acetone
Manufacture From Cumene by Emission Point, 1977. . . 60
25 Emission Heights at a Representative Source Manu-
facturing Acetone and Phenol from Cumene 63
26 Maximum Time-Averaged Ground Level Concentrations of
Atmospheric Emissions From a Representative Source
Manufacturing Acetone and Phenol From Cumene, 1977 . 64
27 Source Severities of Atmospheric Emissions From a
Representative Source Manufacturing Acetone and
Phenol From Cumene, 1977 67
28 Estimated Contribution to Total Emissions of Hydro-
carbons by Manufacture of Acetone and Phenol From
Cumene, 1977 73
29 Estimated Affected Population From Manufacture of
Acetone and Phenol From Cumene at Representative
Source, 1977 75
30 Installed Emissions Control Technology at Plants
Manufacturing Acetone and Phenol From Cumene . . . .78
31 Number of Plants Reporting Usage of Emission Control
Methods in Indicated Section of the Plant Manufac-
turing Acetone and Phenol From Cumene 82
32 Amount of Cumene in a Saturated Gas Stream at Various
Conditions 84
33 Material Balance for an Emission Control System on
the Cumene Peroxidation Vent Using Condensations . . 86
34 Stream Information for Vent Gas Scrubber Cooler used
on the Cumene Peroxidation Vent 89
35 U.S. Production of Phenol 97
36 Phenol Capacity and Production 100
37 Phenol Consumption by Major Market 102
38 Acetone Consumption by Major Market 103
39 Projected Production and Capacity for Phenol, 1980
and 1982 105
40 Anticipated Expansion and New Facilities in the
Phenol Industry 107
XI
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ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
AA — atomic absorption
GC — gas chromatography
GC/FID — gas chromatography with flame ionization detection
GC/MS — gas chromatography/mass spectroscopy
FID — flame ionization detector
HVOSS — high volume organic sampling system
MS — mass spectroscopy
SASS — source assessment sampling system
SSMS — spark source mass spectroscopy
TLV — threshold limit value, mg/m3
SYMBOLS
a — variable in horizontal dispersion equation
A — area, km2
A_ — Q/aciiu
BR H2/2c2
c — variable in horizontal dispersion equation
C — diameter factor
GC — gram moles of carbon that a gram mole of material
contains
C^ — phenol production capacity of plant i, metric tons/yr
Ct — tank capacity, gal/tank
Cap — representative source phenol capacity, kg/yr
CAP — production capacity for the material, tons/yr
Caps — total capacity on a state or national basis, metric
tons/yr
d — variable in vertical dispersion equation
D — tank diameter, ft
xn
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ABBREVIATIONS AND SYMBOLS (continued)
D. — inside stack diameter, m
Dp — population density, persons/km2
Dp — capacity weighted mean county population density,
persons/km2
Dp. — county population density for plant i, persons/km2
e — 2.72
E — emission factor, g/kg phenol produced
E1 -- emission factor, Ib/ton phenol produced
E — g of stack gas per kg phenol produced
s
EF — total emission factor for nonmethane hydrocarbons,
g/kg phenol produced
f — degrees of freedom
f — variable in vertical dispersion equation
F -- hazard factor, g/m3
F — equivalent gasoline working loss, bbl/yr
F — paint factor
G — conversion factor, 1/300
h — tank height, ft
h' — physical stack height, m
H -- effective emission height, m
H1 — average tank outage, ft
AH — plume size, m
ki — conversion factor, yr/s
k2 — conversion factor, gal/ft
ks — conversion factor, Ib/ton
ki+ — conversion factor, kg/g
ks — conversion factor, m3/g mole
K — paint factor
K — seal factor
S
K. — tank factor
K — turnover factor
L — total petrochemical loss, bbl
LI — total petrochemical loss, Ib/yr
Xlll
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ABBREVIATIONS AND SYMBOLS (continued)
L — total equivalent gasoline loss, bbl/yr
L — equivalent gasoline breathing loss, bbl/yr
M -- molecular weight, g/g mole, kg/kg mole, Ib/lb mole
M — material molecular weight, g/g mole, kg/kg mole,
c Ib/lb mole
M — molecular weight of methane, g/g mole, equivalent
m Ib/lb mole
M — molecular weight of stack gas, g/g mole
s
MEEF -- methane equivalent emission factor, g equivalent
methane/kg phenol produced
n — number items averaged
N — number of turnovers per year
N' — number of tanks
P — vapor pressure of material stored at bulk temperature,
psia
P — atmosphere pressure, mb
P — stack gas pressure, KPa
S
Q — mass emission rate, g/s
R — universal gas constant, KPa Q m3
,,,,... g mole o °K
s — standard deviation '
S — source severity
t — value from statistical tables for "Student t"
distribution
T — throughput per year of the stored material, gal/yr
T — ambient temperature, °K
3.
T — stack gas temperature, °K
s
TE — total emissions of hydrocarbons from stationary sources
on a state or national, metric ton/yr
tj, t — averaging time, min
u — wind speed, m/s
U -- utilization
u — average wind speed, m/s
u — average wind speed, mph
V — tank capacity, bbl
V — volume liquid withdrawn from tank, bbl
xiv
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SECTION 1
INTRODUCTION
The purpose of this document is to supply the data base necessary
for the assessment of emissions from the manufacture of acetone
and phenol from cumene. This document has been prepared from
information compiled from literature, industry contact, field
sampling and contact with Federal and state environmental pro-
tection agencies.
Phenol is an industrially important synthetic organic chemical
intermediate whose main uses are in production of resins, capro-
lactam, and bisphenol A. Currently, the major industrial route
to phenol is the peroxidation of cumene, although three other
processes are also presently used in the United States (sulfona-
tion of benzene, chlorination of benzene, and oxidation of
toluene). Cumene peroxidation is now regarded as the only avail-
able process having future industrial significance.
In addition to phenol, acetone is produced as a coproduct. The
main uses of acetone are in making methacrylate esters, protec-
tive coatings, methyl isobutyl ketone, and solvent derivatives.
Acetone is produced by three other processes in the United
States: 1) catalytic oxidation and dehydrogenation of isopro-
panol, 2) fermentation, and 3) propylene oxidation.
The cumene peroxidation process has two reaction steps: 1) oxi-
dation of cumene with oxygen from air to cumene hydroperoxide,
and 2) cleavage of cumene hydroperoxide by acid to phenol and
acetone.
The major results of this study are summarized in Section 2 and
include emission factors for materials emitted to the atmosphere
from the emission points within a representative cumene per-
oxidation phenol plant. Also tabulated are several factors
designed to measure the environmental hazard potential of the
representative cumene peroxidation plant emissions and opera-
tions. These consist of source severity, industry contribution
to total atmospheric emissions of criteria pollutants, the number
of persons exposed to high contaminant levels, and future trends
in emissions.
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Section 3 provides a detailed description of the cumene per-
oxidation process, including process chemistry, major processing
steps, flow diagrams, material balances, and geographic loca-
tions. The two process technologies using the cumene peroxida-
tion reaction to produce acetone and phenol, the Allied process
and the Hercules process, are discussed.
Atmospheric emissions from plants manufacturing acetone and
phenol from cumene are discussed in Section 4. The species
known to be emitted are detailed, and each emission point within
the plant is described. Emission factors for each point and
species are given. A representative source, a plant manufactur-
ing acetone and phenol from cumene, is defined. The emission
factors are used to determine source severity, calculate the
industry contribution to total emissions of criteria pollutants,
estimate the affected population, and determine future trends in
emissions.
Section 5 considers the present and future aspects of pollution
control technology. Emission controls presently installed at
plants manufacturing acetone and phenol from cumene are dis-
cussed.
Economic and production trends in phenol and acetone manufacture,
and in those industries that are major consumers of phenol and
acetone, are analyzed in Section 6.
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SECTION 2
SUMMARY
Phenol is currently manufactured in the United States by four
processes: cumene peroxidation, benzene sulfonation, benzene
chlorination, and toluene oxidation. Acetone is also currently
manufactured in the United States by four processes: cumene per-
oxidation, isopropanol oxidation and dehydrogenation, fermenta-
tion, and propylene oxidation. The cumene peroxidation process
is the major producer of phenol and acetone, a coproduct. Table 1
lists the production in 1975 and the capacities in 1977 for total
acetone and phenol and for cumene-based acetone and phenol.9»b
TABLE 1. 1975 PRODUCTION AND 1977 CAPACITY
FOR PHENOL AND ACETONE
Production, 19759, D
Material
Phenol, total
Phenol, cumene based
Acetone, total
Acetone, cumene based
10 3 metric tons
792
703
744
432
Percent
100
89
100
58
Capacity, 1977&
10 * metric tons
1,470
1,360
1,380
830
Percent
100
93
100
60
Last year for which cumene-based production was reported separately.
Puerto Rico is not included in this study. Capacity information for Puerto
Rico has been excluded, but Puerto Rican production is not reported sepa-
rately, and therefore cannot be excluded.
There are 10 plants manufacturing phenol from cumene in the
continental United States. The plants are located in rural and
nonrural counties having population densities of 10 to 5,836
persons/km2.
Cumene is oxidized to cumene hydroperoxide by liquid phase con-
tact with air. The cumene hydroperoxide may be washed, depend-
ing on the process, then concentrated to 80% by weight or higher
cumene hydroperoxide. Cleavage to acetone, phenol, and other
byproducts occurs by contact with an acid catalyst in the cleav-
age section. The product stream is washed to remove the acid
catalyst. In the product purification section, acetone, phenol,
acetophenone, a-methylstyrene, light ends, heavy ends, and wastes
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are separated and purified. The acetone, phenol, and any by-
products in demand are sold or used captively.
Sources of emissions within plants manufacturing acetone and
phenol from cumene are:
Cumene peroxidation vent.
Cleavage section vents, combined.
Product purification vents, combined.
Storage tank vents, combined.
Product transport loading vents, combined.
Fugitive sources.
The only criteria pollutant emitted to the atmosphere is non-
methane hydrocarbons. (There is no primary ambient air quality
standard for hydrocarbons. The value of 160 yg/m3 used in this
report is a recommended guideline for meeting the primary ambient
air quality standard for photochemical oxidants.)
Process technology to produce phenol and acetone from cumene via
peroxidation is licensed in the United States by Allied Chemical
Corp., and Hercules Inc. Emissions from both processes are
similar.
Emissions from the cumene peroxidation step are caused by vola-
tile hydrocarbons present in the spent air off-gas. This step
contacts cumene and air to form cumene hydroperoxide. This emis-
sion source accounts for 51% of the mass of emissions from this
process (based on total nonmethane hydrocarbons). All plants use
some form of emission control on this off-gas, with an average
81% efficiency (based on total nonmethane hydrocarbons).
Emissions from the cleavage section are vented nonmethane hydro-
carbons. The major step in this section is the cleavage of
cumene hydroperoxide to acetone and phenol using an acid catalyst.
Various auxiliary operations, such as washes and concentrations,
are also performed. The Allied process vents only the cumene
hydroperoxide concentration step. The Hercules process vents
the cumene hydroperoxide wash, the cumene hydroperoxide concentra-
tion, the cumene hydroperoxide cleavage, and the product stream
wash. Some plants use condensation or absorption to control
emissions from some or all of these vents, and some vents are
uncontrolled.
Emissions from the product purification section are vented hydro-
carbons from the columns separating and purifying product streams
and recycle streams. These vents have emission controls.
Storage tanks are used to hold feedstock and products. Emissions
from this area were determined by engineering estimates. The
control methods used are floating roofs, vent condensers, sealed
roofs, and conservation vents.
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Emissions from product transport loading occur from the displace-
ment of vapors in the item being filled. Absorption and vapor
recovery are used for control. Not all plants control emissions
from this source.
Fugitive emissions occur from pump seals, compressor seals, pipe-
line valves and flanges, relief valves, and process drains.
Emission factors are summarized in Table 2 for manufacture of
acetone and phenol from cumene. The emission factors were used
to generate a number of other factors designed to quantify the
potential hazard of production acetone and phenol from cumene.
To assess the impact of atmospheric emissions from the manufac-
ture of acetone and phenol from cumene, the source severity for
each material emitted from each emission point was estimated.
Source severity is defined as the pollutant concentration to
which the population may be exposed divided by an "acceptable
concentration." The exposure concentration is the maximum time-
averaged ground level concentration as determined by Gaussian
plume dispersion methodology. The "acceptable concentration"
is that pollutant concentration at which an incipient adverse
health reaction is assumed to occur. The "acceptable concentra-
tion" is defined as the corresponding primary ambient air quality
standard for criteria pollutants, and as a surrogate air quality
standard for chemical substances determined by reducing thres-
hold limit values (TLVs®) using an appropriate safety factor.
Source severities were calculated for a representative source,
which is a plant producing acetone and phenol from cumene with
a phenol capacity of 136 x 103 metric tons per year. The plant
is utilized at 80% of production capacity. The capacities of
the 10 plants producing phenol from cumene in the continental
United States range from 25 x 103 metric tons/yr to 272 x 103
metric tons/yr of phenol. The source severities for the repre-
sentative plant are presented in Table 3.
The maximum source severity was 3.5 for total nonmethane hydro-
carbons, in methane equivalents, from the cumene peroxidation
vent.
Atmospheric emissions of nonmethane hydrocarbons in methane equiv-
from the manufacture of acetone and phenol from cumene in 1977
were estimated to be 3,900 metric tons. This is 0.024% of the
total hydrocarbon emissions from stationary sources.
The percentages of total hydrocarbons from stationary sources
attributable to nonmethane hydrocarbon emissions, in methane
equivalents, from the manufacture of acetone and phenol from
cumene were estimated for the individual states and the nation
and are listed in Table 4.
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TABLE 2. AVERAGE EMISSION FACTORS FOR THE MANUFACTURE OF ACETONE
AND PHENOL FROM CUMENE BY EMISSION SOURCE, 1977
Cumene
peroxidation
Material vent*
Emission
Cleavage
section
vents ,
combined* •• «c
i factors, q/kg o
Product
purification
vents.
combined* •«
f phenol prod
Storage
tank
vents.
combined'- 3
Product
transport
loading vents,
combined" • '
Fugitive
emissions.)
Criteria pollutants!
Total nonmethane
hydrocarbons*
Chemical substances;
Acetaldehyde
Acetone
1.8
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TABLE 3. SOURCE SEVERITIES OF ATMOSPHERIC EMISSIONS
FROM A REPRESENTATIVE SOURCE MANUFACTURING
ACETONE AND PHENOL FROM CUMENE, 1977
Cleavage
Cumene section
peroxidation vents.
Source severit
Product Storage Product
purification tank transport
vents, vent* loading vents. Fugitive
Material
Criteria pollutants:
Total nonmethane
hydrocarbons'
Chemical substances:"
Acetaldehyde
Acetone
Benzene
2-Butanone
Cumene
Ethylbenxene
Formaldehyde
a-Methylstyrene
Naphthalene
Phenol
vent*
3.5
<0.0076
0.0090
0.43
0.0055
0.23
0.000063
0.022
<1.4 x 10-*P
<0. 00013
combined* • «•* ccMbirtsda.t ccwbinedf.9 combined^ emissions.!
0.58 0.96 0.10 1.2 0.58
_n
1.6 X 10~7 -" 0.0039
1.2 X 10-*°
3.5 x 10-'
0.066 -n
1.3 x 10-7
<1.0 x 10-'
0.17" 1.3r
Note.—Blanks indicate no emissions for sampled plants and no reported emissions for the other sources.
'sampling performed.
b£missions are from 1 to 4 vents.
CData are from industry sources for 1976 and 1977.
dEmissions are from 5 to 7 vents.
8Data used are from industry sources for 1976.
Values used are for the 4 phenol tanks.
^Emission factors are calculated.
^Loading of 2 to 5 product types.
1Data used are from industry sources for 1975 and 1978.
3Data used are from industry sources for 1975. The fugitive emission estimate includes those from pumps
and sewers only. The other sources of fugitive emissions are not included in this estimate.
kOnly hydrocarbons (organic materials) are emitted.
'source severity for total nonmethane hydrocarbons will not equal the source severity for the total of the non-
methane hydrocarbons emitted. Source severities for the nbnmetbane organic materials are based on the toxicity
of the chemicals. The source severity for total nonmethana hydrocarbons is based on the guideline for meeting
the primary ambient air quality standard for photochemical oxidants.
mOnly substances which have a TLV are listed.
"Qualitatively Identified.
°The beniene emission factors used are not representative. A process upset at one of the two plants sampled
resulted in a high level of beniene emissions.
pAssumed to be the a form.
'rne emission factor used is the average of a calculated value and an estimate supplied by B. Walker, Monsanto
Chemical Intermediates Co., Alvin, Texas, 6 September 1978.
rThe emission factor is an average of two estimates.
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TABLE 4. ESTIMATED INDUSTRY CONTRIBUTION
TO ATMOSPHERIC EMISSIONS OF
HYDROCARBONS, 1977
Location Percentage
United States
California
Illinois
Kansas
Louisiana
New Jersey
Ohio
Pennsylvania
Texas
0.023
0.0049
0.013
0.050
0.034
0.034
0.049
0.084
0.081
The affected population is determined for source severities
greater than or equal to 0.1. The affected area is determined
and then multiplied by the capacity weighted mean county popula-
tion density. The county population is not uniformly distributed
throughout the county; therefore, in the plant vicinity, the pop-
ulation density may be higher or lower than the average. The
number of persons that may be exposed to concentration above 0.1
of the primary ambient air quality standard (i.e., recommended
guideline) for hydrocarbons for emissions from the representative
source manufacturing acetone and phenol from cumene is estimated
to be 12,600.
In 1975, 703 x 103 metric tons of phenol was produced from
cumene. The 1980 projected production of phenol from cumene
is 1,100 x 103 metric tons. Thus, assuming the same level of
control 1980 exists in 1980 as existed in 1975, emissions from
the manufacture of acetone and phenol from cumene will increase
by 56% over that period; i.e.,
Emissions in 1980 _ 1,100 x 103 _ , -,.
Emissions in 1975 703 x 103 •L-Db
-------
SECTION 3
SOURCE DESCRIPTION
In 1977, phenol and acetone were ranked 37th and 40th, respec-
tively, by production volume of the major chemicals in the United
States (1). Phenol is used in the production of phenolic resins,
caprolactam, bisphenol A, adipic acid, and other chemicals (2).
Acetone is used in the production of methacrylate esters, methyl
isobutyl ketone, protective coatings, solvent derivatives, bis-
phenol A, and other chemicals (3). Four major processes are used
in the United States to produce synthetic phenol. They are:
1) benzene chlorination, 2) benzene sulfonation, 3) toluene oxid-
ation, and 4) cumene peroxidation (4). Synthetic acetone is also
produced by four major processes in the United States: 1) iso-
propanol oxidation, 2) propylene oxidation, 3) fermentation, and
4) cumene peroxidation (5). The cumene peroxidation process has
accounted for 93% of the installed continental U.S. synthetic
phenol production capacity and 60% of the installed continental
U.S. synthetic acetone production capacity (excluding Puerto
Rico).
The process description in this section presents the cumene per-
oxidation process chemistry and technology. An average plant
material balance is presented, and the geographical distribution
is discussed.
(1) Facts and Figures for the Chemical Industry. Chemical and
Engineering News, 56 (18):31-37, 1978.
(2) Chemical Profile, Phenol. Chemical Marketing Reporter,
213(6):9, 1978.
(3) Chemical Profile, Acetone. Chemical Marketing Reporter,
212(21):9, 1977.
(4) Lowenheim, F. A., and M. K. Moran. Faith, Keyes, and
Clarks Industrial Chemicals, Fourth Edition. John Wiley &
Sons, Inc., New York, New York, 1975. 904 pp.
(5) Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 1. John Wiley & Sons, Inc., New York,
New York, 1963. 990 pp.
-------
PROCESS DESCRIPTION
Ma-)or Chemical Descriptions
Acetone is a colorless, volatile, flammable liquid (5, 6).
structure of acetone is (6) :
The
H3C-C-CH3
Phenol is a white crystalline solid which turns .pink or red when
contaminated (7). The solid can absorb moisture from the atmos-
phere and liquefy (7, 8). Phenol is toxic and has a distinctive
odor (8). The structure of phenol is (6):
Cumene, the feed material, is a colorless, volatile, aromatic
liquid (9).
,CH(CH3)2
(6) Handbook of Chemistry and Physics, 52nd Edition, R. C.
Weast, ed. Chemical Rubber Co., Cleveland, Ohio, 1971.
(7) Kirk-Othmer Encyclopedia of Chemical Technology, Second
Edition, Volume 15. John Wiley & Sons, Inc., New York,
New York, 1968. 923 pp.
(8) Fleming, J. B., J. R. Lambrix, and J. R. Nixon. Safety in
* i«°miS??ene Process- Hydrocarbon Processing,
~ J.y O , 19/O.
(9) Kirk-Othmer Encyclopedia of Chemical Technology, Second
wiley s sons-
10
-------
Table 5 lists selected properties of cumene, acetone, phenol, and
the important byproducts, ct-methylstyrene and acetophenone (5-11).
TABLE 5. PROPERTIES OF MAJOR PRODUCTS, BYPRODUCTS AND FEED OF
THE CUMENE PEROXIDATION PROCESS (5-11)
Material
Phenol
Acetone
Cumene
a-Methylstyrene
Acetophenone
Molecular Freezing point, *C
weight
-------
PEROJUDATION
,CH(CH3)2
+ 02 —CATALYST
CUMENE + OXYGEN * CUMENE HYDROPEROXIDE
- 1,000 kJ/kg CUMENE, LIQUID PHASE AT 25°C
CLEAVAGE
,C(CH3)2OOH
H+ + I ( }| + CH3-CO-CH3 -»• AH2
CUMENE HYDROPEROXIDE »• PHENOL + ACETONE
AH2 * - 3,000 kJ/kg PHENOL, LIQUID PHASE AT 25°C
Figure 1. Chemistry of the main reactions in the
cumene peroxidation process.
Side reactions, which produce acetophenone and a-methylstyrene,
are shown in Figure 2 (7, 12, 14). The free radical form of
oxygen, 0", is used because the oxygen produced by formation of
2-hydroxy-2-phenylpropane will be consumed in other reactions
(personal communication with H. Walker, Monsanto Chemical
Intermediates Co., Alvin, Texas, 7 October 1977). In addition,
cumene impurities, such as alkylbenzene, can oxidize and cleave
to form phenol and an aldehyde or ketone (e.g., acetaldehyde or
ethyl methyl ketone) (14). Some of the a-methylstyrene and
phenol are polymerized by the sulfuric acid catalyst. The hydro-
carbons present will not sulfate under operating conditions. A
small amount of a-methylstyrene may form styrene during the
cleavage reaction. Styrene formation is not favored thermo-
dynamically (personal communication with R. Canfield, Monsanto
Chemical Intermediates Co., Alvin, Texas, 17 October 1977). The
acidic conditions prevent the formation of styrene oxide, a
known carcinogen (personal communication with G. A. Richardson,
Monsanto Research Corporation, Dayton, Ohio, 4 August 1976).
12
-------
1. ACETOPHENONE
,C(CH3).-OOH
•f 1/2
CO-CH:
CH20 + H20
CUMENE HYDROPEROXIDE + OXYGEN ••ACETOPHENONE + FORMALDEHYDE + WATER
2. 2-HYDROXY-2-PHENYLPROPANE
a.
CH(CH3);
1/2 0
C(CH3)2OH
CUMENE + OXYGEN—»-2-HYDROXY-2-PHENYLPROPANE
b. ^ .C(CH5)2OOH ^*^ XC(CH3)2OH
CUMENE HYDROPEROXIDE 2-HYDROXY-2-PHENYLPROPANE + OXYGEN
3. g-METHYLSTYRENE
,C(CH3)2OH
> 100°C
/C=CH2
CH3 + H20
2-HYDROXY-2-PHENYLPROPANE—^a-METHYLSTYRENE + WATER
Figure 2. Main side reactions of the cumene
peroxidation process.
13
-------
^-c-CH, +
f*^N H* *' CH2 CM>
• XlDO^O'
a- MtnmsiY«B»
*a- MOMVISIYMIE
r^CX
OH J • mom -?-
J. «.«-T«IS
2 • man •
I • 14 • HYOMMV PKJNYl | I-IOMNE
' S
2. t • OlMtTHYl
I. >-NCPTMICNI-4-ow
CHj-CH-CH-CH-'cH,
OH OH CM.
')
««IHni$OIUTfl.C«i||(Ol
3. Phenol £rom
bypro
-------
The peroxidation reaction proceeds by a free radical mechanism
with the selectivity for cumene hydroperoxide being greater at
lower temperatures than at high temperatures (7, 8, 12). However,
the reaction is faster at higher temperatures. The peroxidation
reaction is autocatalytic, poisoned by phenols, and inhibited by
unsaturated compounds, sulfur compounds, and styrene (7, 8, 12).
The cleavage reaction is instantaneous and 99.9% complete in the
presence of sulfuric acid (8). Cumene hydroperoxide is stable at
normal conditions, but decomposes rapidly upon exposure to copper,
zinc, cobalt, acidic conditions, and/or high temperatures
(greater than 140°C) (7, 8, 10). The decomposition reaction is
autocatalytic (8).
Process Technology
There are two versions of the cumene peroxidation process
presently licensed and in use in the United States. They were
developed by Allied Chemical Corp. and Hercules, Inc. (15-19).
The Allied technology represents 45% of the 1977 installed
capacity for synthetic phenol production from cumene, and the
Hercules technology represents 55% (excluding Puerto Rico).
Process flow diagrams of the Allied process and the Hercules
process are shown in Figures 4 and 5 (8, 12, 15, 18-20 and
personal communications with L. B. Evans, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
9 February 1976, and with H. Walker, 7 October 1977). Both
processes exhibit the same general operation in the following
areas:
(15) Petrochemicals Handbook. Hydrocarbon Processing, 56(11):
193, 1977.
(16) Sittig, M. Organic Chemical Process Encyclopedia, Second
Edition. Noyes Development Corporation, Park Ridge, New
Jersey, 1969. 712 pp.
(17) Preparation of Aralkyl Hydroperoxides. Netherlands Appli-
cation 64/08468 (to Allied Chemical Corporation), January
26, 1965.
(18) Cumene Oxidation. U.S. Pat. App. 214,864, August 6, 1962;
British Patent 999,441 (to Allied Chemical Corporation),
July 28, 1965.
(19) Feder, R. L. , R. Fuhrmann, J. Pisanchyn, S. Elishewitz,
T. H. Insinger, and C. T. Mathew. Continuous Process for
Preparing Cumene Hydroperoxide. U.S. Patent 3,906,901
(to Allied Chemical Corporation), September 23, 1975.
(20) Stobaugh, R. B. Phenol: How, Where, Who - Future. Hy-
drocarbon Processing, 45(1):143-152, 1966.
15
-------
PRODUCT TRANSPORT I
LOADING SECTION
Figure 4. Process flow diagram for the Allied Chemical process technology.
(continued)
-------
Figure 4 (continued)
KEY
IDENTIFICATION
STREAM
Al AIR
A2 FEED CUMENE
A3 CUMENE STORAGE TANK EMISSIONS
A4 CLEAVAGE CATALYST
A5 CLEAVAGE CATALYST STORAGE TANK EMISSION
Bl RECYCLE CUMENE, TREATED AND WASHED
B2 CUMENE AND CUMENE HYDROPEROXIDE
B3 SPENT GAS
B4 COOLING WATER
B6 SPENT GAS AND HYDROCARBONS TO ATMOSPHERE
B7 RECYCLE CUMENE
B8 SPENT GAS AND NONCONDENSED VAPORS
B9 RECYCLE CUMENE
BIO RECYCLE CUMENE
Bll TREATING AND WASHING STREAM
B12 TREATING AND WASHING WASTES
C8 RECYCLE CUMENE
C9 VAPOR STREAM
CIO COOLING HATER
Cll NONCONDENSABLE VAPORS TO ATMOSPHERE
C13 CONCENTRATED CUMENE HYDROPEROXIDE
CIS PRODUCT STREAM
C25 "WASHED" PRODUCT STREAM
Dl LIGHT FRACTION
D2 HEAVY FRACTION
D3 CRUDE ACETONE
D4 REFINED ACETONE
D5 ACETONE
D6 ACETONE STORAGE TANK EMISSIONS
D7a ACETONE TRANSPORT LOADING EMISSIONS
D8 CRUDE PHENOL
D9 REFINED PHENOL
D10 PHENOL
Dlla PHENOL STORAGE TANK EMISSIONS
Dl2a PHENOL TRANSPORT LOADING EMISSIONS
D13 VAPORS
D14 COOLING WATER
D153 NONCONDENSABLE VAPORS TO ATMOSPHERE
D16 RECYCLED CONDENSATE
D18 VAPORS
D19 COOLING WATER
D203 NONCONDENSABLE VAPORS TO ATMOSPHERE
D21 RECYCLED CONDENSATE
IDENTIFICATION
STREAM
D22 HEAVY ENDS
D23a HEAVY ENDS STORAGE TANK EMISSIONS
D24 WASTES
D25 STEAM
D26 BOTTOMS
D27 WATER
D28 RECYCLE
D29 VAPORS
D30 COOLING WATER
D31a NONCONDENSABLE VAPORS TO ATMOSPHERE
D32 RECYCLED CONDENSATE
D33 RECYCLE CUMENE
D34 TREATING AND WASHING STREAM
D35 TREATING AND WASHING WASTES
D36 RECYCLE CUMENE, TREATED AND WASHED
D37 PRODUCT STREAM
D38 VAPORS
D39 COOLING WATER
D40a NONCONDENSABLE VAPORS TO ATMOSPHERE
D41 RECYCLED CONDENSATE
D4 2 CRUDE-d-METHYLSTYRENE
D43 VAPORS
D44 COOLING WATER
D45a NONCONDENSABLE VAPORS TO ATMOSPHERE
D46 RECYCLED CONDENSATE
D47 REFINED a-METHYLSTYRENE
D48 a-METHYLSTYRENE
D493 a-METHYLSTYRENE STORAGE TANK EMISSIONS
D503 a-METHYLSTYRENE TRANSPORT LOADING EMISSIONS
D51 RECYCLE
D52 VAPORS
D53 COOLING WATER
D54a NONCONDENSABLE VAPORS TO ATMOSPHERE
D55 RECYCLED CONDENSATE
D56 CRUDE ACETOPHENONE
D57 VAPORS
D58 COOLING WATER
D593 NONCONDENSABLE VAPORS TO ATMOSPHERE
D60 RECYCLED CONDENSATE
D61 REFINED ACETOPHENONE
D62 ACETOPHENONE
D633 ACETOPHENONE STORAGE TANK EMISSIONS
D64a ACETOPHENONE TRANSPORT LOADING EMISSIONS
EMISSION TO ATMOSPHERE.
-------
CO
I
' PRODUCT PURIFICATION SECTION
Figure 5. Process flow diagram for the Hercules process technology.
-------
STREAM
IDENTIFICATION
STREAM
IDENTIFICATION
Al AIR
A2 FEED CUMENE
A3a CUMENE STORAGE TANK EMISSIONS
A4 CLEAVAGE CATALYST
A5a CLEAVAGE CATALYST STORAGE TANK EMISSION
A6 BUFFER
A7a BUFFER STORAGE TANK EMISSION
Bl RECYCLE CUMENE, TREATED
B2 CUMENE AND CUMENE HYDROPEROXIDE
B3 SPENT GAS
B4 COOLING HATER
B5 REFRIGERANT
B6fl SPENT GAS AND HYDROCARBONS TO AIR
B7 RECYCLE CUMENE
B8 SPENT GAS AND NONCONDENSED VAPORS
B9 RECYCLE CUMENE
BIO RECYCLE CUMENE
Bll TREATING STREAM
B12 TREATING WASTES
Cl WASH HATER
C2 WASTEHATER
C3 VAPOR STREAM
C4 COOLING HATER
C5a NONCONDENSABLE VAPOR TO ATMOSPHERE
C6 CONDENSATE RECYCLE
C7 WASHED CUMENE HYDROPEROXIDE
C8 RECYCLE CUMENE
C9 VAPOR STREAM
CIO COOLING WATER
Clla NONCONDENSABLE VAPORS TO ATMOSPHERE
C12 CONDENSATE RECYCLE
C13 CONCENTRATED CUMENE HYDROPEROXIDE
C14 VAPOR STREAM
CIS COOLING HATER
C16 NONCONDENSABLE VAPORS
C17 CONDENSATE RECYCLE
C18 PRODUCT STREAM
C19 VAPOR STREAM
C20 COOLING WATER
C21 NONCONDENSABLE VAPORS
C22 CONDENSATE RECYCLE
C23 WASH WATER
C24 WASTEWATER
C25 WASHED PRODUCT STREAM
C26 VAPORS TO ATMOSPHERE
Dl LIGHT FRACTION
D2 HEAVY FRACTION
D3 CRUDE ACETONE
D4 REFINED ACETONE
D5 ACETONE
D6a ACETONE STORAGE TANK EMISSION
D7a ACETONE TRANSPORT LOADING
D8 CRUDE PHENOL
D9 REFINED PHENOL
D10 PHENOL
Dlla PHENOL STORAGE TANK EMISSION
D12a PHENOL PRODUCT LOADING
D13 VAPORS
D14 COOLING WATER
D15a NONCONDENSABLE VAPORS TO ATMOSPHERE
D16 RECYCLED CONDENSATE
D17 LIGHT ENDS
D18 VAPORS
D19 COOLING WATER
D20a NONCONDENSABLE VAPORS TO ATMOSPHERE
D21 RECYCLED CONDENSATE
D22 HEAVY ENDS
D23a HEAVY ENDS STORAGE TANK EMISSION
D70 CRUDE o-METHYLSTYRENE
D71 VAPORS
D72 COOLING WATER
D73a NONCONDENSABLE VAPORS TO ATMOSPHERE
D74 RECYCLED CONDENSATE
D75 RECYCLE CUMENE
D76 HYDROGEN
D77 a-METHYLSTYRENE
D78a a-METHYLSTYRENE STORAGE TANK EMISSION
D79a a-METHYLSTYRENE TRANSPORT LOADING EMISSION
D80 MIDDLE FRACTION
D81 TREAT STREAM
D82 TREAT WASTES
D83 TREATED FRACTION
D84 VAPORS
D85 COOLING WATER
D86a NONCONDENSABLE VAPORS TO ATMOSPHERE
D87 RECYCLED CONDENSATE
D88 RECYCLE
D89 CRUDE WET PHENOL
D90 VAPORS
D91 COOLING WATER
D92a NONCONDENSABLE VAPORS TO ATMOSPHERE
D93 RECYCLED CONDENSATE
D94 WATER
D95 RECYCLE
EMISSION TO ATMOSPHERE.
-------
a) feed material preparation
b) cumene peroxidation
c) cleavage section
d) product purification
e) waste disposal
f) storage
g) product transport loading
h) intermittent emissions.
The flow diagrams are for the processing of cumene to phenol and
acetone. Similar streams have similar stream numbers in the
figures.
In the peroxidation section, the processes differ in that the
Hercules process uses a buffer and the Allied process uses no
promoters or additives. The Allied technology formerly involved
the use of a suspended promoter and subsequent filtration (18,
19). The latest technology developed by Allied Chemical Corp.,
involves no promoter (19). The majority of the Allied licensees
have converted to this technology or are planning the conversion
(personal cummunication with L. A. Mattioli, Allied Chemical
Corp., Marcus Hook, Pennsylvania, 14 October 1977). Therefore,
the major design in use does not involve a filtration step to
remove a suspended promoter.
In the cleavage section, the process differences between the two
technologies are that the Allied process concentrates the cumene
hydroperoxide by flash distillation, cleaves it to acetone and
phenol with acid, and neutralizes the acid using ion exchange.
The Hercules process washes the cumene hydroperoxide, concen-
trates it by stripping, cleaves the cumene hydroperoxide to ace-
tone and phenol, and removes the acid by a water wash.
In the product purification section, the major process difference
in the two process technologies is that the Allied process sepa-
rates acetophenone but the Hercules process does not. There are
also differences in the actual compositions of the exit streams
from the columns in this section, but both designs separate
acetone, phenol, a-methylstyrene (if desired), recycle streams,
and heavy ends.
The following subsections describe the process operations in the
Allied process and the Hercules process separately.
Allied Process Technology—
Feed materials preparation—The feed materials required are
cumene, air, and cleavage catalyst. Feed material streams are
designated with the letter A before the stream number.
The cumene (Stream A2 in Figures 4 and 5) must be at least 99.8%
pure and may be obtained captively or on the open market (12, 14,
19, 20, and personal communication with L. B. Evans, 9 February
20
-------
1976). If cumene is prepared captively, a purification step may
be necessary. If so, that step is considered to be part of the
manufacture of cumene, not phenol.
The air (Stream Al) is fed to the peroxidation vessels at slight
pressure (18, 19). Air rather than oxygen is used because of
economics (21).
The cleavage catalyst (Stream A4) is sulfuric acid. It is
diluted before addition to the cleavage reactor with water, ace-
tone, phenol, or another hydrocarbon or mixture of hydrocarbons
(22) .
Cumene peroxidation—Figure 6 shows this section of the Allied
process technology. Streams in this section are designated with
the letter B before the stream number.
CUMENE PEROXIDATION SECTION
t'©
r^S
©
Ar1
@ n
fr T
,/Vi
((OXIDATION
A A
V V
BY
STREAM IDENTIFICATION STREAK
Al AIR
A2 FEED CUMENE
A3* CUMENE STORAGE TAN
Bl HECKLE CUMENE, TR
HASHED
82 CUMENE AND CUMENE
B3 SPENT GAS
B4 COOLING HATER
"EMISSION TO ATMOSPHERE
®y~\ ®
-------
In the cumene peroxidation area, feed cumene, recycle cumene, and
air (Streams A2, Bl, and Al) are fed to a vessel where cumene is
peroxidized to cumene hydroperoxide in the liquid phase (7, 8,
14). The vessel is equipped for intimate gas-liquid contact,
with the air stream providing agitation. The vessel cooling sys-
tem is necessary to control the temperature by removing the
approximately 1,400 kJ/kg of cumene heat of reaction (which in-
cludes the contribution of side reactions) (8, 12).
The air flow to the peroxidation step is at least 25% of the
maximum oxygen requirement on a mole basis and where the exit gas
contains 3% to 10% oxygen on a mole basis (19). That is, for
each 1.00 kg of cumene, at least 0.32 kg of gas containing 21%
oxygen is supplied.
Present economics favor the use of air rather than oxygen as the
oxidizing gas. Future events could change that. The favorable
aspects of oxygen use are the reduction in the total liquid en-
trainment and the smaller volumes of waste gas and vaporized
hydrocarbons. Also, some equipment can be reduced in size. The
favorable aspects of air use are the lower cost of air use as
compared to buying oxygen, and safety considerations (13, 23).
The explosive limits of cumene and air mixtures are shown in
Figure 7 as a function of temperature and pressure (23).
Figure 7.
MOL* OXYGEN
(DRY GAS BASIS)
60
71 82 93
SATURATION TEMPERATURE
104
116
127
Upper explosive limits for the cumene-air system
as a function of temperature and pressure (23).
Reprinted from Hydrocarbon Processing by
permission of Gulf Publishing Co.
(23) Saunby, J. B., and B. W. Kiff.
Hydrocarbons to Petrochemical.
55(11):247-252, 1976.
Liquid-Phase Oxidation.
Hydrocarbon Processing,
22
-------
The effects of kinetic and mass transfer rate limitations need to
be investigated to determine whether air or oxygen.is favored at
operating conditions (23).
The operating temperatures decrease stepwise from 120°C to 80°C
in the four reaction vessels (17-19).
Entrained cumene, vaporized cumene, and other vaporized organic
materials are recovered from the waste gas exit stream (Stream
B3) by condensation and carbon adsorption, and then recycled
(Streams B7 and Bl) after being treated and washed. The gas is
released to the atmosphere (Stream B6).
Cleavage section—Figure 8 shows this section of the Allied
Process technology. Streams in this section are designated by
the letter C before the stream number.
The cumene hydroperoxide concentration area concentrates the rel-
atively low concentration of cumene hydroperoxide in the stream
(Stream B2) from the peroxidation section to 80% by weight or
higher (7, 8, 12, 15, 19). Vacuum flash distillation separates
the unreacted cumene (Stream Bl) from the cumene hydroperoxide
(Stream C13) for recycle after treating and washing. The noncon-
densable vapors (Stream Cll) are vented to the atmosphere.
CLEAVAGE SECTION
CLEAVAGE
CATALYST
KEY
STREAM
IDENTIFICATION
A4 CLEAVAGE CATALYST
AS' CLEAVAGE CATALYST STORAGE TANK
EMISSION
B2 CUMENE AND CUMENE HYDROPEROXIDE
C8 RECYCLE CUMENE
C9 VAPOR STREAM
STREAM
IDENTIFICATION
CIO. COOLING HATER
Cll* NOMCONDENSABLE VAPORS TO
ATMOSPHERE
C13 CONCENTRATED CUMENE HYDROPEROXIDE
CIS PRODUCT STREAM
C25 "WASHED" PRODUCT STREAM
'EMISSION TO ATMOSPHERE
Figure 8. Cleavage section of the Allied process
23
-------
In the cleavage area, the concentrated cumene hydro-peroxide
(Stream C13) is cleaved to acetone and phenol (Stream CIS) in
the presence of sulfuric acid (Stream A4) or other strong mineral
acid (12).
Details of the cleavage reactors are not available in the tech-
nical literature. However, no streams are vented to the atmos-
phere (personal communication with L. B. Evans, 9 February 1976) •
The acid cleavage catalyst is neutralized by ion exchange. There
is no emission from this operation (personal communication with
L. B. Evans, 9 February 1976) .
Product purification—The product stream (Stream C25) at this
point contains phenol, acetone, cumene, acetophenone,
ot-methylstyrene, and other materials. The recovery and purifi-
cation section consists of numerous columns. Streams in this
section are designated by the letter D before the stream number.
Figure 9 shows this section of the Allied process technology.
The products (Stream C25) are fed to a separation column which
produces a light fraction (Stream Dl) and a heavy fraction
(Stream D2). The noncondensable vapors are vented to the atmos-
phere (Stream D15).
Acetone (Stream D4) is recovered and purified from the light ends
fraction (Stream Dl) by a dilution column and a concentration
column. Wastes (Stream D23) are condensed and return to the
process or otherwise disposed. Acetone (Stream D4) is removed
from the acetone concentration column and the bottoms (Stream D26)
are recycled (Stream D28) after excess water (Stream D27) is
removed. The noncondensable vapors are vented to the atmosphere
(Stream D20).
Cumene is recovered for recycle from the heavy fraction (Stream
D2) in a cumene column. The noncondensable vapors are vented to
the atmosphere (Stream D31). The cumene (Stream D33) is treated,
washed, and recycled, generating treatment wastes (Stream D35)•
The cumene column bottoms (Stream D37) are fed to an ot-methyl-
styrene column, a-methylstyrene (Stream D42) is separated from
a crude phenol stream (Stream D8). The noncondensable vapors
(Stream D38) are vented to the atmosphere.
a-Methylstyrene is refined in another column, producing product
(Stream D47), a stream recycled to the process (Stream D51), an
noncondensable vapors (Stream D45) are vented to the atmosphere.
Phenol (Stream D9) is recovered from Stream D8 as the distillate
of the phenol column. The noncondensable vapors (Stream D54) are
vented to the atmosphere.
24
-------
KEY
STREAM
C25
Dl
D2
D3
D4
D5
a
D7a
D8
D9
D10
Oil
D12
013
D14
D15
016
018
019
020
021
022
D23
024
D2S
026
027
D28
IDENTIFICATION
030
D31a
D32
"WASHED PRODUCT STREAM
LIGHT FRACTION
HEAVY FRACTION
CRUDE ACETONE
REFINED ACETONE
ACETONE
ACETONE STORAGE TANK EMISSIONS
ACETONE TRANSPORT LOADING EMISSIONS
CRUDE PHENOL
REFINED PHENOL
PHENOL
PHENOL STORAGE TANK EMISSIONS
PHENOL TRANSPORT LOADING EMISSIONS
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
HEAVY ENDS
HEAVY ENDS STORAGE TANK EMISSIONS
WASTES
STEAM
BOTTOMS
WATER
RECYCLE
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
STREAM
D33
034
D3S
D36
D37
D38
O39
D40a
041 .
D42
D43
D44
P«5
D46
047
D48,
D49a
D50
D51
DS2
D53
D54a
D55
D56
D57
D58
D59a
D60
D61
D62
D63*
D64a
IDENTIFICATION
RECYCLE CUMENE
TREATING AND WASHING STREAM
TREATING AND HASHING WASTES
RECYCLE CUMENE, TREATED AND WASHED
PRODUCT STREAM
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
CRUDE a-METHYLSTYRENE
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
REFINED a-METHYLSTYRENE
a-METHYLSTYRENE
a-METHYLSTYRENE STORAGE TANK EMISSIONS
a-METHYLSTYRENE TRANSPORT LOADING EMISSIONS
RECYCLE
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
CRUDE ACETOPHENONE
VAPORS
COOLING WATER
NONCONDENSABLE VAPORS TO ATMOSPHERE
RECYCLED CONDENSATE
REFINED ACETOPHENONE
ACETOPHENONE
ACETOPHENONE STORAGE TANK EMISSIONS
ACETOPHENONE TRANSPORT LOAIDNG EMISSIONS
EMISSIONS TO ATMOSPHERE
Figure 9. Product purification section of the Allied process.
25
-------
The bottoms (Stream D56) are fed to the acetophenone column,
which produces acetophenone (Stream D61), a residue (heavy ends,
Stream D22), and noncondensable vapors (Stream D59) which are
vented to the atmosphere.
Hercules Process Technology—
Feed materials preparation—The feed materials required are
cumene, air, buffer, and cleavage catalyst. Feed material
streams are designated by the letter A before the stream number.
The cumene (Stream A2) must be at least 99.8% pure and may be
obtained captively or on the open market (12, 14, 19, 20, and
personal communication with L. B. Evans, 9 February 1976). If
cumene is prepared captively, a purification step may be necessary-
Such a step is considered to be part of the manufacture of cumene,
not phenol.
The air (Stream Al) is fed to the peroxidation vessels at approxi"
mately 620 kPa (personal communication with H. Walker, 7 October
1977). Air rather than oxygen is used because of economics (23).
The buffer, sodium carbonate (Na2CC>3) is fed to the process in an
aqueous solution (Stream A6).
The cleavage catalyst (Stream A4) is sulfuric acid. It is diluted
before addition to the cleavage reactor with water, acetone,
phenol, or another hydrocarbon or mixture of hydrocarbons (22).
Cumene peroxidation—Figure 10 shows this section of the
Hercules process technology. Streams in this section are
designated by the letter B before the stream number.
CUMENE PEROXIDATION SECTION
»' HI M* SKIT MS MD HtOdOCMBOKS TO
U FEfOCUCIC All
M* CUM ITMMC TIMK MStlMS 17 MCfUC CUHCM
»• ^S&tmm^m^m S S^reuISi"0^0015"
u
u
M
H
HNISSIM TO MMWMK.
Figure 10. Cumene peroxidation section of the Hercules process
26
-------
In the cumene peroxidation area, feed cumene, recycle cumene, air,
and Na2CO3, a buffer, in aqueous solution (Streams A2, Bl, Al, and
A6) are fed to a vessel where cumene is peroxidized to cumene
hydroperoxide in the liquid phase (1, 8, 14). The vessel is
equipped for intimate gas-liquid contact, with the air stream
providing the agitation. The vessel cooling system is necessary
to control the temperature by removing the approximately 1,400 kJ/
kg of cumene heat of reaction (which includes the contribution of
side reactions) (7, 8, 12, 14).
The air flow to the peroxidation step is at least 0.20 kg of air
containing 21% oxygen per 1 kg of cumene fed (personal communi-
cation with L. B. Evans, 9 February 1976).
Present economics favor the use of air rather than oxygen; see
the previous discussion in Section 3.A.3.a(2).
The operating temperatures range from 90°C to 120°C at pressures
of approximately 620 kPa (personal communications with H. Walker,
7 October 1977, and with R. Canfield, 10 February 1978).
Entrained cumene, vaporized cumene, and vaporized hydrocarbons
are recovered from the spent gas (Stream B3) by condensation,
using cooling water and a refrigerant as heat transfer agents.
The stream (B6) is released to the atmosphere.
Cleavage section—Figure 11 shows this section of the Hercules
process technology. Streams in this section are designated by
the letter C before the stream number.
STUB*
ci
a
a
CI.
a'
C6
cr
Cf
c»
U.UVMC MTAinT
CUAMBE CATAIMT I10MGC TMK
aitm at COCK maemaim
HUH mini
CIO. MOLIM WTU
C1I* •MOBItiaiUl.t MMMS TO ATNBMttE
COO. Mi WTU
mtntattmt wot to *i
OMMttTI KCTCU
HUMD cue* mtwuoim
MCTCLI OHM
wot ITKM
CMXOMC KCTCU
cmcamwno OHM mwenmiM
>«HM smw
coo. IK turn
C1Z
Cll
C14
Cll
Clt ... .
C17 tOBOOATI KCTOI
Ctl MWCT inUM
Clt WO* STKM
cn coaiw WTCX
cti •encgpoimu uran
Ol OMOMTE KCTCU
—
I
*OUJH« TO «TmmuE
CM HMO WOOOCT 1TKM
CM! MAMS
Figure 11. Cleavage section of the Hercules process
27
-------
The cumene hydroperoxide stream (B2) is washed to remove the
buffer and any water soluble material. The noncondensable vapors
are vented (Stream C5) to the atmosphere. The wastewater (Stream
CD is sent to the process wastewater system.
The cumene hydroperoxide concentration area concentrates the
relatively low cumene hydroperoxide concentration in the stream
(Stream C7) from the wash operation to 80% by weight or
higher (7, 8, 12, 15, and personal communication with H. Walker,
7 October 1977). Vacuum distillation or stripping is used to
separate the cumene hydroperoxide (Stream C13) from the recycle
cumene (Stream C8) which is treated before recycle. A thin or
falling film evaporator may be used. The noncondensable vapors
(Stream Cll) are vented to the atmosphere.
In the cleavage area, the concentrated cumene hydroperoxide
(Stream C13) is cleaved to acetone and phenol in the presence
of sulfuric acid (Stream A4) or other strong mineral acid. Con-
centrated cumene hydroperoxide is fed to a small, constant flow/
stirred tank reactor along with sulfuric acid diluted to 5% to
10% by weight with acetone. Water, phenol or other hydrocarbons
can be used for dilution (22) . The liquid phase reaction is
typically held at 50°C to 95°C at slightly elevated pressure,
typically 136 kPa (4, 7, 8, 12, 13, 20-22). The reaction heat
of approximately 1,500 kJ/kg cumene hydroperoxide boils approxi-
mately 1.26 kg acetone per 0.45 kg cumene hydroperoxide fed. The
acetone stream (C6) is condensed and returned. The noncondensable
vapors (Stream C5) are vented to the atmosphere (7, 8, 12, 13,
23) .
The acid cleavage catalyst is removed by a water wash that con-
tains a compound such as sodium sulfate, sodium phenolate, or
other, to neutralize the acid (7, 8, 12, 13). The noncondensable
vapors (Stream C21) are combined with those from the cleavage
step (Stream C16) to be vented to the atmosphere (Stream C26).
The wastewater (Stream C24) is sent to the process wastewater
system.
Product purification—The product stream (C25) at this point con-
tains phenol, acetone, cumene, acetophenone, a-methylstyrene, and
other materials. The recovery and purification section consists
of numerous columns. Streams in this section are designated by
the letter D before the stream number.
Figure 12 shows this section of the Hercules process technology.
The products (Stream C25) are fed to a separation column which
produces a light fraction (Stream Dl) and a heavy fraction
(Stream D2). The noncondensable vapors (Stream D15) are vented
to the atmosphere.
28
-------
YPRODUCT TRANSPORT!
LOADING
vo
C25 WASHED PRODUCT STREAM
Dl LIGHT FRACTION
D2 HEAVY FRACTION
D3 CRUDE ACETONE
D4 REFINED ACETONE
D5 ACETONE
D6a ACETONE STORAGE TANK EMISSION
D7a ACETONE TRANSPORT LOADING
D8 CRUDE PHENOL
D9 REFINED PHENOL
D10 PHENOL
Dlla PHENOL STORAGE TANK EMISSION
D12a PHENOL PRODUCT LOADING
D13 VAPORS
D14 COOLING WATER
Dl5a NONCONDENSABLE VAPORS TO ATMOSPHERE
D16 RECYCLED CONDENSATE
D17 LIGHT ENDS
D18 VAPORS
D19 COOLING WATER
D20a NONCONDENSABLE VAPORS TO ATMOSPHERE
D21 RECYCLED CONDENSATE
D22 HEAVY ENDS
D23a HEAVY ENDS STORAGE TANK EMISSION
D70 CRUDE o-METHYLSTYRENE
EMISSION TO ATMOSPHERE.
D71 VAPORS
D72 COOLING WATER
D73a NONCONDENSABLE VAPORS TO ATMOSPHERE
D74 RECYCLED CONDENSATE
D75 RECYCLE CUMENE
D76 HYDROGEN
D77 a-METHYLSTYRENE
D78a a-METHYLSTYRENE STORAGE TANK EMISSION
D79a a-METHYLSTYRENE TRANSPORT LOADING EMISSION
D80 MIDDLE FRACTION
D81 TREAT STREAM
D82 TREAT WASTES
D83 TREATED FRACTION
D84 VAPORS
D85 COOLING WATER
D86a NONCONDENSABLE VAPORS TO ATMOSPHERE
D87 RECYCLED CONDENSATE
D88 RECYCLE
D89 CRUDE WET PHENOL
D90 VAPORS
D91 COOLING WATER
D92a NONCONDENSABLE VAPORS TO ATMOSPHERE
D93 RECYCLED CONDENSATE
D94 WATER
D95 RECYCLE
Figure 12. Product purification section of the Hercules process.
-------
Acetone (Stream D4) is recovered and purified from the light ends
fraction (Stream Dl) by distillation in a light ends column and
in an acetone column. The light ends (Stream D17) removed in the
first distillation are condensed and returned to the process, or
otherwise disposed, such as for use as fuel. Acetone (Stream D4)
is distilled from the second column, and the bottoms (Stream D70)
may be sold as crude a-methylstyrene, if the demand is present,
or the stream can be hydrogenated to produce recycle cumene
(Stream D75). If the crude a-methylstyrene is sold, the emis-
sions are from storage tanks and product transport loading
(Streams D78 and D79). If the crude a-methylstyrene is hydro-
genated, the emissions are from the noncondensable vapors
(Stream D73).
The heavy fraction (Stream D2) is separated into a middle frac-
tion (Stream D80) and heavy ends (Stream D22). Acetophenone
could be recovered from the heavy ends, but with the minor
demand for it, it is not. The heavy ends may be sold, cracked,
burned, or otherwise disposed of. The column is not vented. The
middle fraction (Stream C80) is treated to remove impurities and
fed to a separation column. The treatment wastes (Stream D82)
are sent to the process wastewater system. A stream recycled to
the process (Stream D88) is separated from the crude wet phenol
(Stream D89). Noncondensable vapors (Stream D86) are vented to
the atmosphere.
The crude wet phenol (Stream D89) is dewatered to produce a
water stream (D94), crude phenol (Stream D8), and noncondensable
vapors (Stream D92) which are vented to the atmosphere.
Phenol (Stream D9) and a stream recycled to the process (Stream
D95) are produced from the phenol column.
Other Process Operations—
Waste disposal—Gaseous and liquid wastes are generated by the
manufacture of acetone and phenol from cumene.
The gaseous wastes consist of light ends from acetone purifica-
tion, and vapors. The light ends may be condensed and returned
to the process, scrubbed and released to the atmosphere, released
as is to the atmosphere, burned as fuel, or used in another pro-
cess (personal communication with L. B. Evans, 9 February 1976).
The vapors are hydrocarbons that were not condensed and were
subsequently released to the atmosphere. The origins of these
vapors were discussed in detail previously.
Liquid wastes include wastewater and heavy ends. The process
wastewater system receives all wastewater and waste treatment
streams and subsequently disposes of the wastes. A variety of
methods, such as deep well injection, plant treatment systems,
and municipal treatment systems, are used. Heavy ends are used
30
-------
as fuel, sold as a byproduct, cracked in a furnace, extracted, or
used in another process (personal communication with L. B. Evans,
9 February 1976).
Tankage—The tankage requirements for a plant manufacturing ace-
tone and phenol from cumene were estimated (see Appendix A) and
are summarized in Table 6.
TABLE 6. TANKAGE REQUIREMENTS FOR A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
(136 x 103 metric tons/yr)
Composition
Number
Size, each Turnovers, Temperature,
Phenol3.
Acetone
Cumene^
Acetophenone9
a-Methylstyrene
Heavy endsD
Oxidation catalyst
Cleavage catalyst
Wastewater
4
4
3
1
1
1
1,200
1,000
3,800
23
95
190
15
21
16
5
27
102
50 to 60
ambient
ambient
30
30
70
N°te.—Blanks indicate no data available.
a
Fixed roof tank, vents to atmosphere.
Floating roof tank.
Product loading—Phenol, acetone, and the various byproducts are
transported to the customer by railroad tank car, tanker truck,
barge, or 0.21-m3 drum.
Railroad tank cars, tanker trucks, barges, and drums are loaded
by means of loading racks which meter and deliver the various
materials from storage. The emission is caused by displacement
°f the vapors present in the item being filled. The vapors are
a mixture of hydrocarbons and air. The hydrocarbon amounts de-
pend on what was in the item previously, the material being
loaded, and the method of filling (24).
Loading racks contain equipment to meter and deliver products
into tank vehicles from storage either by overhead filling
through the top hatch in the tank vehicle or by bottom filling
(24) Air Pollution Engineering Manual, Second Edition,
J. A. Danielson, ed. Publication No. AP-40, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, May 1973. 987 pp.
31
-------
t around level. The elevated platform structure employed for
overhead filling, constructed with hinged side platforms attached
to the sides of a central walkway, can be raised when not in use.
For loading, a tank vehicle is positioned adjacent to the central
walkway and a hinged side platform is lowered to rest upon the
top of the tank vehicle to access the top hatch. The meters,
valves, loading tubes or spouts, motor switches, and similar
necessary loading equipment are located on the central walkway-
Bottom loading facilities are simpler since the tank vehicle is
easily filled through accessible fittings on its underside.
Loading of barges at modern terminals uses equipment similar to
that used for elevated tank vehicle loading except for size. A
pipeline manifold with flexible hoses is used for loading at
older terminals. Marine installations are considerably larger
and operate at much greater loading rates than inland loading
facilities.
The loading arm assembly refers to the equipment at the discharge
end of a product pipeline that is necessary for filling tank _
vehicles. Component parts include piping, valves, meters, swivel
joints, fill spouts, and vapor collection adaptors.
Overhead loading arms can be pneumatic, counterweighted, or ten-
sion spring depending upon the manner in which the vertical move-
ment of the arm is achieved. Bottom loading employs a flexible
hose or a nonflexible, swing-type arm connected to the vehicle
from the ground level storage facility.
Loading arms at modern marine terminals are similar in design to,^
those used for overhead loading of tank vehicles. The barge lo .^
ing arms are too large for manual operation, requiring a hydrauli
system to effect arm motion. Older installations use reinforced
flexible hoses to convey products from pipeline discharge mani-
folds to the barge. The hoses are positioned by means of a wincn
or crane (24).
Other process equipment—Hydrocarbon emissions other than from
stacks and/or vents are considered fugitive. They occur from
pressure relief valves, pump seals, compressor seals, pipeline
valves and flanges, equipment purges, process drains, waste-
water separators, and laboratory analysis sampling. Fugitive
emissions may occur due to accidents, inadequate maintenance,
or poor planning, although fugitive emissions occur even in the
absence of such conditions and are unavoidable characteristics
of some process operations.
Shutdowns and regenerations—Plants manufacturing phenol and
acetone from cumene use continuous operations. Shutdowns, turn-
arounds, and startups to permit maintenance are scheduled.
During this time equipment is purged of hydrocarbon vapors to
allow maintenance access.
32
-------
Ion exchange resin regeneration, which removes the acid cleavage
catalyst/ will contribute to wastewater streams.
Regeneration of carbon adsorption emission control equipment will
also contribute to wastewater streams and vary the emission rate
when the carbon bed is replaced on stream, if the system is in
parallel. Also, the emissions will vary as the carbon bed be-
comes spent.
PLANT MATERIAL BALANCE
Figure 13 is a very simplified process diagram for the manufacture
of acetone and phenol via cumene peroxidation. Table 7 contains
an estimated material balance for a representative plant having
136 x 103 metric tons/yr phenol capacity utilized at 80%. The
material balance was estimated using the product specifications
in Appendix B, the emission information in Section 4, and
stoichiometry.
GEOGRAPHIC DISTRIBUTION
Production of Phenol and Acetone
Phenol and acetone are produced by varied routes nationwide.
Tables 8 and 9 list the companies, processes and capacities for
phenol and acetone (2-4, 13, 25-33, and personal communication
with L. A. Mattioli, 18 November 1976).
(25) World Wide HPI Construction Boxscore. Hydrocarbon Proces-
sing, 54(2, Section 2):10, 1975.
(26) World Wide HPI Construction Boxscore. Hydrocarbon Proces-
sing, 55(2, Section 2):3, 9, 10, 14, 1976.
(27) World Wide HPI Construction Boxscore. Hydrocarbon Proces-
sing, 57(2, Section 2):4-19, 1978.
(28) Chem Sources U.S.A., 1976 Edition. Directories Publishing
Company, Inc., Flemington, New Jersey, 1974. pp. 5, 6,
220, 519.
(29) 1978 Buyers' Guide Issue. Chemical Week, October 26, 1977,
Part 2, pp. 306, 307, 415, 516, 523, 549, 568, 635.
(30) OPD Chemical Buyers Directory, 1977-1978. Schnell Publishing
Company, New York, New York, 1977. pp. 23-24, 294, 556, 638.
(31) Preliminary Report on U.S. Production of Selected Synthetic
Organic Chemicals, Preliminary Totals, 1976. S.O.C. Series
C/P-77-1, United States International Trade Commission,
Washington, D.C., 16 March 1977. 6 pp.
(32) Phenol Users Want to Be Phenol Makers. Chemical Week,
121(3):11-12, 1977.
(33) Phenol Producers Face Capacity Problems. Chemical and
Engineering News, 55(30):8-9, 1977.
33
-------
i:
r
CUMENE
PEROXI DATION
CLEAVAGE
SECTION
\^\ Irz^ l<
j
PRODUCT
PURIFICATION
STORAGE
TANKS
PRODUCT
LOADING
STREAM KEY
STREAM
NUMBER DESCRIPTION
1 CUMENE
2 AIR
3,7.11 WATER
4,8.12 WASTEWATER
5 CUMENE PEROXIDATION
EMISSIONS
6 CUMENE HYDROPEROX IDE
9 CLEAVAGE SECTION
EMISSIONS
10 PRODUCT STREAM
13 PRODUCT PURIFICATION
SECTION EMISSIONS
14,20 PHENOL
15.21 ACETONE
16,22 ACETOPHENONE
17.23 « -METHYLSTYRENE
18 HEAVY ENDS
19 STORAGE TANK EMISSIONS
24 PRODUCT TRANSPORT
LOADING EMISSIONS
25 FUGITIVE EMISSIONS
a EMISSIONS
Figure 13.
Simplified process flow diagram for the manufacture
of acetone and phenol from cumene.
-------
U)
Ul
TABLE 7. ESTIMATED MATERIAL BALANCE FOR A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
(g/kg phenol produced)
Stream number: 1 2 3, 7, 11
Description:8 Cumene Air Water
Component :
Phenol
Acetone
Acetophenone
a-Methylstyrene
Cumene 1,416.45
Cumene hydroperoxide
Water
Nitrogen (N2) 2,054
Oxygen (O2) 546.0
Acetaldehyde
Benzene
2-Butanone
2-Butenal
t-Butylbenzene 1.420
Dimethyl styrene
Ethylbenzene 1.420
Formaldehyde
2-Hydroxy-2-phenylpropane
Isopentanal
Mesityl oxide
Naphthalene
Propanal
Hydrocarbons 0.710
Totald 1,420 2,600
4, 8, 12 5 6
Cumene Cumene
Waste- peroxidation hydro-
water emissions peroxide
0.60
<0.0086
<0.0001
0.86
__
2,054
180
0.20
0.050
<0.0055
<0.0022
0.00005
0.00042
0.0010
<0.0009
<0.0001
<0.0011
2,236
9
Cleavage
section
emissions
6 x 10~6
4.4 x 10"6
0.14
3.1 x 10~5
1.8 x 10"6
8.5 x 10~8
2.3 x 10~5
5.0 x 10"6
<2.6 x 10~7
3.4 x 10~6
8.5 x 10~7
0.1401
10
Product
H*-Y-»aTn
_ —
_ —
__
__
—
—
Note.—Blanks indicate the component is not present; dashes indicate the quantity is unknown.
aTemperature and pressure are dependent upon the process technology used.
Individual materials, especially those present in small amounts, will not balance due to information on the
actual compounds listed as hydrocarbons not being known.
Hydrocarbons in methane equivalents, based on carbon content, if known.
Totals do not add due to rounding.
-------
TABLE 7 (continued)
Stream number:
Description :a
Component:
Phenol
Acetone
Acetophenone
a-Me thy 1 s tyr ene
Cumene
13
Product
purification
section
emissions
14, 20 15, 21 16, 22
Aceto-
Phenol Acetone phenone
999.75
608.45
1.078
17, 23
a-Methyl-
styrene
21.18
0.0427
18 19
Storage
Heavy tank
end 36 emissions
0.051
0.060
5.5 x 10~5
0.0020
0.028
24
Product
transport
loading
emissions
0.11
0.074
25
Fugitive
emissions
Cumene hydroperoxide
Hater
Nitrogen (N2)
Oxygen (02)
Ace taldehyde
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Dimethylstyrene
Ethylbenzene
Formaldehyde
2-Hydroxy-2-phenylpropane
Isopentanal
Mesityl oxide
Naphthalene
Propanal
Hydrocarbons
Totald
0.2000 1.831
0.0002
0.0500
1.20
1.20
1,000
0.0214 0.022
610.3 1.100
0.1071
21.33
149.5
0.1411
0.184
0.0220
0.0220
Note.—Blanks indicate the component is not present; dashes indicate the quantity is unknown.
aTemperature and pressure are dependent upon the process technology used.
Individual materials, especially those present in small amounts, will not balance due to information on the actual
compounds listed as hydrocarbons not being known.
CHydrocarbons in methane equivalents, based on carbon content, if known.
''Totals do not add due to rounding.
eHydrocarbon content of wastewater is not known. The amount is aggregated with the heavy ends so the total flow of
hydrocarbons will balance. Hydrocarbons in methane equivalents based on carbon content if known.
-------
TABLE 8. PHENOL PRODUCERS
Company and location
^Process
Allied Chemical Corp.
Frankford, PA
Clark Oil and Refining Co.
Blue Island, IL
Dow Chemical Co.
Midland, MI
Oyster Creek, TX
Ferro Corp.
Santa Fe Springs, CA
Georgia-Pacific Corp.
Plaquemine, LA
Getty Oil Co.
El Dorado, KS
Kaiser Steel
Fontana, CA
Kalama Chemicals Co.
Kalama, WA
Koppers Co.
Follansbee, WV
Merichem Co.
Houston, TX
Monsanto Co.
Chocolate Bayou, TX
Reichold Chemicals*1
Tuscaloosa, AL
Shell Chemical Co.
Deer Park, TX
Sherwin-Williams
S.O. of Calif.: Chevron
Richmond, CA
Stimson Lumber Co.
Anacortes, WA
Union Carbide
Bound Brook, NJ
Marietta, OH
U.S. steel Corp.
Haverhill, OH
Clairton, PA
Total
Allied cumene
peroxidation.
Allied cumene
peroxidation.
Benzene chlorination.
Allied cumene
peroxidation.
Natural.
Hercules cumene
peroxidation.
Allied cumene
peroxidation.
Natural.
Toluene oxidation.
Natural.
Natural.
Hercules cumene
peroxidation.
Benzene sulfonation.
Hercules cumene
peroxidation
Hercules cumene
peroxidation.
Natural.
Allied cumene
peroxidation.
— «
Hercules cumene
peroxidation.
Natural.
272
39
18
180
_a
120
43
_a
25
a
227
68
227
_a
25
_a
77
_a
147
_a
1,468
*Not available.
Production suspended in March 1978. Plant permanently closed
December 1978.
37
-------
TABLE 9. ACETONE PRODUCERS
Company and location
Raw material
or process type
Annual capacity,
106 metric tons
Allied Chemical Corp
Frankford, PA
Clark Oil and Refining Co.
Blue Island, IL
Dixie Chemical Co.
Bayport, TX
Dow Chemical Co.
Oyster Creek, TX
Eastman Kodak
Kingsport, TN
Exxon Corp.
Bayway, NJ
Georgia-Pacific Corp.
Plaquemine, LA
Getty Oil Co.
El Dorado, KS
Goodyear Tire and Rubber Co.
Bayport, TX
Monsanto Company
Chocolate Bayou, TX
Oxirane Corp.
Bayport, TX
Publicker Industries
Philadelphia, PA
Shell Chemical Co.
Deer Park, TX
Deer Park, TX
Dominquez, CA
Norco, LA
Skelly Oil Company
El Dorado, KS
S.O. of California: Chevron
Richmond, CA
Union Carbide
Bound Brook, NJ
Institute and S. Charleston,
Texas City, TX
U.S. Steel Corp
Haverhill, OH
Total
WV
cumene
cumene
_a
cumene
isopropanol
isopropanol
cumene
cumene
a
cumene
propylene
fermentation
cumene
isopropanol
isopropanol
isopropanol
cumene
cumene
cumene
isopropanol
isopropanol
cumene
0.15
0.02
_a
0.13
0.04
0.06
0.08
0.03
a
0.14
0.03
stand-by
0.14
0.18
0.05
0.05
0.03
0.01
0.05
0.05
0.05
0.09
1.38
Not available.
38
-------
The area covered by this study does not include Puerto Rico.
Whenever possible Puerto Rico's industry is not included in any
calculations or tables.
Phenol is produced by 18 companies at 21 locations. The 1977
installed capacity for phenol production is 1,468 x 103 metric
tons, of which approximately 93% or 1,358 x 103 metric tons is
cumene based.
Acetone is produced by 17 companies at 22 locations. The cumene-
based process accounts for approximately 60% or 831 x 103 metric
tons of installed annual acetone capacity of 1,380 x 103 metric
tons.
Location of Plants Manufacturing Acetone and Phenol from Cumene
There are currently 10 locations in the continental United States
where phenol and acetone are produced from cumene (2, 3). They
are listed in Table 10 by company. The locations are plotted in
Figure 14.
Location of Cumene Producers
The 11 current producers of cumene in the continental United
States (34) are listed in Table 11. Four of these manufacture
acetone and phenol from cumene. All of the cumene production
locations are indicated in Figure 14. Shell Chemical Company is
Planning construction of a 280 x 106 metric ton cumene plant (34).
Chemical Profile, Cumene. Chemical Marketing Reporter,
207(14):9, 1975.
39
-------
TABLE 10.
PLANTS MANUFACTURING ACETONE
AND PHENOL FROM CUMENE
Company
Allied Chemical Corp
Specialty Chemicals Division
Frank ford, PA
Clark Oil and Refining Corp.
Clark Chemical Corp.
Blue Island, XL
Dow Chemical, U.S.A.
Oyster Creek, TX
Georgia-Pacific Corp.
Chemicals Division
Plaquemine, LA
Getty Oil Co.
Getty Refining and Marketing Co.
El Dorado, KS
Monsanto Company
Monsanto Chemical Intermediates
Chocolate Bayou, TX
Shell Oil Co.
Shell Chemical Co.
Deer Park, TX
S.O. of California
Chevron Chemical Co.
Richmond, CA
Union Carbide Corp.
Chemicals and Plastics Division
Bound Brook, NJ
U.S. Steel Corp.
Haverhill, OH
Total
Phenol capacity.
Licenser metric tons/yr
Allied
Allied
Allied
Hercules
Allied
Hercules
Hercules
Hercules
Allied
Hercules
272,000
39,000
181,000
120,000
43,000
227,000
227,000
25,000
77,000
147,000
1,358,000
aPuerto Rico is not included in this study.
Figure 14.
Locations of plants manufacturing phenol
from cumene, and cumene.3
A • indicates a plant manufacturing acetone and phenol from
cumene. A * indicates a plant manufacturing cumene.
40
-------
TABLE 11. CUMENE PRODUCERS
Annual cumene
capacity,
Company and location 106 metric tons
Ashland Oil, Inc.
Ashland Chemical Co.
Ashland, KY 0.148
Clark Oil and Refining Corp.
Clark Chemical Corp.
Blue Island, IL 0.054
Coastal States Gas Corp.
Coastal States Marketing, Inc.
Corpus Christi, TX 0.068
Dow Chemical Co.
Midland, MI 0.005
Getty Oil Co.
Getty Refining and Marketing Co.
El Dorado, KS 0.068
Gulf Oil Corp.
Gulf Oil Chemical Co.
Philadelphia, PA 0.170
Port Arthur, TX 0.204
Marathon Oil Co.
Texas City, TX 0.095
Monsanto Co.
Monsanto Chemical Intermediates
Chocolate Bayou, TX 0.306
S.O. of California
Chevron Chemical Co.
Richmond, CA 0.041
Sun Oil Co.
Sun Oil Co. of PA
Suntide Refining Co.
Corpus Christi, TX 0.113
Texaco, Inc.
Westville, NJ 0.068
Total 1.340
41
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SECTION 4
EMISSIONS
In this section, air emissions are characterized by location,
effective emission heights, and emission factors for criteria
pollutants and selected pollutants; the hazard potential of
each pollutant is quantified, and the affected population is
determined; the national and state emission burdens are calcu-
lated; and the growth factor of the industry's emissions is
determined. The data in this section were obtained through
industry cooperation.
SELECTED POLLUTANTS
Compounds identified as potential emissions from the manufacture
of acetone and phenol from cumene are listed in Table 12 (13, 14
and personal communication with L. B. Evans, 9 February 1976).
A sampling program was undertaken to quantify these compounds
plus others which may not previously have been known to be
present. (See Appendices C through H.) Table 13 lists the
materials identified during sampling plus those materials re-
ported as emissions, along with the TLV's of the forms emitted,
their primary ambient air quality standards where applicable,
and their health effects (35-39).
(35) TLVs® Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1977. American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1977. 94 pp.
(36) Air Quality Data - 1973 Annual Statistics. EPA-450/2-74-
015, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, November 1974. 151 pp.
(37) The Condensed Chemical Dictionary, Eighth Edition, G. G.
Hawley, ed. Van Nostrand Reinhold Company, New York,
New York, 1971. 971 pp.
(38) National Research Council. Vapor-Phase Organic Pollutants
Volatile Hydrocarbons and Oxidation Products. EPA-600/1-
75-005 (PB 249 357), U.S. Environmental Protection Agency/
Research Triangle Park, North Carolina, October 1975.
(39) Sax, N. I. Dangerous Properties of Industrial Materials.
Van Nostrand Reinhold Company, New York, New York, 1975.
1258 pp.
42
-------
TABLE 12. SUSPECTED EMISSIONS FROM ACETONE AND PHENOL
MANUFACTURE FROM CUMENE PRIOR TO SAMPLING
Acetaldehyde
Acetic acid
Acetone
a-Hydroxyacetone
Diacetone alcohol
Acetophenone
Benzene
Ethylbenzene
n-Propylbenzene
Methyl isobutyl carbinol
Cumene
Cumene hydroperoxide
Dicumyl peroxide
1,1,2,2-Tetraraethyl-l,2-diphenylethane
Formaldehyde
Formic acid
2-Methylbenzofuran
Methylgloxal
Heavy tars
2,6-Dimethyl-2,5-heptadiene-4-one
1-Hydroxyethyl methyl ketone
Methyl isobutyl ketone
Lactic acid
Mesityl oxide
Methanol
a-Methyls tyrene
Dimers of a-methylstyrene
2-Methyl-3,4-pentanediol
4-Hydroxy-4-methyl-2-pentanone
Phenol
2,4,6-Tris(2-phenyl-2-propyl)phenol
2-Hydroxy-2-phenylpropane
2-Phenyl-2-(2-hydroxyphenyl)propane
2-Phenyl-2-(4-hydroxyphenyl)propane
Toluene
43
-------
TABLE 13.
CHARACTERISTICS OF EMISSIONS IDENTIFIED DURING SAMPLING OR REPORTED
FROM ACETONE AND PHENOL PLANTS USING CUMENE PEROXIDATION
Material emitted
TLV,
mg/iB3
Primary
ambient
air quality
standard,
Health effects
Nonmethane hydrocarbons
Acetaldehyde
Acetone
Acetophenone
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethyl benzene
Formaldehyde
Heavy ends
2-Hydroxy-2-phenylpropane
o-Hethylatyrene
Naphthalene
Phenol
Propanal
Toluene
Arsenic
Barium
Calcium
Chlorine
Fluorine
Magnesium
Manganese
Phosphorus
Potassium
Sodium
Sulfur
Titanium
180
2,400u
_b
30
590L
_b
_b
24!b
435
_b
_b
480
SO
19
_b
-b
0.5
0.5
_b
3
_b
_b
_b
_b
.b
0.000160
(3 hr)
Local irritant, central nervous system narcotic
Skin irritant, narcotic in high concentrations
Narcotic in high concentrations
Carcinogen
Local irritant
Irritant, dangerous to eyes
Details unknown
Narcotic, toxic
_b
Skin and mucous membrane irritant
Irritant, toxic
_b
_b
Toxic
Moderate irritant
Toxic, irritant
Toxic
Toxic
Variable, depends on compound
Variable, depends on compound
Variable, depends on compound
Irritant, toxic
Variable, depends on compound
Variable, depends on compound
Variable, depends on compound
Variable, depends on compound
Variable, dependent on compound
Variable, dependent on compound
Physiologically inert
Note.—Blanks indicate not applicable.
"There is no primary ambient air quajity standard for hydrocarbons; the value used in this report
is a guideline for meeting the primary ambient air quality standard for oxidants.
Not available.
-------
LOCATIONS AND DESCRIPTIONS
The process mechanism and the formation of atmospheric emis-
sions were described in Section 3. Based on that information,
the sources of emissions in a plant manufacturing acetone and
phenol from cumene are listed in Table 14 for the two process
technologies. Emissions for vents that are in closely related
processing areas have been combined, resulting in the emission
locations listed in Table 15. These emission locations apply
to both process technologies used.
Average Emission Factors, Percent Error Bounds, and
Methane Equivalent Emissions
Emission factors are defined to be grams of material emitted per
kilogram of product produced. That is, for this report, emis-
sion factors are given in g/kg phenol produced.
Wherever possible emission factors are an average of several
values for repeat measurements, and then for the two plants
sampled. When this occurs the error bound, 2-> , for the average,
x' of the emission factor is found as:
= s't
"
where s = standard derivation of the emission factors
t = value from statistical tables for "Student t"
distribution
n = number of items
The 95% confidence level and the degrees of freedom, f,
where
f = n - 1 (2)
used to determine the value of t. Table 16 presents the
<: values for the 95% confidence level and various degrees of
reedom. The 95% confidence level error bound is reported as
a ± Percent, ±%, determined by:
.%--£-
if the percentage determined is greater than 100, the minus value
reported only as 100 because negative emissions are physically
^Possible.
45
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TABLE 14. EMISSION SOURCES BY PROCESS TYPE AT A PLANT
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Process
technology
Emission source
Allied
Hercules
Cumene peroxidation.
Cumene hydroperoxide concentration vent.
Separation column vent.
Acetone concentration column vent.
Cumene column vent.
a-Methylstyrene column vent.
Refined a-methylstyrene column vent.
Phenol column vent.
Acetophenone column vent.
Cumene tank vent.
Acetone tank vent.
a-Methylstyrene tank vent.
Phenol tank vent.
Acetophenone tank vent.
Heavy ends tank vent.
Catalyst tank vent.
Acetone transport loading vent.
a-Methylstyrene transport loading vent.
Phenol transport loading vent.
Acetophenone transport loading vent.
Fugitive emissions.
Cumene peroxidation vent.
Cumene hydroperoxide wash vent.
Cumene hydroperoxide concentration vent.
Vent of cumene hydroperoxide cleavage and product
wash operations combined.
Separation column vent.
Acetone column vent.
Separation column vent.
Dewatering column vent.
Hydrogenation column vent.
Acetone tank vent.
a-Methylstyrene tank vent.
Phenol tank vent.
Heavy ends tank vent.
Catalyst tank vent.
Buffer tank vent.
Acetone transport loading vent.
a-Methylstyrene transport loading vent.
Phenol transport loading vent.
Fugitive emissions.
46
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TABLE 15. EMISSION SOURCES AT A REPRESENTATIVE PLANT
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Emission sources ~
Cumene peroxidation vent
Cleavage section vents, combined
Product purification vents, combined
Storage tank vents, combined
Product transport loading vents, combined
Fugitive emissions
TABLE 16. VARIATION OF t WITH DEGREES OF FREEDOM
FOR THE 95% CONFIDENCE LEVEL (40)
n fa
2
3
4
5
6
7
1
2
4
4
5
6
12.706
4.303
3.182
2.776
2.571
2.447
Assuming 1 mean.
The emission factors derived from the sampling program are the
average of the emission factors for two plants. To determine
the ± percent for the average emission factor, the root mean
square of the error bounds for the two plants, A and B, is
determined and changed to percent. The equation is:
±% = -?-= *- 100 (4)
where Y = .§11
t is determined by the 95% confidence level and degrees of
freedom.
The emission factor for total nonmethane hydrocarbons is not the
sum of emission factors for all organic materials except methane,
Jt is the sum of the methane equivalent emission factors for all
°rganic materials except methane. The methane equivalent emis-
factor is based on the material emission factor and the
47
-------
carbon content. It is the amount of methane that would be
emitted based on the carbon content of the material. A methane
equivalent emission factor, MEEF, is calculated as:
tase = 5T Cc Mm <5)
c
where E = material emission factor, g/kg phenol produced
Me = material molecular weight, g/g mole
CG = g moles of carbon that a gram mole of material
contains
Mm = molecular weight of methane, 16.04 g/g mole
Cumene Peroxidation Vent
The cumene feed is contacted with air in a reaction vessel to
peroxidize the cumene. Air is continuously introduced and re-
moved. The off-gas stream carries vaporized hydrocarbons and
some volatile trace elements. Cumene is recovered from the
spent gas for recycle by condensation.
The emission control equipment is the last piece of equipment
before the gas is emitted to the atmosphere. That is, any prior
equipment is process equipment, and the control of any materials
released to the atmosphere is performed by the last piece of
equipment prior to release. For example, in the Allied process
the emission control equipment is the carbon bed system, and in
the Hercules process it is the refrigerated condenser, unless
another piece of equipment is added on.
The average emission factors, determined by sampling at two
plants and through industry cooperation, for the inlet and outlet
of the control device are presented in Table 17. Only the inlet
stream was sampled for trace elements. The control efficiency
for cumene (which is 86% of the total nonmethane hydrocarbon
emission, both calculated as equivalent methane) is 88%.
The emission factor for total nonmethane hydrocarbons as methane
equivalents, based on carbon content, is 9.6 g/kg phenol produced
for uncontrolled emissions and 1.2 g/kg phenol produced for
controlled emissions. The average stack height is 17.1 m (56
ft) .
Cleavage Section Vents, Combined
The composite emission factors, Table 18, are determined by
aggregation of the emission factors available from sampling and
industry communication. These emission factors combine values
for the cumene hydroperoxide concentration vent (Allied process
technology) and the cumene hydroperoxide wash vent, the cumene
hydroperoxide concentration vent, and the combined cumene hydro-
peroxide cleavage and product wash vent (Hercules process
technology).
48
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TABLE 17. AVERAGE EMISSION FACTORS, UNCONTROLLED AND CONTROLLED,
FROM THE PEROXIDATION VENT AT A PLANT MANUFACTURING
ACETONE AND PHENOL FROM CUMENE, 1977
Emission factor, g/kg phenol produced,
±95% confidence level bound3'"
Material emitted
Criteria pollutants:0
Total nonmethane hydrocarbons
Chemical substances:
Acetaldehyde
Acetone
Acetophenone
Benzene6
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethylbenzene
Formaldehyde
2-Hydroxy-2-phenylpropane
a-Methylstyrene
Naphthalene
Propanal
Elements:
Arsenic
Barium
Calcium
Chlorine
Fluorine
Magnesium
Inlet to control
device
9.6
-------
TABLE 17 (continued)
— " Emission factor, g/kg phenol produced,
±95% confidence level bounda'b
Material emitted
Manganese
Phosphorus
Potassium
Sodium
Sulfur
Titanium
Inlet to control
device
•
0.000005 * J|jo%
+ 400%
<0.0002 _ 100%
+ 400%
<0.0006 _ 10Q%
<0.002 * JJJJ
+ 260%
<0.0006 _ 1QO%
. <°-00005 ! 3i4o2%
Outlet from control
device _
L h
1 h
1 h
1 h
1 h
1 _h
Note.—Values given as -less (<) are the amount in the sample only, becaus
the amount in the in the blank was either greater than the amount in the
sample, or not detected.
aThe percent error bound for the average emission factor is the root
mean square of the 95% confidence level error bounds at Plant A and
Plant B. It is calculated by
±% = J-^2 *=£— 100
and £ = S^
/n~~
Materials without the 95% confidence level error bound were tested once;
therefore, no error bound can be determined.
CNo particulates, nitrogen oxides (NOX), sulfur oxides (SOx)f or carbon
monoxide are emitted.
The total nonmethane hydrocarbon emission factor is the sum of the meth-
ane equivalent emission factors, based on carbon content, for the Cz
through C16 materials determined by gas chromatographic (GC) analysis.
The total nonmethane hydrocarbon emission factor is not the sum of emis*
sion factors for all nonmethane organic materials.
eThe benzene emission factors are not representative. A process upset a.o0g,
one of the two plants sampled resulted in a high level of benzene emiss
The GC/MS analysis does not distinguish among forms. It was assumed to
be the ct form.
gThe error bound determined from the accuracy for atomic absorption
sampled.
error bound determined from the accuracy for spark source mass
spectrometry (SSMS).
50
-------
TABLE 18. AVERAGE EMISSION FACTORS FOR THE CLEAVAGE SECTION
VENTS COMBINED AT A PLANT MANUFACTURING ACETONE
AND PHENOL FROM CUMENE, 1976 and 1977
Emission factor,
__ _ Material emitted _ g/kg phenol produced9
Criteria pollutants:
Total nonmethane hydrocarbons 0.17
Chemical substances:
Acetone 0.0000060
Acetophenone 0.0000044
Benzene d 0.000031
2-Butanone 0.0000018
2-Butenal 0.000000085
t-Butylbenzene 0.000023
Cumene 0 . 14
Ethylbenzene 0.0000050
Formaldehyde < 0.00000026
2-Hydroxy-2-phenylpropane 0 . 0000034
Isopentanal 0.00000085
Note. — Values given as less than are the amount in the
sample only, because the amount in the blank was either
greater than the amount in the sample or not detected.
Calculation of the 95% confidence level error bounds is
not possible because some materials were tested once and
because data obtained from industry and used to form the
average emission factors do not have error bounds.
No particulates, NOX/ SOX, or carbon monoxide are emitted.
c
The total nonmethane hydrocarbon emission factor is the
sum of the methane equivalent emission factors, based on
carbon content, for all nonmethane organic materials.
The benzene emission factors are not representative.
A process upset at one of the two plants sampled
resulted in a high level of benzene emissions.
, in tne cleavage section the cumene hydroperoxide stream
ls washed (Hercules process only) and concentrated to 80% or more
e ercues process ony an c
cumene hydroperoxide, the cumene removed is recycled, the cumene
JjYdroperoxide is cleaved to products using an acid catalyst, and
te catalyst is removed from
more detailed description.
catalyst is removed from the product stream. Section 3 has
a
total nonmethane hydrocarbon emission factor (as methane
ivalents based on carbon content) is 0.17 g/kg phenol
Produced. The average stack height is 12.8 m (42 ft).
51
-------
duct purification Vents, Combined
Pro
The average emission factors, Table 19, for the product puri-
fication vents combined were determined from industry-supplied
information. These emission factors combine the seven vents
(Allied process technology) and the five vents (Hercules process
technology) in this area. Briefly, the product purification
section separates and purifies products and recycle streams.
Section 3 describes this section in more detail.
TABLE 19. AVERAGE EMISSION FACTORS FOR THE PRODUCT PURIFICATION
SECTION VENTS COMBINED AT A PLANT MANUFACTURING
ACETONE AND PHENOL FROM CUMENE, 1976
Emission factor,
g/kg phenol produced,
Material emitted ±95% confidence level bound--
Criteria pollutants:
Total nonmethane hydrocarbons 1.2 ± 53%
Chemical substances: .
Acetaldehyde -j
Acetone -~.
Cumene -j
a-Methylstyrene -~.
Phenol -°
aThe ± percent error bound determined using the 95% confidence
level of the Student t distribution is found from:
±% =
No particulates, SOX, NOX, or carbon monoxide are emitted.
The total nonmethane hydrocarbon emission factor is determined
from the reported methane equivalent annual emissions.
Qualitatively identified.
The total nonmethane hydrocarbon emission factor (as methane
equivalents based on carbon content) is 1.2 g/kg phenol produced'
The average stack height is 26.5 m.
Storage Tank Vents, Combined
The storage tank requirements for a representative plant pro-
ducing acetone and phenol from cumene are listed in Table 6.
Appendix A details the calculation procedures for estimating
emission factors from tankage. The emission factor for the
52
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Phenol tanks in an average of the calculated value 0.06
9 phenol/kg phenol produced and an estimate of 0.012 g phenol/
^9 phenol produced supplied by H. Walker, Monsanto Chemical
Intermediates Co., Alvin, Texas, 6 September 1978. H. Walker's
Phenol storage tank emission estimate was determined using the
Procedure described in Appendix A. However, based upon plant
exPerience, he used other data for some of the input variables
such as storage temperature, vapor pressure, etc. The two esti-
mates were determined using the same procedure but different input
variables; therefore, the estimates were averaged. The storage
tank vent emission factors are listed in Table 20. The total
nonmethane hydrocarbon emission factor for all storage tanks is
0.14 g nonmethane hydrocarbons/kg phenol produced. (The emission
heights are discussed and listed later in Table 25.)
Product Transport Loading Vents, Combined
The emissions from product transport loading are caused by dis-
placement of hydrocarbon-containing vapors in the compartment
being filled. One source reports emissions of 0.061 g acetone/
K9 Phenol produced from the acetone loading area and 0.20 g
Phenol/kg phenol produced from the phenol loading and shipping
area. (Personal communication with Vernon C. Parker, Air Quality
, Louisiana State Division of Health, New Orleans,
iana, 10 March 1976.) Another source estimates emissions
the phenol loading area as 0.010 g phenol/kg phenol produced.
(Personal communication with H. Walker, Monsanto Chemical Inter-
pellates, Alvin, Texas, 6 September 1978.) H. Walker's transport
•Loading estimate is based on the working loss calculation from
Appendix A for filling of based transport means such as barges.
plant experience provided data for the input variables. The two
estimates were averaged. Table 21 lists the nonmethane hydro-
carbon emission factor which is 0.17 g hydrocarbons/kg phenol
Produced, the acetone emission factor, and the phenol emission
actor. The emission height was assumed to be 9.1 m.
U9itive emissions occur from pressure relief valves, pump seals,
compressor seals, pipeline valves and flanges, equipment purges,
Process drains, wastewater separators, and laboratory analysis
sampling. An estimate of the total nonmethane hydrocarbons (as
methane equivalents) from pumps and sewers has been reported to
0.022 g/kg phenol produced in 1975 (personal communication
Vernon C. Parker, 10 March 1976) . Pump and sewer caused
ive emissions are not the total fugitive emissions, nor are
necessarily the most significant.
53
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TABLE 20. CALCULATED EMISSION FACTORS FOR STORAGE
TANK VENTS AT A PLANT MANUFACTURING
ACETONE AND PHENOL FROM CUMENE
Emission factor. qAq phenol produced
Tanks"
Heavy
Material emitted Acetone Acetophenone Cumane ends a-Methylstyrene Phenol Total
Criteria pollutants:''
Total nonmethane hydrocarbonsc 0.050 5.9 x 10~s 0.034 0.011 0.0024 0.041 0.14
Chemical substances:
Acetone 0.060 0.060
Acetophenone 5.5 x 10~s 5.5 x 10~5
Cumene 0.026 0.026
a-Methylstyrene 0.0020 0.0020
Phenol 0.0116 0.040^ 0.051
a " ~~~ ' ~~~~' '
There are 4 acetone, 1 acetophenone, 3 cumene, 1 heavy ends, 1 o-methylstyrene and 4 phenol tanks. Emis-
sion factors are for the appropriate number of tanks.
b
No particulate, NO*, SO*, or carbon monoxide are emitted.
The total nonmethane hydrocarbon emission factor is the sum of the methane equivalent emission factors,
based on carbon content, for all organic materials except methane.
d
Blanks indicate no emissions.
Actual content of emission unknown. It was assumed to be phenol.
The emission factor used is the average of a calculated value and an estimate supplied by H. Walker,
Monsanto Chemical Intermediates Co., Alvin, Texas, 6 September 1976.
TABLE 21. REPORTED EMISSION FACTORS FOR PRODUCT TRANSPORT
LOADING VENTS3 COMBINED AT A PLANT MANUFACTURING
ACETONE AND PHENOL FROM CUMENE, 1975 AND 1978b
Emission factor,
Material emitted g/kg phenol produced
Criteria pollutants:0
Total nonmethane hydrocarbons^ 0.17
Chemical substances:
Acetone 0 . 074
Phenol6 0.11
Loading of 2 to 5 product types.
Personal communication with Vernon C. Parker, Air
Quality Section, Louisiana State Division of Health,
New Orleans, Louisiana, 10 March 1976, and H. Walker,
Monsanto Chemical Intermediates Co., Alvin, Texas,
6 September 1978.
CNo particulate, NOX, SOX, or carbon monoxide are emitted.
The total nonmethane hydrocarbon emission factor is the
sum of the methane equivalent (based on carbon content)
emission factors of the nonmethane organic materials.
Average.
54
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DEFINITION OF A REPRESENTATIVE SOURCE
A representative source was defined for plants manufacturing
acetone and phenol from cumene to determine source severities
for the emission points and compounds emitted. The data used
to determine the representative source are presented in Table 22
(2, 3, 41, 42, and personal communication with L. B. Evans,
9 February 1976).
The representative source is a plant utilizing either technology
licensed in the United States, and it has annual capacities of
• 136 x 103 metric tons of phenol
• 83 x 103 metric tons of acetone
• 2.9 x 103 metric tons of ct-methylstyrene
• 150 metric tons of acetophenone
A capacity weighted mean county population of 1,333 persons/km2
was used to calculate the affected population. The population is,
of course, not distributed uniformly throughout the county; there-
fore, in the plant vicinity, the population density may be lower
or higher than the county average. The national average wind
speed of 4.5 m/s is used as the wind speed for the representa-
tive source (42).
The representative source is utilized at 80% of capacity (0.8
stream-day factor), which reflects the industry-wide utilization
of phenol from cumene plants (43).
The representative source utilizes the emissions control tech-
nologies listed in Table 23.
SOURCE SEVERITY
To assess the environmental impact of atmospheric emissions from
plants manufacturing acetone and phenol from cumene, the source
severity, S, for each material from each emission point was
estimated. Source severity is defined as the pollutant concen-
tration to which the population may be exposed divided by an
(41) Chemical Profile, a-Methylstyrene. Chemical Marketing
Reporter, 212(16):9, 1977.
(42) The World Almanac & Book of Facts, 1976; G. E. Delury,
ed. Newspaper Enterprise Association, Inc., New York,
New York, 1976. 984 pp.
(43) Capacity Use in Basic Chemicals Is Very Low. Chemical and
Engineering News, 55(41):15-17, 1977.
55
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TABLE 22. PLANT PARAMETERS USED IN DETERMINING THE REPRESENTATIVE SOURCE FOR A PLANT
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Cow-any and location"
Allied Chemical Corp.
Frank ford. Pa
Clark Oil and
Refining Corp.
Blue Island, IL
Dow Chemical Company
Oyster Creek, TX
Georgia-Pacific Corp.
P laquemine , LA
Getty Oil Company
El Dorado, KS
Monsanto Company
Chocolate Bayou, TX
Shall Chemical Co.
De«r Park. TX
Ul
CTl S.O. of California
Richmond, CA
onion Carbide Corp.
Bound Brook, NJ
U.S. Steel Corp.
Haverhill, OH
Mean or parameter used
Percent error bounds
Phenol capacity,
Process type 103 metric tons/yr
Allied
Allied
Hercules
Hercules
Allied
Hercules
Hercules
Hercules
Allied
Hercules
Either
_f
272
39
181
120
43
227
227
25
77
147
136
±46%
Acetophenone
Acetone capacity, capacity,
Ip3 metric tons/yr metric tons/yr
150
24 910
127 0
77 0
26 181
136 0
136 0
15 0
49
91 0
Representative plant
83 ISO
±44%
Population Average
o-Methylstyrene density, wind
capacity ,b persons/km^ speed
103 metric tons/vr County (42) •/•
11 Philadelphia 5,836
2.3 Cook 2,224
0 Brazoria 29
4.5 Iberville 19 -6
0.91 Butler 10
0 Brazoria 29
0 Harris 390 -"
0 Contra Coeta 292
3.6 Scmmerset 249
6.8 Scioto 49 -6
2.9 - 1,3339 4.S6
f f f
±89% - -
"Puerto Rico is not included in the area this study covers.
Capacities are variable
""Population density is
determined on a county basis. The population is, of course, not distributed uniformly throughout the county, therefore.
in the plant vicinity, the population density may be lower or higher than the county average.
Amount unknown.
eThe national average wind speed of 4.5 m/s is used.
Not applicable.
9The population density average is a capacity weighted nean county population density.
h .j.i, where t is aetermi.ned by the 95% confidence level of the Student t distribution and
The i percent error bound was found using: ±% _ /»^.\i.
the degrees ot freedom. V"~j *
- 100
-------
TABLE 23.
EMISSION CONTROL TECHNOLOGIES
USED AT REPRESENTATIVE PLANT
Emission source
Emission control technology
Cumene peroxidation vent
Cleavage section vents,
combined
Product purification vents,
combined
Storage tank vents:
Acetone
Acetophenone
Cumene
Heavy ends
a-Methylstyrene
Phenol
Product transport loading
vents, combined
Fugitive
Adsorption or condensation
Condensation
Condensation
Floating roof
None
Floating roof
Floating roof
None
None
Unknown
Not applicable
acceptable concentration." The exposure concentration is the
time-averaged ground level concentration as determined
Gaussian plume dispersion methodology. The "acceptable con-
is that pollutant concentration at which an incipient
c e health reaction is assumed to occur. The "acceptable
ncentration" is defined as the corresponding primary ambient
^r quality standard for criteria pollutants and as a surrogate
standard for chemical substances determined by
g thresnold limit values (TLVs) using an appropriate
factor. (See Appendix I for the complete derivation.)
°urce severity, S, is calculated as:
S =
vmax
(6)
ere Xn\ax is the maximum time-averaged ground level concentra-
p °n °f each pollutant emitted from a representative plant, and
is defined as the primary ambient air quality standard for
Po1 pollutants (particulate, SOx/ NOx/ CO, and hydrocarbons3)
r noncriteria pollutants, F is defined as:
F = TLV • 8/24 • 0.01, g/m3 =
TLV
300
(7)
ale c°nversion factor, G = 1/300, converts the TLV to an "equiv-
ent" primary ambient air quality standard. The factor 8/24
There
is no primary ambient air quality standard for hydrocar-
u •»•= utJ primary amoient air qudiity stcuiuaiu J-V.L iiyu.Luua.L-
t,ns; the value used in this report is a guideline for meeting
e Primary ambient air quality standard for oxidants.
57
-------
adiusts the TLV from an 8-hr work day to continuous (24-hr)
exposure. The 1/100 factor is designed to account for the fact
that the "general population constitutes a higher risk group than
healthy workers.
Thus, the source severity represents the ratio of the exposure
concentration to the acceptable concentration given pollutant.
The maximum ground-level concentration Xmax» is calculated
according to Gaussian plume dispersion theory:
x = 2 Q <8)
max TTH'eu
where Q = mass emission rate, g/s
rr_ = 3.14
u = average wind speed, m/s
H = effective emission height, m
e = 2.72
The effective emission height, H, is equal to the physical stack
height, h1, plus the amount of plume rise, AH. Plume rise in
plants producing acetone and phenol from cumene represents less
then 50% of the physical stack height as determined in Appendix
L. See Appendix L for a determination of plume rise and its
subsequent effect on the source severity.
The mass emission rate, Q in g/s, is calculated as:
Q = (E) (Cap) {9)
where E = emission factor, g/kg phenol produced
Cap = representative source phenol capacity, kg/yr
U = utilization
kj = conversion factor, yr/s
Equation 8 yields a value for a short-term averaging time
which the Gaussian plume dispersion equation is valid. The sho
term averaging time was found to be 3 min in a study of publislV
data on lateral and vertical diffusion. For a continuously ern^on
ting source, the time-averaged maximum ground level concentrati
for time intervals between 3 min and 24 hr can be estimated fr°"
the relation:
x = x
Amax ^
O . 1 7
where to = short-term averaging time (3 min)
ti = averaging time
58
-------
The average emission factors for a plant manufacturing acetone
and phenol from cumene were discussed previously and are summa-
rized in Table 24. The average emission heights are presented
m Table 25.
Table 26 lists the maximum time-averaged ground level concentra-
tion for each emission and each emission point in a representa-
tive plant.
Source severities for emissions which have TLVs or primary am-
bient air quality standards are listed by emission and emission
Point in Table 27 for a representative plant.
The largest source severity value listed in Table 27 is 3.5 for
total nonmethane hydrocarbon emissions from the cumene perodixa-
tion vent.
The emissions from two emission points, the cumene peroxidation
vent and the product purification vents, combined, represent 86%
°f the average emissions from a plant manufacturing acetone and
Phenol from cumene. Simulated source severity distributions,
using methodology from Reference 44, for the total nonmethane
hydrocarbon emissions (based on carbon content for methane equiv-
alent) from those two points are presented in Figures 15 and 16.
The simulated source severity distributions for the materials
emitted from the cumene peroxidation vent are presented in
Appendix j. The ordinate of the graph is interpreted as the per-
centage of plants manufacturing acetone and phenol from cumene
having source severities less than the source severity value on
the abscissa.
INDUSTRY CONTRIBUTION TO TOTAL ATMOSPHERIC EMISSIONS
Hydrocarbons (organic materials were classified as hydrocarbons)
are the only criteria pollutant emitted by the manufacture of
acetone and phenol from cumene, excluding emissions from boilers,
which are assessed in a separate study.
Tne contribution from the manufacture of acetone and phenol from
cumene to statewide and nationwide emissions was measured by the
ratio of mass emissions from this source to total emissions from
stationary sources statewide and nationwide.
Eimutis, E. C., B. J. Holmes, and L. B. Mote. Source
Assessment: Severity of Stationary Air Pollution Sources
—A Simulation Approach. EPA-600/2-76-032e, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, July 1976. 119 pp.
59
-------
TABLE 24.
AVERAGE EMISSION FACTORS FOR PHENOL AND ACETONE
MANUFACTURE FROM CUMENE BY EMISSION POINT, 1977
Material emitted
Emission factor, g/kg of phenol produced
Cleavage Product
Cumene section purification
peroxidation vents, vents,
vent* combined"»"•c combined^ »e
Criteria pollutants
Total nonme thane
hydrocarbons^
Chemical substances:
Ace t aldehyde
Acetone
Acetophenone
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethyl.benzene
Formaldehyde
2-Hydroxy-2-phenyl-
propane
Isopentanal
a-Methylstyrene
Naphthalene
Phenol
Propanal
1.8 0.17 1.2 ± 53%9
<0.0021
0.60
<0.
0.20
0.050
<0.0055
<0.
0.86
0.
0.
0.0010
<0.
<0.
<0.
<0.0011
+ 320%9 _h
- 100% 0.0000060 -h
00086 0.0000044
t 9.4%9>1 0.0000311
- 100% 0.0000018
g
- 100% 0.000000085
0022 0.000023
+ 170%g n .. h
- 100% u<±*
00005
00042 O.OOOOOOSO
- 100% <0. 00000026
0009 0.0000034
0.00000085
0001j -h
0001
-h
• : "S%9
Note.—See footnotes at bottom of page 62.
(continued)
60
-------
.Material emitted
TABLE 24 (continued)
Acetone
tanks
Emission factor, g/kg of phenol produced
Storage tank vents^**
a-Methyl-
styrene
tank
Acetophe-
none tank
Cumene
tanks
Heavy
ends
tank
Phenol
tanks
m
Criteria pollutants
Total nonmethane
hydrocarbonsf
Chemical substances:
Acetaldehyde
Acetone
Acetophenone
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethylbenzene
formaldehyde
2-Hydroxy-2-phenyl-
propane
Isopentanal
a-Methylstyrene
Naphthalene
Phenol
Propanal
0.050
0.060
0.000059
0.034 0.011 0.0024 0.041
0.000055
0.028
0.0020
0.011
n
°te
-------
TABLE 24 (continued)
Emission factor, g/kg of phenol produce<
Product transport
loading vents. Fugitive
Material emitted combined0 »P
Criteria pollutants
Total nonmethane
hydrocarbons^ 0.17
Chemical substances :
Acetaldehyde
Acetone 0.074
Acetophenone
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethylbenzene
Formaldehyde
2- Hydroxy-2-pheny 1-
propane
Isopentanal
a-Methylstyrene
Naphthalene
Phenol 0.1 lr
Propanal
emissions1! Totals __
0.022 3.5
<0.0021
0.73
0.0087
09fl
• if \J
0.050
<0.0055
<0.0022
1.0
0.000050
0.00042
0.0010
<0.0009
0.00000085
<0.0021
<0.0001
0.16
<0.0011
Note.—Blanks indicate no emissions for the sampled points and no
emissions reported for the other sources. Values given as less
than are the amount in the sample because the blank had either a
greater amount than the sample or the material was not detected.
aSampling performed.
Emissions are from 1 to 4 vents.
cData used are from 1976 and 1977.
Emissions are from 5 to 7 vents.
€Data used are from industry sources for 1976.
Emission factors for total nonmethane hydrocarbons do not equal
the sum of all emission factors for all organic materials except
methane. For the sampled emission points, to determine the
total nonmethane hydrocarbon emission factor the methane equiv-
alent emission factors, based on the carbon content, for the
GC determinations of ca through Ci« are calculated and summed.
For reported emissions, the methane equivalent emission factors
based on carbon content for all organic nonmethane materials
are calculated and summed.
(continued)
62
-------
TABLE 24 (continued)
gThe percent error bounds are calculated using the Student t dis-
tribution to obtain:
±% = /Sl± J I 100
Qualitatively identified.
1The benzene emission factors are not representative.
A process upset at one of the two plants sampled resulted
in a high level of benzene emissions.
-'Assumed to be the a form. The GC/MS analysis does not distin-
guish among the forms.
There were assumed to be 4 acetone, 1 acetophenone, 3 cumene,
1 heavy ends, 1 a-methylstyrene, and 4 phenol tanks.
Emission factors are calculated.
The emission factor used is the average of a calculated value
and an estimate supplied by H. Walker, Monsanto Chemical
Intermediates Co., Alvin, Texas, 6 September 1978.
"Emissions assumed to be phenol.
Loading of 2 to 5 product types.
Data used are from industry sources for 1975 and 1978.
™Date used are from industry sources for 1975. The fugitive emissions
estimate includes those from pumps and sewers only. The other sources
of fugitive emissions are not included in this estimate.
The emission factor is an average of two estimates.
TABLE 25. EMISSION HEIGHTS AT A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE3
Emission
Emission point height, m
Cumene peroxidation vent 17.1
Cleavage vents, combined 12.8
Product purification vents,
combined 26.5
Storage tank vents:
Acetone* 15.2
Acetophenone 4.6
Cumene 15.2
Heavy ends 9.1
a-Methylstyrene 6.1
Phenol 15.2
Product transport loading
vents, combined^ 9.1
Fugitive emissions9 4.6
Plume rise represents less than 50% of
the physical stack as determined in
Appendix L. The physical stack height
is used as the effective emission height.
See Appendix L for determinating the plume
rise correction and its subsequent effect
cfn source severity.
Estimated.
63
-------
TABLE 26.
MAXIMUM TIME-AVERAGED GROUND LEVEL CONCENTRATIONS OF
ATMOSPHERIC EMISSIONS FROM A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE, 1977
xmax' 9/m3
Material emitted
Cleavage
Cumene section
peroxidation vents,
venta combined*»'
Product
purification
vents,
combinedd.e
Criteria pollutants
Total nonmethane
hydrocarbonsf
Chemical substances:
Acetaldehyde
Acetone
Acetophenone
Benzene
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
DimethyIstyrene
Ethylbenzene
Formaldehyde
2-Hydroxy-2-phenyl-
propane
Isopentanal
a-MethyIstyrene
Naphthalene
Phenol
Propanal
5.5 x 10-" 9.3 x ID"5
<4.5 x 10-7
7.2 x ID'5 1.3 x 10~9
<1.8 x 10~6 1.7 x ID"9
4.3 x 10~5h 1.2 x 10-8h
1.1 x 10"5 6.9 x 10~10
<1.2 x 10-6 3.3 x 10-11
<4.7 x 10-7 8.8 x ID'9
1.8 x 10-1* 5.4 x lO-5
1.1 x 10~8
9.0 x 10-8 1.9 x 10"10
2.1 x ID'7 <1.0 x 10~10
<1.9 x 10-7
<2.1 x lO-8
<2.1 x lO-8
<2.4 x 10~7
1.3 x 10-9
3.3 x 10-10
Note.—See footnotes at bottom of page 66.
1.5 x 10-
-9
_g
_9
_9
(continued)
64
-------
TABLE 26 (continued)
Storage tank vents J , k
Heavy a -Methyl-
Acetone Acetophe- Cumene ends styrene Phenol
emitted tanks none tank tanks tank tank tanks
Criteria pollutants
Total nonmethane
Hydrocarbons f 1.
9 x 1(T5 2.5 x 10~7 1.3 x 10~5 1.2 x KT5 5.8 x 10~6 1.6 x 10~5
substances:
Acetaldehyde
Acetone 9>1 x 10-6
Acetophenone 1.7 x 10~7
Benzene
2-Butanone
2~Butenal
*-Butylbenzene
CUmene 7.6 x 10-6
Dimethylatyrene
Formaldehyde
2-Hydroxy-2-phenyl-
Propane
laopentanal
o-Methylstyrene 3.4 x 10" 6
Naphthalene
Pheno1 8.3 x 10-6m 1.1 x 10-5
e> See footnotes at bottom of page '66.
(continued)
65
-------
TABLE 26 (continued)
Product transport Fugitive
Material emitted loading facility vents"'0 emissionsP
Criteria pollutants
Total nonraethane
hydrocarbonsf 1.8 x lO"1* 9.3 x 10~5
Chemical substances:
Acetaldehyde
Acetone 3-1 x 1
-------
TABLE 27.
SOURCE SEVERITIES OF ATMOSPHERIC EMISSIONS
FROM A REPRESENTATIVE SOURCE MANUFACTURING
ACETONE AND PHENOL FROM CUMENE, 1977
Source severity
Material emitted
Cuihene
peroxidation
„ vent3
Cleavage
section
vents,
combined3 •"»c
Product
purification
vents.
combined*" »e
Criteria pollutants
Total nonmethane
hydrocarbons^
Chemical substances:"
Acetaldehyde
Acetone
Benzene
2-Butanone
Cumene
Ethylbenzene
Formaldehyde
a-Methylstyrene
Naphthalene
Phenol
Note.See footnotes at bottom of page 69.
3.5
<0.00076
0.0090
0.431
0.0055
0.23
0.000063
0.022
1.4 x 10"sJ
<0.00013
0.58
1.6 x 10-7
1.2 x 10~sl
3.5 x 10"7
0.066
1.3 x 10~7
<1.0 x ID'5
0.96
_h
h
_h
_h
(continued)
67
-------
TABLE 27 (continued)
Source severity _
Storage tank
Material emitted
Acetone
tanks
Acetophe-
none tank
Cumene
tanks
ventsK
Heavy
ends
tank
a-Methyl
styrene
tank
Phenol
Criteria pollutants
Total nonmethane
hydrocarbons^ 0.12 0.0016
Chemical substances:^
Acetaldehyde
Acetone 0.0011
Benzene
2-Butanone
Cumene
Ethylbenzene
Formaldehyde
ct-Methylstyrene
Naphthalene
Phenol
Note.—See footnotes at bottom of page 69.
0.082 0.074
0.036
0.10
0.0094
0.0021
0.13
n
(continued)
68
-------
TABLE 27 (continued)
Source severity
Product transportFugitive
Material emitted loading facility vents,°'p emissions*3
Criteria pollutants
Total nonmethane
hydrocarbons' 1.2 0.58
Chemical substances:9
Acetaldehyde
Acetone 0.0039
Benzene
: 2-Butanone
Cumene
Ethylbenzene
Formaldehyde
oe-Methylstyrene
Naphthalene
Phenol 1.3r
Note.—Blanks indicate no emissions for sampled points and no
emissions reported for other sources.
Sampling performed.
Emissions are from 1 to 4 vents.
c
Data used are from industry sources for 1976 and 1977.
Emissions are from 5 to 7 vents.
Data used are from industry sources for 1976.
Source severity for total nonmethane organic materials will not
equal the source severity for total nonmethane hydrocarbons.
Source severities for the nonmethane organic materials are based
on the toxicity of the chemicals. The source severity for total
nonmethane hydrocarbons is based on the guideline for meeting
the primary ambient air quality standard for photochemical
bxidants.
g
Only substances which have a TLV are listed.
Qualitatively identified.
The benzene emission factors are not representative. A process
upset at one of the two plants sampled resulted in a high level of
benzene emissions.
Assumed to be the a form. The GC/MS analysis does not distin-
quish among the forms.
j£
There were assumed to be 4 acetone, 1 acetophenone, 3 cumene,
1 heavy ends, 1 a-methylstyrene, and 4 phenol tanks.
Emission factors are calculated.
The emission factor used is the average of a calculated value and
an estimate supplied by H. Walker, Monsanto Chemical Intermediates
Co., Alvin, Texas, 6 September 1978.
Emissions assumed to be phenol.
Loading of 2 to 5 product types.
Data used are from industry sources for 1975 and 1978.
Data used are from industry sources for 1975. The fugitive emissions
are from pumps and sewers only. The other sources of fugitive
emissions are not included in the estimate.
The emission factor used is an average of two estimates.
69
-------
SAMPLE SIZE = 5000
MIN. VflLUE = 0-21
MflX. VflLUE = 13-49
MEflN = 2-84
STD. DEV. = 2.05
. - in? TTuTTiins A-W
TOTRL NONHETHRNE HYDROCflRBONS SEVERITY
1^.09
Figure 15.
Simulated source severity distribution for total nonmethane
hydrocarbons emitted from the cumene peroxidation vent.
-------
SflHPLE SIZE = 5000
MIN. VflLUE =0.11
MflX. VflLUE =4.12
MERN = 0.92
SID. DEV. = 0-52
tf-75 o-90 I'.oe I'.zo r-ii r-io
TOTflL NONtlETHRNE HYDROCflRBONS. COMBINED
t'.flO
2.to
Figure 16.
Simulated source severity distribution for total nonmethane
hydrocarbons emitted from the product purification vents, combined
-------
The mass emissions of hydrocarbons resulting from acetone and
phenol manufacture from cumene were calculated by multiplying the
emission factor by the total production in each state and in the
nation. The total production was calculated by multiplying the
utilization factor by the total capacity in each state and in the
nation. The total mass emissions from all stationary sources fo*
each state and nationwide have been reported (45) . The estimated
contribution to total emissions of hydrocarbons (organic material*
are classified as hydrocarbons) by the manufacture of acetone and
phenol from cumene can be calculated using:
EF • U • Cap •
%C = — i - - § - • 100
where %C = percent estimated contribution
EF_ = total emission factor for nonmethane hydrocarbons/
3 . 5 g/kg phenol produced
Cap = total capacity on a state or national basis/
s metric tons/yr
ku = conversion factor, 10~3 kg/g
TE = total emissions of hydrocarbons from stationary
source on a state or national basis,
metric tons/yr
The mass emissions in each state and in the nation, the mass
emissions from acetone and phenol production, and the percent
contributions are shown in Table 28.
AFFECTED POPULATION
A measure of the population exposed to a high contaminant con-
centration due to a representative source producing acetone and
phenol from cumene can be obtained as follows.
The value of the time-averaged ground level concentration, X, as
a function of the downwind dispersion distance from the source
of emission release, x, can be determined from the equation (46)
(45) Eimutis, E. C., and R. P. Quill. Source Assessment:
State-by-State Listing of Criteria Pollutant Emissions.
EPA-600/2-77-107b, U.S. Environmental Protection Agency.
Research Triangle Park, North Carolina, July 1977. 138 pP'
(46) Eimutis, E. C., and M. G. Konicek. Derivations of Con-
tinuous Functions for the Lateral and Vertical Atmospheric
Dispersion Coefficients. Atmospheric Environment,
6(11):859-863, 1972.
72
-------
TABLE 28.
ESTIMATED CONTRIBUTION TO TOTAL EMISSIONS OF
HYDROCARBONS BY MANUFACTURE OF ACETONE AND
PHENOL FROM CUMENE, 1977
Location3
Nationwide
California
Illinois
Kansas
Louisiana
New Jersey
Ohio
Pennsylvania
Texas
1977
Total emissions
of hydrocarbons , b
10 6 metric tons/yr
16.58
1.423
0.8286
0.2397
1.008
0.6341
0.8387
0.9022
2.184
1977
Emissions from
manufacture of
acetone and
phenol from cumene,
metric tons/yr
3,800
70
110
120
340
220
410
760
1,800
Percent
of
total
0.023
0.0049
0.013
0.050
0.034
0.034
0.049
0.084
0.081
Does not include Puerto Rico.
Only hydrocarbons (organic materials were classified as hydro-
carbons) are emitted by the manufacture of acetone and phenol
from cumene, exclusive of boilers.
wher<
Th
X (x) =
- exp
ozux
Q = mass emission rate, g/s
H = effective emission height, m
x = downwind dispersion distance from the source of
_ emission release, m
u = average wind speed (4.5 m/s)
(12)
a =
= standard deviation of vertical dispersion, m
Phv ?ffective emission height, H, is equal to the sum of the
-Cal stack height plus the amount of plume rise, AH. The
stack height has been used since plume rise amounts to
of the physical stack height. See Appendix L for the
ermination of plume rise and its impact on dispersion
The
values of x for which
(13)
then determined by iteration,
73
-------
For atmospheric stability, class C (neutral conditions) , oz is
given by (46) :
o = 0.113 x°-911 {14)
A = Hx22 - Xl2), km2 <15)
z
The affected area is then computed as:
2
where XL and x2 are the two roots of Equation 12.
The affected area is computed based on the area outside the plan
boundaries. The representative plant area is 2.9 km2, thus in
terms of the radial distance, ^ must be at least 0.96 km. i"
value has been used to compute all affected areas and popular
If x2 is not greater than 0.96 km, then all the affected area ±
inside plant boundaries and the affected area and population
reported as zero.
The capacity-weighted mean county population density, Dp, is
calculated as follows:
persons/km2
where C. = phenol production capacity of plant i, metric tons/Y
Dp = county population density for plant i, obtained
i from Reference 41, persons/km2
Population density is determined on .a county basis. The popu
tion is, of course, not distributed uniformly throughout the
county; therefore, in the plant vicinity, the population densi
may be lower or higher than the county average.
The product of A x Dp is designated the "affected population.
The affected population was computed for each compound and ea
emission point for which the source severity, S, exceeds 9*j"cate
The results are presented in Table 29, where blank areas inai
the material shown is not discharged from the emission points
listed; hence there is no affected population. Zeros indica^v1at
that the material is discharged from the emission point but t ^
the resulting ambient levels have source severities less than
equal to 0.1, or that the affected area is entirely within tn
plant boundaries.
The total number of persons affected by a representative sou
manufacturing acetone and phenol from cumene is 12,600. This
74
-------
TABLE 29.
-j
Ul
ESTIMATED AFFECTED POPULATION FROM MANUFACTURE OF ACETONE AND
PHENOL FROM CUMENE AT REPRESENTATIVE SOURCE, 1977
Affected population, ' >C persons
H
Component
Total nonmethane hydrocarbons
Acetaldehyde
Acetone
Benzene
2-Butanone
Cumene
Ethylbenzene
Formaldehyde
a-Methylstyrene
Naphthalene
Phenol
a
Cumene
peroxidation
vent
8,300
0
0
0
0
0
0
0
0
0
Cleavage
section
vents,
combined
0
0
0
0
0
0
0
Product
purification
vents , *
combined
4,300
-i
J
J
J
Storage
tank
vents,
combined"
0
o
o
0
Product
transport
loading vents,
• combined"
0
Fugitive
emissions
~J
•!
V
•!
*!
•?
-j
_
Blank areas indicate that the material shown is not discharged from the emission point listed; zeros
indicate that ambient levels resulting from discharged material produce source severiteries less than or
equal to 0.1.
b
The affected population is calculated for the affected area outside of the representative plant area.
which is 2.9 knr.
The capacity weighted mean county population density is used to determine affected population. The popu-
lation is, of course, not distributed uniformly throughout the county; therefore, in the plant vicinity
the population density may be lower or higher than the county average.
Only materials which have TLV's or hazard factors are listed.
e
Combination of 1 to 3 vents.
Combination of 5 to 7 vents.
g
There are 4 acetone, 1 acetophenone, 3 cumene, 1 heavy ends, 1 a-methylstyrene, and 4 phenol tanks.
Affected population has been summed for all tanks.
Loading of 2 to 5 product types.
Emitted from this emission point, but no quantitative information is available.
Unknown.
-------
affected population represents the number of persons exposed to
nonmethane hydrocarbons which exceed the one-tenth of the primary
ambient air quality standard (guideline) for hydrocarbons of
160 x 10~6 g/m3 (see Appendix K).
G. GROWTH FACTOR
In 1975, 703 x 103 metric tons of phenol were produced from
cumene in the United States. As discussed in Section 6, produc-
tion of phenol from cumene in 1980 is expected to reach ^
1,100 x 103 metric tons. Assuming that the same level of contr
technology exists in 1980 as existed in 1975, the emissions
the cumene peroxidation phenol industry will increase by 50%
that period; i.e.,
Emissions in 1980 _ 1,100 x 103 _ . _,.
Emissions in 1975 ~ 703 x 103 ~
76
-------
SECTION 5
CONTROL TECHNOLOGY
ir emissions from the manufacture of acetone and phenol from
umene consist of hydrocarbons. Existing emission control tech-
oiogies for the industry are described in this section. These
ontrol methods include condensation, absorption, adsorption,
ioating roof tanks, and incineration. Future considerations in
Missions control technology are also discussed in this section.
^STALLED EMISSIONS CONTROL TECHNOLOGY
fission control technologies now being used in plants manufac-
ing acetone and phenol from cumene are listed in Table 30.
table lists the eight companies for which information was
NO information was available on the emission control
used by Shell Chemical Co., Deep Park, Texas, and Union
CorP-/ Bound Brook, New Jersey. There are a variety of
control methods used for each emission source. Table 31
cs the number of plants reporting the use of each emission
°ntrol method for each emission source.
* Adsorption is the most commonly used method to control emis-
sions from the cumene peroxidation vent. Condensation,
absorption, and incineration are also used, however.
' Emissions in the cleavage section are most often controlled
condensation. Absorption and incineration are also used.
Emissions in the product purification section are controlled
condensation, adsorption, absorption, and incineration.
Floating roofs are used to control emissions from tanks ,
Particularly acetone and cumene storage tanks. Condensation,
sealed dome roofs, and conservation vents are also used for
this purpose, but not as commonly as floating roofs.
* Product transport loading emissions are controlled by
absorption or vapor recovery. Not all plants control this
emission source.
" The scope of fugitive emissions and control methods are
under study by EPA.
77
-------
TABLE 30.
INSTALLED EMISSIONS CONTROL TECHNOLOGY AT PLANTS
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Installed emission controls by company and location
Emission source
Allied Chemical Corp.,
FranXford, PA"
Clark Oil and Refining Corp.,
Blue Island, ILC
oo
Cumene peroxidation vent
Cleavage section vents:
Cumene hydroperoxide wash vent
Cumene hydroperoxide concentration vent
Cumene hydroperoxide cleavage vent
Product wash vent
Product purification vents, combined
Storage tank vents
Product transport loading vents,
combined
Fugitive emissions
Wastewater
Carbon adsorbers.
Not applicable.
2 steam jets vented to brine cooled
condenser.
Not applicable.
Not applicable.
0-3 Steam Jet Condensers in series
with final condenser vented to
atmosphere. One steam jet con-
denser vented to packed water
scrubber.
2 acetone floating roof, 2 cumene
floating roof. Miscellaneous addi-
tional to atmosphere.
Vapor recovery system.
Preventive maintenance program.
Contaminated waste discharged to city
treatment plant. Some streams dis-
charged directly to waterway under
NPDES permit.
Carbon adsorbers.
Not applicable.
To incinerator
Not applicable.
Not applicable.
All to incinerator except two
vents to carbon adsorbers.
2 acetone: floating roofs.
1 AMS: pressure vacuum vents
1 cumene: pressure vacuum vents.
2 phenol: none.
1 acetone: none.
1 AMS: none.
No control.
Not known.
Nastewater discharged to Metro-
politan Sanitary District of
Greater Chicago.
aThis study does not include Puerto Rico.
Personal communication with M. W. Hunt, 10 April 1978.
"•"Personal cora&unication with R. H. Brugginfc, 5 May 19"78.
(continued)
-------
TABLE 30 (continued)
Installed emission controls by company and location'
Emission source
Cumene peroxidation vent
Cleavage section vents:
Cumene hydroperoxide wash vent
Cumene hydroperoxide concentration vent
Cumene hydroperoxide cleavage vent
Product wash vent
Product purification vents, combined
Storage tank vents
Dow Chemical Co.,
Oyster Creek. TX"
Carbon adsorber and
thermal incinerator.
Not applicable.
Not available.
Not applicable.
Not applicable.
Not available.
2 cumene: floating roof
4 phenol: none.
4 acetone: none.
1 cumene: none.
Product transport loading vents,
combined
Fugitive emissions
Wastewater
a "
This study does not include Puerto Rico.
d
Personal communication with L. B. Evans,
e
Personal communication with J. J. Davies
Not available.
Not available.
Deep well injection.
9 February 1976.
22 May 1978.
Georgia-Pacific Coi
Placquemine,
Carbon bed system.
Not applicable.
Condenser.
Condenser.
Not applicable.
Acetone topping column condenser; acetone column
condenser; AMS tower incineration.
1 phenol and acetone: water cooled condenser
1 phenol and heavy ends: none.
2 heavy ends: none.
2 phenol: none.
2 acetone: none.
3 AMS: none
2 cumene: conservation vent.
2 acetone: vent condenser.
2 phenol: conservation vent.
1 oxidate surge tank: none
None.
Not available.
Treatment system.
(continued)
-------
TABLE 30 (continued)
Installed emission controls by company and location
Emission source
Getty Oil Co.
El Dorado, KS^
Monsanto Co.,
Chocolate Bayou, TX
oo
o
Cumene peroxidation vent
Cleavage section vents:
Cumene hydroperoxide wash vent
Cumene hydroperoxide concentration vent
Cumene hydroperoxide cleavage vent
Product wash vent
Product purification vents, combined
Storage tank vents
Product transport loading vents,
combined
Fugitive emissions
Hastewater
This study does not include Puerto Rico.
Personal communication with R. G. Soehlke, 16 May 1978.
^Personal communication with H. Keating, 20 January 1978.
Cumene recovery system including
carbon adsorption.
Not applicable.
Steam jet vent to atmosphere.
Not applicable.
Not applicable.
3 vents to atmosphere; 5 steam jet
vents to atmsophere.
2 cumene: none.
1 raw products: none.
1 refined AMS: none.
2 acetone: none and floating roof.
2 phenol: none.
1 crude AMS: none.
1 waste oils: none.
3 wastewater: none.
No control.
Preventative maintenance.
Refinery treatment system.
Cooling water condenser, demister
separator, refrigerated condenser,
demister-separator.
Condenser.
Condenser
Condenser and no control.
Vent condensers and incinerators.
Not available.
Not available.
Not available.
Deep well injection.
(continued)
-------
TABLE 30 (continued)
Installed emission controls by company and location
Emission source
Standard Oil of California
Richmond, CA^
U.S. Steel Corp.,
Haverhill, OH1
Cumene peroxidation vent
Cleavage section vents:
Cumene hydroperoxide wash vent
Cumene hydroperoxide concentration vent
Curaene hydroperoxide cleavage vent
Product wash vent
Product purification vents, contained
Storage tank vents
Product transport loading vents,
combined
Fugitive emissions
Wastewater
Vapor scrubber and condenser.
Not applicable.
Vapor condenser.
Vapor condenser.
Scrubber.
Separation: vapor condenser.
Acetone column I: scrubber.
Acetone column II: vapor condenser.
Phenol recovery: vapor condenser.
5 cumene: floating roof
Cooling water condenser, demis-
ter-separator, NHs condenser,
demister separator.
Not applicable.
Not applicable.
Tank vent with cooling water
condenser.
Thru CW and NHs vent condensers
and conservation vents to Atm.
Crude AMS: none
1 cumene and CHP-. floating roof. Cumene:
1 acetone and phenol: dome roof, sealed. Phenol:
6 acetone: dome roof, sealed. Acetone:
7 phenol: dome roof, sealed.
conservation vent.
conservation vent.
2 floating roofs and 1
cooling water condenser.
2 residual oil:
in H2O:
floating roof.
cone roof with vent.
Scrubber on tank truck loading.
Double seals on pumps.
Refinery treatment system.
Heavy hydrocarbons:
No control.
Minor - no estimate.
Deep well injection.
cooling water
condenser.
This study does not include Puerto Rico.
Personal communication with J. Blickman, 27 April 1978.
Personal communication with C. Parris, 4 April 1978.
i
-------
TABLE 31.
oo
NJ
NUMBER OF PLANTS REPORTING USAGE OF EMISSION CONTROL METHODS IN INDICATED
SECTION OF THE PLANT MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Emission source
Cumene
peroxidation
vent
Cleavage
section vents,
combined*-
Product
purification
vents,
combined*1
Storage
tank
vents,
combined6
Product transport
loading vents,
combined f
Fugitive
emissions
Number of plant reporting usage
Absorp-
tion Incin-
Conden- Adsorp- (scrub- era-
sation tion bing) tion
3511
5011
5123
2000
0010
- - - -
of control method for each emission location
Vapor
Float- Sealed Conser- recov-
ing dome vation ery on
roof roof vent on load- No
tank tank tanks ing Other control
-a - Ob 0
- - - - 0 2
- 0 0
51 3006
- - 1 0 3
-9 o
Dashes indicate control method not applicable to emission source such as floating roof tank for the
cumene peroxidation vent.
Zeros indicate control suitable for emission source but no reported use.
cThere are 1 to 4 vents.
There are 5 to 7 vents.
There are various numbers of tanks.
There are 2 to 5 products.
lunovn; preventive maintenance programs; double seals on pumps-, minor emissions.
-------
The following subsection briefly describes the emission control
Methods reported in use at cumene peroxidation plants.
Condensation
compounds can be removed from an air stream by condensa-
tion. A vapor will condense when, at a given temperature, the
Partial pressure of the compound is equal to or greater than its
vapor pressure. Similarly, if the temperature of a gaseous mix-
ture is reduced to the saturation temperature (i.e., the tempera-
ture at which the vapor pressure equals the partial pressure of
one of the constituents), the material will condense. Thus,
either increasing the system pressure or lowering the temperature
Can cause condensation (47). In most air pollution control
Applications, decreased temperature is used to condense organic
materials, since increased pressure is usually impractical (48).
E(3uilibrium partial pressure limits the control of organic emis-
Slons by condensation. As condensation occurs, the partial pres-
sure of material remaining in the gas decreases rapidly,
Preventing complete condensation (48).
figure 17 illustrates the effects of temperature and pressure on
. ^uilibrium cumene concentration in a gaseous stream. Under
/•sobaric conditions, the concentration of cumene is directly
Proportional to its vapor pressure (49). Table 32 gives some
Camples of the amount of cumene contained in a saturated gas
tream at various temperatures and pressures. These tempera-
tures are typical of the exit gas temperatures from cooling water
nd refrigerated condensers.
ne system employing condensation for emission control on the
umene peroxidation vent is shown in Figure 18. Table 33 pre-
ents the material balance for this system. The stream compon-
nts were determined by material balance calculations performed
l97lndustry (Personal communication with L. B. Evans, 9 February
This system sends the off-gas (Stream A) from the cumene peroxi-
ation reactor through a cooling water condenser, separates the
1(3uid and gaseous streams, and sends the gaseous stream through
Control Techniques for Hydrocarbons and Organic Solvent
Emissions from Stationary Sources. Publication No. AP-
68, U.S. Department of Health, Education, and Welfare,
Cincinnati, Ohio, March 1970. 114 pp.
(48) Hydrocarbon Pollutant Systems Study, Volume I: Stationary
Sources, Effects and Control. EPA 71-12 (PB 219 073), U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina, 20 October 1972. 377 pp.
9> Jordan, T. E. Vapor Pressures of Organic Compounds.
Interscience Publishers, Inc., New York, New York, 1954.
83
-------
1,000,000
800,000
toaooo
400.000
0 10 20 30 « 50 60 70 » 90 100 120 140 160180
1EMPERATURE, °C
Figure 17. Variation of cumene concentration
with temperature and pressure.
TABLE 32.
AMOUNT OF CUMENE IN A SATURATED
GAS STREAM AT VARIOUS CONDITIONS
Pressure, Temperature
kPa
101
101
1,010
1,010
°C
15
4
15
4
, Cumene,
ppm by volume
3,100
1,400
310
140
84
-------
PRESSURE
CONTROL VALVE
8.40 kg/s
COOLING
WATER
oo
107.8 °C
551.6kPa
143.3 °C
503.3kPa
RECYCLE TO
PROCESS
©•-« —
SPENT AIR
COOLER
2. 34 kg/ s
SPENT AIR
SEPARATOR
SPENT AIR
CHILLER
X^X
CHILLED
AIR SEPARATOR
Figure 18. Condensation used as emission control
on the cumene peroxidation vent.3
,6.06kg/s
SPENT AIR
TO ATMOSPHERE
Personal communication with L. B. Evans, 9 February 1976.
-------
TABLE 33. MATERIAL BALANCE FOR AN EMISSION CONTROL SYSTEM ON
THE CUMENE PEROXIDATION VENT USING CONDENSATION3
Component
02
N2
Cumene
Acetophenone
2-Hydroxy-2-phenylpropane
Cumene hydroperoxide
Water
In
Stream A,
kg/s
0.44
5.61
1.275
0.001
0.004
0.02
1.05
Out
Stream B,
kg/s
0.44
5.61
0.005
0
0
0
0.005
Stream C,
kg/s
0
0
1.270
0.001
0.004
0.02
1.040
Total 8.40 6.06 2.34
Personal communication with L. B. Evans, 9 February 1976.
a demister. The gaseous stream then is passed through a refrig-
erated condenser, separated from the liquid, and passed through a
demister before it is released to the atmosphere (Stream B).
Liquid collected in the two separators is recycled (Stream C).
The control efficiency is 99.6% by weight for total organic
materials.
2. Activated Carbon Adsorption
Adsorption is a phenomenon in which molecules become attached.to
the surface of a solid. The process is highly selective, and a
given adsorbent, or adsorbing agent, will adsorb only certain
types of molecules. The material adhering to the adsorbent is
called the adsorbate (24). Adsorption involves three steps.
First, the adsorbent comes in contact with the stream containing
the adsorbate, and separation due to adsorption results. Next,
the unadsorbed portion of the stream is separated form the ad-
sorbent. Finally, the adsorbent is regenerated by removing the
adsorbate.
Activated carbon is the most suitable adsorbent for organic
vapors(24). Carbon adsorbs 95% to 98% of all organic vapor from
air at ambient temperature regardless of variations in concentra-
tion and humidity given a sufficent quantity of carbon. The
adsorption of a mixture of organic vapors in air by carbon is not
uniform (48) , however, higher boiling point components are pre-
ferentially adsorbed.
When a contaminated gas stream is passed over an activated carbon
bed, the organic vapor is adsorbed and the purified stream passes
through. Initially, adsorption is rapid and complete, but as the
86
-------
carbon bed approaches its capacity to retain vapor, traces of
vapor appear in the exit air. This is the breakpoint of the
activated carbon. If gas flow is continued, additional amounts
°r organic material are adsorbed, but at a decreasing rate (24).
fter breakthrough has occurred, the adsorbent is regenerated by
eating the solids until the adsorbate has been removed. A car-
ler gas must be used to remove the vapors released. Low pres-
cur® saturated steam is used as the heat source for activated
arbon and also acts as the carrier gas. When high boiling
Compounds have reduced the carbon capacity to the point where
m raPf-ete regeneration is necessary, super-heated steam at 350°C
Ca K necessary to remove high boiling compounds and return the
and tO "*"ts original condition (47) . The steam is condensed
sent to the process wastewater system for disposal.
TH
fo Control efficiency of carbon adsorbers is greater than 90%
w-£ cumene peroxidation vent emissions, (personal communication
tn L. B. Evans, 9 February 1976).
' Solvent Absorption
nes°rPtion is a process for removing one or more soluble compo-
nts from a gas mixture by dissolving them in a solvent.
sorption equipment is designed to insure maximum contact be-
een the gas and the liquid solvent to permit interphase diffu-
fa !h between the materials. Absorption rate is affected by
ctors such as the solubility of gas in the particular solvent
he degree of chemical reaction; however, the most important
or is the solvent surface exposed (24).
Ve ®nt gas scrubber-cooler system used on a cumene peroxidation
th is iHustrated in Figure 19. The information known about
L enstreams is presented in Table 34 (personal communication with
' fi- Evans, 9 February 1976).
s system off gases are scrubbed in a tray tower to absorb
arb°ns into the scrubbing liquid, which is an aqueous
oxj 3. solution. Some of the scrubbing liquid is sent to the
Withtion section, and some is recycled through the scrubber
re makeup solution. The scrubbed gas is cooled, condensate is
and sent to tne oxidation section, and the gas is re-
to the atmosphere.
4
incineration
combustion of the hydrocarbons present in the emissions
cumene peroxidation phenol plant produces carbon dioxide
bu *ater- NOX may be produced depending on the method of com-
fur n an<* the temperature. SOX production depends on the sul-
c°ntent of the auxiliary fuel, if any. The types of
87
-------
7 % Na2C03
INH20< AMBIENT
37.8°C
oo
oo
COOLER
100m2
REFRIGER
ATION UNIT
( FREON 12 )
VENT
PRESSURE
CONTROLLER
^Jk VENT GAS
' ^ CONDENSATE
SCRUBBER
MPG: CALIF. STEEL PRODUCTS
CO. AND ASME 1951
MODEL: CODE VESSEL
REFRIGERATION UNIT
MFC : CARRIER CORP.
MODEL :5H60 AND SH40
COOLER
MFC : DRAYER - HANSON
MOD a : ASME 1951
CODE VESSEL
CONDENSATE DRUM
MfG: CALIF. STEEL PRODUCTS
CO./ASME 1951
MODEL : CODE VESSEL
DRUM
m? x 1.83m
FLOW; UNKNOWN
RECYLE PUMP
UTILITIES
OXIDATION
SECTION
7460W < 10 HP ): RECYCLE PUMP
37300W { 50 HP h REFRIGERATION COMPRESSOR
FLOW; UNKNOWN
WATER :0.36 nT/s
Figure 19. Vent gas scrubber-cooler.'
lPersona\ communication •with "L. B. Evans, 9 February 1916.
-------
TABLE 34. STREAM INFORMATION FOR VENT GAS SCRUBBER COOLER
USED ON THE CUMENE PEROXIDATION VENT*»b
Component
02
N2
Water
Na2CO3
CO2
Cumene
Cumene hydroperoxide
Oxidized organics
Flow rate, m3/s^
Temperature, °C
Pressure, kPa
In
Stream A, Stream B,c
wt % wt %
7.0
60
13
0
Trace
16
Trace
Trace
1.75 1.75
110 21.4
551.6 3.4
Personal communications with L. B. Evans,
9 February 1976.
No information is available on Streams C, D,
E, F, G, and H, except that Stream C con-
tains 200 ppm of hydrocarbons.
C
Blanks indicate no information.
Basis for volume measurement as standard or
actual conditions not defined.
burnnerators (i.e., direct flame afterburners, catalytic after-
S' or flares) , used to combust hydrocarbons at plants
acturing acetone and phenol from cumene were not reported.
General
r evaP°ration loss from storage of organic materials
fc1 . Breathing, standing storage, filling, emptying, wetting,
ej£Pan * ng' Vapors expelled from a tank because of thermal
Barometric expansion/ or additional vaporization are
losses- Vapor loss from such areas as seals, hatches,
ot^er openings (but not due to breathing or level
tank C0nstitute standing storage loss. Vapors expelled from
9 *~*~ ^s fm&d constitute filling loss. Vapors expelled
ta^k during emptying (due to the fact that vaporization
r
stabii- slowlv' a^r enters to equalize pressure, vaporization
loss Zes* and there is excess vapor in the tank) are emptying
ett*n? loss ^-s tne vaporization of liquid from wetted
wall in a floating roof tank when the roof is lowered.
e*pelled because of boiling are boiling loss.
89
-------
Floating Roof Tanks
Floating roof tanks are of various designs but the basic concep
is that the roof floats on the surface of the stored material-
A seal provides intimate contact between the roof and the ta^
wall. These tanks reduce breathing and filling losses by redu
ing the space available for vapor accumulation. Wetting losse
are small and not a problem (50).
Sealed Dome Roof Tanks
This type of tank can withstand relatively large pressure
tions without incurring a loss. There is little or no brea
loss. Filling loss will depend on the tank design (50).
Conservation Vent for Tanks
The conservation vent is a device to inhibit evaporation loss
while protecting the tank from possible damage due to underp^6 .
sure or overpressure. The vent has two set points/ an upper a ^
a lower pressure. If the pressure is outside this range the
opens to allow pressure equalization with the atmosphere (51;•
This reduces evaporation losses.
Vapor Recovery System on Product Loading Facilities .
This control device collects the vapors produced from product
loading and disposes of them by one of the control methods P* ^
viously described, such as condensation, adsorption, etc. (2 ''^
Vapor recovery is a general term for emission control practic
Fugitive Emission Control
Fugitive emissions are controlled by preventive maintenance P ^Q
grams, double seals on pumps, and other measures of this type
eliminate or reduce emissions from relief valves, pump
compressor seals, pipeline valves and flanges, and process
FUTURE CONSIDERATIONS
Air Resources, Inc., and Harshaw Chemical Co., have developed^
catalytic incinerator that permits lower temperature operatic
and lower fuel costs than thermal or flame incineration ig
(50) Evaporation Loss in the Petroleum Industry - Causes
Control. Bulletin 2513, American Petorleum Institute/
York, New York, February 1959. 57 pp.
(51) Use of Pressure-Vacuum Vent Valves for Atmospheric pr
Tanks to Reduce Evaporation Loss. Bulletin 2521, Ame
Petroleum Institute, New York, New York, September 1966-
14 pp.
90
-------
for treatment of organic emissions (52). A pilot demonstration
program at the Clark Oil and Refining Corp., Clark Chemical Corp.,
phenol plant in Blue Island, Illinois, was successful. Good
catalyst activity for a variety of organic compounds and a low
catalyst deactivation rate were observed (52). This method could
prove feasible on a large scale, and economically attractive, if
the claims are correct.
(52) Hardison, L. C., and E. J. Dowd. Air Pollution Control:
Emission Control Via Fluidized Bed Oxidation. Chemical
Engineering Progress, 73(8):31-35, 1977.
91
-------
SECTION 6
GROWTH AND NATURE OF THE INDUSTRY
Phenol is used in the production of resins, caprolactam, bis-
phenol A, alkyl phenols, adipic acid, and salicylic acid (2, 53,
54). The markets for these products are expected to grow,
leading to a projected 1982 phenol capacity in the United States
of 2,050 x 10^ metric tons (53, 54). Of that capacity, 92% is
projected to be based on cumene.
Acetone is used in the production of methyl isobutyl ketone,
methyl-aerylate esters, protective coatings, solvent derivatives,
cellulose acetate, bisphenol A, Pharmaceuticals, and acetylene
(3, 55-57). The coproduction of acetone from the cumene peroxi-
dation phenol process in 1982 could account for approximately
71% of the projected acetone demand. However, since acetone is
a product of phenol production, strong phenol demand could cause
an acetone surplus.
This section contains the information collected on available
technologies to produce phenol and acetone. Emerging technolo-
gies and possible modifications to the cumene peroxidation proc-
ess -are discussed. Market and use trends for phenol, acetone,
acetophenone, cumene hydroperoxide, and a-methylstyrene are
presented. Production trends for phenol are also discussed and
projected to 19'80 and 1982.
(53) Chemical Profile, Phenol. Chemical Marketing Reporter,
207(7):9, 1975.
(54) Chemical Briefs, Phenol. Chemical Purchasing, 10(4):27-32,
1974.
(55) Chemical Profile, Acetone. Chemical Marketing Reporter,
206(21):9, 1974.
(56) Acetone. Chemical Purchasing, (10 (6):24-27, 1974.
(57) Chemical Briefs, Acetone. Chemical Purchasing, 10(3):32-
48, 1974.
92
-------
PROCESS TECHNOLOGY
Phenol
Phenol can be commercially produced from benzene, chlorobenzene,
toluene, and natural sources (4, 7, 58, 59). Figure 20 displays
the chemical relationships between the major synthetic phenol
processes. A brief description of each major process and of
other possible processes is given below.
Chlorobenzene Process—
Only one plant, comprising approximately 4% of the 1976 total
synthetic phenol capacity in the continental United States, uses
this process. The feedstock may be either benzene or chloroben-
zene. Benzene and chlorine are reacted at 80°C to produce
chlorobenzene, HC1, and about 5% polychlorobenzenes (7, 54, 56,
57). The chlorobenzene is hydrolyzed at 400°C to 500°C and
27.6 MPa to 34.5 MPa (4,000 psi to 5,000 psi) with a catalyst to
produce a stream of sodium phenate sodium chloride, and unchanged
reactants (4, 7, 20, 22). Sodium phenate is treated with HCl to
produce phenol and sodium chloride. The NaCl is often electro-
lyzed to form NaOH and chlorine. The byproducts, 2-biphenylol,
4-biphenylol, and phenyl ether, must also be recovered to make
the process economical (4, 7, 21, 23, 58-64). The overall phenol
(58) Hahn, A. V., R. Williams, and H. Zabel. The Petrochemical
Industry. McGraw-Hill Book Co., New York, New York, 1970.
620 pp.
(59) Witt, P. A., Jr., and M. C. Forbes. By-Product Recovery Via
Solvent Extraction. Chemical Engineering Progress, 67(10:
90-94, 1971.
(60) U.S. Petrochemicals: Technologies, Markets, and Economics;
A. M. Brownstein, ed. The Petroleum Publishing Company,
Tulsa, Oklahoma, 1972. 351 pp.
(61) Sittig, M. Pollution Control in the Organic Chemicals
Industry. Noyes Data Corporation, Park Ridge, New Jersey,
1974. 305 pp.
(62) Background Information for Establishment of Standards of
Air Pollution Control in the Petrochemical Indsutry: Ben-
zene and Xylene Products and Carbon Black. Office of Air
Programs, U.S. Environmental Protection Agency, 13 August
1971. pp. 1 through 7 and D-l through D-20.
(63) Banciu, A. S. Phenol Manufacture. Chemical and Process
Engineering, 48(l):31-35, 1967.
(64) Hay, J. M., D. W. Stirling, and C. W. Weaver. How Synthetic
Phenol Processes Compare. Oil and Gas Journal, 64(1); 83-88,
1966.
93
-------
BENZENE
CUMENE PCROXIDMIOM PROCESS
t CHj-CH-CH, CATAIYST|
* PROPYLENE CATAIYST^ CUMENE,
BEMZQg SUUPNATIOH PROCESS
CH]
* SULFURtC ACID
BENZBffSUlFONIC ACID 'SODIUM SUUITE —K- SODIUM BENZENESULFONATE « CAUSTIC
t+ WATCH] t* SULFUR DIOXIDE «
* HYDRATED SODIUM SULFATE )
ONa
• 1/2 S0
CATALYSI
SODIUM PHENATE*SULFUR DfOXIO£«WATE«
f SODIUM SULFITE* WATER)
CW.OBOBENZENE PROCESS
Clj CATALYST
+ 2MOH
ONa
'HCI •
+ CHLORINE
RASCHIC PROCESS
CATALYST C*OROBENZENE*CAUSTIC
"— « HCI*1« 0,
• SODIUM PHENOLATE+ HYDROCHLORIC ACID '
[+ SALT WATEIO
CATALYST
HYDROCHLORIC ACID'OXYGEN —•• CHLOROBENZENE«WATER
TOLUENE OXIDATION PROCESS
CATALYSJ
COOH
CATALYST
TOLUENE* OXYGEN • CATALYST 6ENZOIC ACID+OXYCEN
[+ WATER]
CATALYST
PMENOl
INJCI)
:6Hj i2 o
[HCI]
[H2OJ
[Hen
Figure 20. Chemical relationship between major
synthetic phenol processes.3
[1 indicate byproducts produced from reactions.
94
-------
yield is 81% based on the weight of benzene input to the
process (65).
Sulfonation Process—
One plant, which has 5.5% of the 1976 total synthetic phenol
capacity of the continental United States, uses this process.
Vaporized benzene is contacted with concentrated sulfuric acid
at approximately 150°C to produce benzenesulfonic acid and
water (4, 7, 21, 23, 58-64). The benzenesulfonic acid is neu-
tralized with sodium sulfite which produces sodium benzenesul-
fonate, sodium sulfate, and sulfur dioxide. Caustic fusion of
the sodium benzenesulfonate at 300°C to 380°C for five to six
hours produces a sodium phenate-sodium hydroxide-sodium sulfate
solution. This solution is then acidified with sulfur dioxide
and sulfuric acid to form phenol and sodium sulfite. The yield
is approximately 75% phenol, based on the weight of benzene
charged to the reactor (65). A variant of the process is to
caustic-fuse the benzene-sulfonic acid, and then treat with
dilute sulfuric acid to produce phenol, with sodium sulfate as
a byproduct.
Raschig and Raschig-Hooker Process—
At this time there are no plants in the United States using this
process. All plants that were using this process were phased out
between 1972 and the present (4, 7, 21, 23, 58-64). The Raschig
process was originally developed in the 1930's and later modified
to the Raschig-Hooker Process. Benzene is chlorinated in the
vapor phase, at 220°C to 300°C and approximately atmospheric
pressure, with gaseous hydrochloric acid over a catalyst. The
chlorobenzene produced contains approximately 6% polychlorinated
benzenes. The chlorobenzene is hydrolyzed over a catalyst at
400°C to 500°C to produce phenol and hydrochloric acid. Benzene
is converted to chlorobenzene at a rate of 10% per pass over the
catalyst. The conversion of chlorobenzene to phenol is 10%, with
the reaction proceeding at a selectivity of less than 10% for
phenol. The low reaction rates and selectivities necessitate
numerous separation and recycle steps. The overall yield is 80%
phenol, based on the weight of benzene consumed (65).
Cumene Peroxidation Process—
The cumene to phenol process is described in detail in Section 3.
The long version of the process includes the reaction of benzene
and propylene in the presence of a catalyst to form cumene. The
yield is/81% based on the weight of benzene reacted (65).
Toluene Oxidation Process—
This process accounts for 1.6% of the 1976 total synthetic phenol
capacity of the continental United States, and is used in only
(65) Blackford, J. L. Chemical Conversion Factors and Yields.
Chemical Information Services, Menlo Park, California,
1977. pp. 3, 76.
95
-------
one Plant (4, 7, 21, 58, 60). Toluene is oxidized to benzoic
acid by passing air through liquid toluene in the presence or
catalyst, at 125°C or above and two atmospheres pressure or
above. A distilled benzoic acid stream is reacted with air an
steam, in the presence of a catalyst, at 230°C and 138 kPa
(20 psi to 25 psi) to form phenol. The yield is 78% phenol,
based on the weight of toluene (65).
Benzene Oxidation Process (20)—
Schenectady Chemical Co., in Rotterdam Junction, New York, once
operated a plant using this process. Little information about
the process was found, except that its yields were poor compare
to other processes. No U.S. producers currently use this
process.
Cyclohexane Oxidation Process (7)— n'ch
Cyclohexane is oxidized to cyclohexanone and cyclohexanol, wni
are dehydrogenated to produce phenol. This process has been us
commercially in other countries, but is not currently being us
in the United States.
Natural Sources (2, 31, 66-72)—
Five firms in the continental United States produce phenol from
natural sources. Natural phenol is recovered from coke ovens,
(66) Preliminary Report on U.S. Production of Selected
Organic Chemicals; November, December, and Cumulative To
1977. S.O.C. Series C/P-77-12, United States Internationa
Trade Commission, Washington, D.C., 15 February 1978. •» vv
(67) Synthetic Organic Chemicals, United States Production and
Sales, 1975. USITC Publication 804, United States inter-
national Trade Commission, Washington, D.C., 1977.
pp. 39, 40, 214.
(68) Synthetic Organic Chemicals, United States Production and
Sales, 1974. USITC Publication 776, United States Inter-
national Trade Commission, Washington, D.C., 1976.
pp. 22, 39, 42.
(69) Synthetic Organic Chemicals, United States Production and
Sales, 1973. USITC Publication 728, United States Inte*~i
national Trade Commission, Washington, D.C., 1975. P- ^
(70) Synthetic Organic Chemicals, United States Production aJJ
Sales, 1972. TC Publication 681, United States Tariff COJl
mission, Washington, D.C., 1974. p. 22.
(71) Synthetic Organic Chemicals, United States Production and
Sales, 1971. TC Publication 614, United States Tariff c°
mission, Washington, D.C., 1973. p. 22.
(72) Synthetic Organic Chemicals, United States Production anr
Sales, 1970. TC Publication 479, United States Tariff c°
mission, Washington, D.C., 1972. p. 24.
96
-------
coal tars, and petroleum operations. The importance of natural
phenol is declining (see Table 35). Natural phenol accounted for
2.7% of the total U.S. production of phenol in 1970 and 1.3% in
1976.
TABLE 35. U.S. PRODUCTION OF PHENOL (2, 31, 66-72)
(103 metric tons)
Year
1976
1975
1974
1973
1972
1971
1970
Natural
13.1
_a
13.8
15.7
20.1
18.4
21.4
Cumene Other
based synthetic
a
"" K
703. OP
947.0°
914.6°
821. 4D
629.8
529.6
_a
89.2
95.4
102.0
109.3
161.1
245.5
Total
synthetic
990. 4b
792.2.
1,042.4?
1,016.6?
930. 7b
790.9
775.1
Total
1,003. 5b
_a
1,056.2?
1,032.3?
950.8°
809.3
796.5
Not available.
Includes Puerto Rico's contribution.
Acetone
Acetone may be produced in a variety of ways. A brief descrip-
tion of each technology is given below.
Cumene Peroxidation Process (5)—
Acetone is produced as a byproduct of this process, which is
described in detail in Section 3.
Catalytic Dehydrogenation of Isopropyl Alcohol (4, 5
Acetone is produced from vapor phase dehydrogenation
5) —
of isopropyl
alcohol at 325°C to 500°C and 275 kPa to 350 kPa {40 psi to
50 psi) over a catalyst. The yield of acetone is 95% by weight
based on isopropyl alcohol.
Catalytic Oxidation-Dehydrogenation Process (4, 5) —
The above process can be modified to produce acetone from a mix-
ture of isopropyl alcohol and air at 400°C to 500°C over a cata-
lyst. The yield is 85% to 90% acetone by weight based on
isopropyl alcohol.
Fermentation Process (4, 5) —
Acetone is one of several substances produced by distillation of
the mixture resulting from the fermentation of diluted sterile
molasses by a bacteria culture. The overhead product is a mix-
ture of normal butyl alcohol, acetone, and ethyl alcohol. The
bottoms contain proteins and vitamins. The solvent yield is 28%
to 33% by weight of sugar charged.
97
-------
Wacker Process (7)—
The Wacker process produces acetone by oxidation of propylene
over a palladium catalyst.
Propylene Oxidation Process (7)—
The oxidation of propylene to propylene oxide produces crude ace-
tone as a byproduct.
Glycerol Process (5)—
Acrolein is produced by vapor phase oxidation of propylene over
a catalyst. Isopropyl sulfate is then produced by abdorbing the
propylene in sulfuric acid, and the isopropyl sulfate is hydro-
lyzed to isopropyl alcohol. Acrolein and isopropyl alcohol are
reacted to form acetone and allyl alcohol. Liquid isopropyl
alcohol is sparged with oxygen to form acetone and hydrogen
peroxide. The hydrogen peroxide is used to convert allyl alcohol
to glycerol, and acetone is obtained as a byproduct.
Propane-butane Oxidation (7)—
Acetone is one of a number of oxygenated compounds which are
formed during the oxidation of propane-butane mixture.
Wood Distilling Industry Process (5)—
The dry distillation of calcium acetate produces acetone. Cal-
cium acetate is obtained by neutralizing pyroligneous acid with
lime and evaporating.
Steam Hydrolysis (58)—
In Romania, acetone has been produced by the steam hydrolysis of
acetylene over a catalyst.
Hydrogen Peroxide Process (4)—
Acetone is a byproduct of the manufacture of hydrogen peroxide
by isopropyl alcohol oxidation.
Hydroquinone Production (4)—
Acetone is a coproduct from the manufacture of hydroquinone from
p-diisopropyl benzene.
Butene Dehydrogenation (4)—
Acetone can be a coproduct from the dehydrogenation of butene to
methyl ethyl ketone (MEK).
Important Byproducts
Acetophenone—
This compound can be produced as a byproduct from the cumene
peroxidation product of phenol, oxidation of ethylbenzene, or
the Friedel-Crafts reaction of benzene, aluminum chloride, and
acetic anhydride (5). The Friedel-Crafts reaction was the
principal source before 1949, but is not in use today.
98
-------
a-Methylstyrene—
This compound can be produced as a byproduct of the cumene per-
oxidation production of phenol or by the dehydrogenation of
cumene (11).
EMERGING TECHNOLOGY
The trend in phenol production has been a shift to manufacture
from cumene (see Table 36), which is economically favored (7).
Research is currently being done on the process to find improve-
ments. Some of the ideas under consideration are: 1) the use
of oxygen instead of air in order to reduce reactor volume and
atmospheric emissions, 2) hydrocarbon recovery systems to enable
best usage of feedstocks, and 3) pump seal improvements (4,7,
12, 13).
The future of acetone processing is intimately related to the
growth of the cumene process for phenol. As phenol growth con-
tinues, more acetone will be available at low coproduct Prices
(4 12 13). Cumene peroxidation coproduct acetone has accounted
for an increasing share of the acetone market (3, 56, 57). In
1970 405 x 103 metric tons of acetone were produced from all
othei processes, and 328 x 103 metric tons of acetone were pro-
duct from the cumene peroxidation process (70) The cumene
peroxidation total accounted for 45% of the acetone Produced in
1968 In 1975, 312 x 103 metric tons of acetone were produced
from'all other processes and 432 x 103 metric tons of acetone
were produced from the cumene peroxidation process (4, 56, */,
61). The cumene peroxidation process accounted for 58.1% of tne
acetone produced in 1975.
INDUSTRY PRODUCTION TRENDS
Phenol
Phenol is an intermediate synthetic organic chemical with many
uses and markets, which are summarized in Figure 21 (73).
Table 37 shows the relative amount of phenol consumed in each
major market area during 1974, 1975, and 1977 (2, 32, 53, 54).
The manor use for phenol is phenolic resins which are used as
moldings in the automotive, appliance, and electrical industries,
and as adnesives in the bonding and laminating of plywood and
(73) Chemical Origins and Markets, Flow Charts and Tables, Fifth
Edition. Chemical Information Services, Stanford Research
Institute, Menlo Park, California, 1977. 118 pp.
99
-------
TABLE 36. PHENOL CAPACITY AND PRODUCTION
o
o
Capacity,
10 3 metric tons/yr
Year
1977
1976
1975
1974
1973
1972
1971
1970
1969
1968
1967
1966
1965
1964
Total
1,468
1,193
1,132
1,17.5
1,145
1,347
959
875
728
680
605
583
508
Cumene based
1,358
1,054
1,020
1,032
955
1,048
660
_d
434
249
239
Percent of Production,
cumene based 10 3 metric tons/yr
capacity
93
88
90
fi
83
78
69
_d
?§
41
-3
Total Cumene based
a b c
1'083a!b!c
1,004 '*
792
1/032a'C
951*'C
809^
797^
768r
686^
615c
611C
557C
505°
d
~d
703
947
915
821
630
530
434
381
327
278
254
201
Percent of
cumene based
production
d
"d
89
90
89
86
78
67
57
56
53
45
46
40
Includes Puerto Rico's contribution.
'preliminary.
'Includes natural sources.
Not available.
-------
PHENOL-
BISPHENOL A — — — —
CYCLOHEXANONE
2.t-XYLENOL. SYNTHETIC
AUCYLPHENOLS (OTHER THAN
MMVLPKNOL ANB
Z'4-DICHLOROPHENOXYACETIC-
ACID (2.4-D)
MANCHB) DOOECYLPHENOL
SODIUN ~^-*T-
SOLVENT REFINING
"-CRESOL
PtCNOLPHTHALEIN 1
PHtNYLSALlCYLATE J
F-NITOTPHENOL
DYES
/ UUHMTCS
1 fotmutr timeia
I PLYWOOD, nuncLE MAW. AND
/ MOLDED MOD PRODUCTS
I HUBttK FmceSS ING
I PAPER TftEATIMS >
J POtrcAnioiiifE IESIRS
J POIISULFORE IESIIS
1 COMOSIOK IESISTAIIT POLTESTEHS
[ADIPIC ACID (ill IEIOU)
CtCLOHEI<«0«E OIINE-1
SOtfEIIT (t.J., F0« LACQVEiS.
CLASTOMEIS. lEATHEH CEStEAS 1 US )
f POLYPHENYLENE OXIDE
— H POLYHEKS
L ANTIOXIDANTS
[PHENOLIC RESINS
RUBBER TACKIFIERS AND
OIL OEMJLSIFIERS f PLASTICIZERS
PHOSPHATE ESTERS FUNCTIONAL
L FLUIDS
[CICLOHEIYI ESTEIS (1.1..
STAIR1ZEK AID DTE SOLVEJiT
t* TEITUE IKOUSTIY
[SURFACE-ACTIVE AGENTS
PHENOLIC RESINS
[DYES
PHAnMCEUTICAU
J ESTERS T (t^^jjjj
,T LUK OIL ADDITIVES
T. SURFACE-ACTIVE AGENTS
[SURFACE-ACTIVE AGENTS
ANTIOXIDANTS
f SALICYLIC ACID
,f HOOD PRESERVATIVES
I FUNGICIDES
t PLASTICIZERS (E.G.. TRIPHENYL PHOSPHATE)
HYDRAULIC FLUIDS musm.it>
TDYES
I EXPLOSIVES
r ntrecriYC commcs I "Pn««Cf cmmmrs
I niirtna ritsri" («.,.. /or / Aan%rite6ue"f *"° S""s
' ,S \ OFFICE A«D BUSIKESS HACHKES
.S L Euemoiics CIHIPIIIIE»TS
"\ f P0«, TOOl »OUSI«S \f ItZitt?"""
N Msj,ss,sias!«sfl«. i""'"'""-'
L AHO APPLIAHCES
••CAnoi*cr»n . ,,L
-------
TABLE 37. PHENOL CONSUMPTION BY MAJOR
MARKET (2, 32, 53, 54)
Percent
Uses
Phenolic resins
Caprolactum
Bisphenol A
Adipic acid
All other3
1977
40 to 50
15
15
3
17 to 27
1975
46
16
14
3
21
1974
50
20
10
3
17
Includes alkyl phenols, salicylic aoid,
exports, and miscellaneous uses.
fiber board. Further growth in this area is tied to the
automotive, and highway construction industries (2, 32, 53,
These industries are now showing increasing strength.
Caprolactum is the monomer for nylon 6 fibers, polyamide til™
molding resins. This phenol market is forecast to increase at
approximately 6% to 7.5% per year (32, 72).
Bisphenol A, another major phenol-based product is a principal ^
raw material for epoxy and polycarbonate resin manufacture (2'
32, 53, 54, 72). These resins are used in protective coatings/
molded products, and road and runway surfaces (2, 32, 53/ 54 /
72). Bisphenol A is the fastest growing market for phenol-
The use of phenol in the production of adipic acid (used in V' _
manufacturing) is expected to decline because competitive
can be produced more economically (2, 4, 7, 53, 54, 73).
Alkyl phenols are used in lubricating oil additives, oil-compa
ible resins, nonionic surface active agents, rubber chemicals/
and antioxidants (72) .
Salicylic acid is used in the manufacture of Pharmaceuticals*
especially aspirin (acetylsalicylic acid) (2, 4, 7, 54, 72)-
Miscellaneous market areas for phenol include perfume in
photographic developers, dyes, herbicides, insecticides,
and preservatives (2, 4, 7, 53, 54, 73).
Acetone
Acetone has a wide variety of uses because of its solvent p£°P
ties. The primary outlet until 1950 was as a solvent.
102
-------
acetone in its
TABLE 38. ACETONE CONSUMPTION BY MAJOR MARKET (3, 55, 57)
These
Uses
Methyl methacrylate and esters
Methyl isobutyl ketone
Coatings solvent
Bisphenol A
Cellulose acetate
Pharmaceutical
Exports
All other
Percent
1977
35
13
10
7
5
5.5
3.4
21.1
1974
31
14
10
5
5
5.5
6
23.5
v °ther markets for acetone are shown in Figure 22 (73)
of zl:. lsobutyl ketone is a potentially troubled market because
(55_57\ P°llution controls that may reduce usage by up to 75%
of the Manufacture of Acetone and Phenol from Cumene
—
ro dePicts tne uses and markets for acetophenone , cumene
Peroxide, mesityl oxide, and a-methylstyrene (73).
°f the nistorical information on phenol production and
ctir ln Table 36 led to the results in Figures 24 and 25. Pro-
56-gJ s for 198° and !982 are given in Table 39 (2, 21, 22, 31,
°«, 74-79).
Synthetic Organic Chemicals, United States Production and
kales, 1969. TC Publication 412, United States Tariff
Commission, Washington, D.C., 1971. p. 25.
ynthetic Organic Chemicals, United States Production and
kales, 1968. TC Publication 327, United States Tariff
^ Commission, Washington, D.C., 1970. p. 25.
ynthetic Organic Chemicals, United States Production and
kales, 1967. TC Publication 295, United States Tariff
Commission, Washington, D.C., 1969. p. 13.
ynthetic Organic Cehmicals, United States Production and
kales, 1966. TC Publication 248, United States Tariff
Ommission, Washington, B.C., 1968. p. 14.
^ynthetic Organic Chemicals, United States Production and
s, 1965. TC Publication 206, United States Tariff
ission, Washington, D.C., 1967. p. 14.
(continued)
103
-------
ACHYLIC SHEET
SUBFACE COATINC RESINS
MOLDING AND EXTRUSION PONDERS
EMULSION POLYMERS (E.G.. FOR
ADHESIVES. PAPER COATINGS.
POLISHES)
UNSATURATED POLYESTER RESIN
MODIFIER
(-SOLVENT (E.G.. FOR PROTECTIVE
COATINGS. CELLULOSE
ACETATE. SPINNING, CHEMICAL
PROCESSING. PRINTING INKS*
ADHESIVES)
I PHARMACEUTICALS
KETHYL BUTYMOL
METHACRYLATE . ESTERS (E.G..
'-BUTYL. ETHYL. 2-ETHYL-
HEXYL. AND ISOBUTYL
"-BUTYL. ETHYL. 2-ETHYL-
HEXYL. ISOBUTYL)
ACRYLIC FIBERS
ACRYLIC FILM
—^
CARBOXYLATED POLYMERS
EMULSION POLYMERS FOR ADHESIVES
METHYL ISOBUTYL KETONE (MIBK) •
SOLVENT (E.G.. FOR CELLULOSE
ESTERS AND ETHERS. RES IKS. GUMS)
HYDRAULIC BRAKE FLUIDS
PRINTING INKS
FUEL ADDITIVE
SOLVENT (E.G.. FOR SURFACE
COAT [H6S. INSECTICIDES.
ADHESIVES. PHARMACEUTICAL
MANUFACTURE)
RARE METAL EXTRACTION
ALCOHOL DENATUR/UIT
---^ r
CORROSION RESISTANT POLYESTERS N. front* TOOL HOUSINGS [
^Vl PARTS FOR ELECTRONICS
SOLVENT FOR VINYL RESINS j EauImENT. AUTOMOBILES,
1 AND APPLIANCES
ACETIC ANHYDRIDE f
ACCTYL CHLORIDE |
FPIGMEKTS [^
PESTICIDES
SURFACE COATINGS \
ADHESIVES
MOLDING COMPOUNDS
ACRYLATE ESTERS (E.G.. ETHYL.
BUTYL. 2-ETHYLHEXYL.
ISOBUTYL. AND METHYL
ACRVLATES)
[PHARMACEUTICALS
ADVERTISING SIGHS AND DISPLAYS
GLAZING
PLUMBING FIXTURES
LIGHTING FUTURES
BUILDING PANELS
SURFACE COATING RESINS
ACRYLIC LACQUERS
ACRYLIC EMULSION POLYMERS
LUBE OIL ADDITIVES
FROTHER IN MINERAL AND
ORE FLOTATION
COAL IENEFICIATIOK
SOLVENT FOR LACOUERS
PROTECTIVE COATINGS
I REINFORCED PLASTICS (E.G.. FOR
ELECTRONIC CIRCUIT BOARDS. PIPES)
[ ADHESIVES
I FLOORING AND PAVING
GLAZING
APPLIANCE COMPONENTS
OUTDOOR LIGHTING AND SIGNS
AUTOMOTIVE LIGHTING (E.G..
TAIL LIGHT LENSES)
TELEPHONE EQUIPMENT
POKER TOOLS
OFFICE AND BUSINESS KACHIMES
ELECTRONICS COMPONENTS
Figure 22. Uses and markets for acetone and derivatives (73).
Reprinted from Chemical Origins and Markets
by permission of Stanford Research Institute.
-------
PERFUMES
A f. PHARMACEUTICALS
HENONE" ~~ " PLASTICS, RESINS, AND RUBBERS
SOLVENT
ACETONE
'a-METHYLSTYRENE
ACETOPHENONE
AVIATION FUEL
CUMENE HYDROPEROXIDE-
SOLVENT
CUMENE SULFONIC ACID,
AMMONIUM SALT
PHENOL
SPECIALITY CHEMICALS
Figure 23. Markets and uses for acetophenone, cumene
hydroperoxide, and a-methylstyrene (73).
Reprinted from Chemical Origins and Markets by
permission of Stanford Research Institute.
TABLE 39. PROJECTED PRODUCTION AND CAPACITY
FOR PHENOL, 1980 AND 1982 (2, 21,
22, 31, 56-64, 74-79)
~~~ " Projections ~
Production/capacity 1980 1982
Production:
Phenol, 103 metric tons 1,225 1,350
Cumene based phenol, 103 metric tons 1,100 1,240
Percent of cumene based production 90 92
Capacity:
Phenol, 103 metric tons 1,850 2,050
Cumene based phenol, 103 metric tons 1,675 1,890
Percent of cumene based capacity 91 92
rud
(79) Synthetic Organic Chemicals, United States Production and
Salas, 1964. TC Publication 167, United States Tariff
Commission, Washington, D.C., 1965. p. 13.
105
-------
o
cr>
3,000
1 1,000
900
19641966 1968 1970 1972 1974 1976 1978 1980 1982
YEAR
Figure 24.
Capacity and production
trends for phenol projected
to 1978 (2, 21, 22, 31, 56-64,
56-64, 74-79).
CUMENE BASED
PHENOL CAPACITY
CUMENE BASED
PHENOL PRODUCTION
CUMENE BASED
PHENOL CAPACITY
CUMENE BASED
PHENOL PRODUCTION
1964 1966 1968 1970 1972 1974 1976 1978 1980 1982
YEAR
Figure 25.
Historical and projected
trends in curtvene-based phenol
production and capacity (.2, 21,
3L. 56-64, 14
-------
phenol demand and capacity is expected to increase at an
rate of 5% (2). However, the announced expansions and new
which are listed in Table 40 would bring the phenol
to 2,220 x 103 metric tons by 1982 (2, 21, 32, 33 and
communication with C. Paris, 4 April 1978). This in-
in caPacity would mean decreased capacity utilization if
growth rate in demand for phenol remains as projected.
TABLE 40.
ANTICIPATED EXPANSION AND NEW FACILITIES
IN THE PHENOL INDUSTRY (2, 21, 32, 33)
and location (process)
Added phenol
capacity
103 metric
tons/yr
Scheduled
completion
date
Chemical Company
, WA
^toluene oxidation)
eorgia_Pacific corporation
SW
, LA
cumene peroxidation process)
nion Carbide Corporation
Br°°k' NJ
cumene peroxidation process)
- Corporation
Chemicals Company
ll, OH
cules cumene peroxidation process)
45
64
23
88
Postponed.
Planned.
Planned.
Early 1979.
facilities:
Electric
Vernon, IN (Unknown)
Oil Chemicals
Coast location (Unknown)
181
227
1980.
Late 1981.
£t0mproJected production of 1,240 x
tons curnene in 1982 would yield app]
^ert; acetone coproduct. The pro;
f, ^vlj O4-«._s fc _ . _ >4 *•» ••
103 metric tons of phenol
—- *„ ^»,. „„„*« yield approximately 760 x 103 metric
of acetone coproduct. The projected acetone demand, using a
lte<3 growth rate of 4%, is 1,070 x 103 metric tons (3).
--ore, about 71% of the acetone demand will be supplied by
manufacture of acetone and phenol from cumene. However, if
Piants were to operate at full utilization, approximately
x 103 metric tons of acetone coproduct would be produced.
phenol demand could lead to an oversupply of acetone.
107
-------
REFERENCES
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1962. 38 pp.
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Loss. Bulletin 2520, American Petroleum Institute, New
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American Petroleum Institute, New York, New York, November
1969. 14 pp.
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q-5
*• Code of Federal Regulations, Title 42 - Public Health,
Chapter IV - Environmental Protection Agency, Part 410 -
National Primary and Secondary Ambient Air Quality Stand-
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Qc
• Standard for Metric Practice. ANSI/ASTM Designation
E 380-76E, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
115
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APPENDIX A9
STORAGE TANKAGE CALCULATIONS
The procedures for calculating the storage capacities of the
tankage needed by a representative cumene peroxidation plant ana
the emissions from storage tanks are outlined in this section.
CALCULATION OF TANK SIZE
Tankage requirements for the representative plant were determine
by aggregation of the data available on tank sizes, number of
tanks, and plant production (personal communication with L. B.
Evans, 9 February 1976). Tank capacity was then determined.
Estimates of the tank diameters and heights were made using
D =
where D = tank diameter, ft
Ct = tank capacity, gal/tank
k2 = conversion factor, 7.481 gal/ft3
h = tank height, ft
This formula neglects the height under the slanted roof area.
Number of turnovers per year were found using
N =
(A-2)
N1
where N = number of turnovers per year
T = throughput per year of the stored material, gal/yr
Ct = tank capacity, gal
N' = number of tanks
Nonmetric units in this appendix correspond to those used f°r
these calculations during the study.
116
-------
and throughput was determined by
T = !L^_ k3 (A.3)
where CAP = production capacity for the material, tons/yr
U = utilization, 0.80
W = liquid density of the chemical stored, Ib/gal
k3 = conversion factor, 2,000 Ib/ton
Storage tank emissions consist of breathing and working losses
from fixed-roof storage tanks, and evaporation and withdrawal
Bosses from floating-roof storage tanks. Breathing losses are
c^used by daily changes in ambient temperature. Working losses
^re caused by filling and emptying the tanks. Evaporative losses
from floating-roof storage tanks are caused by vapor leakage be-
tween the float and the tank shell at the seal. The losses are
estimated by the methods described below. All losses are calcu-
^ated as equivalent gasoline losses and then converted to speci-
. lc petrochemical losses. The equations given below were derived
lr> References 50, 80-83.
££ogedure for Calculating Losses from Fixed-roof Storage Tanks
Calculate the equivalent gasoline breathing loss:
where r = equivalent gasoline breathing loss, bbl/yr
P = vapor pressure of material stored at bulk
temperature, psia
D = tank diameter, ft
H1 = average tank outage, ft
AT = average daily ambient temperature change,
F = paint factor
C = diameter factor
Evaporation Loss from Floating Roof Tanks. Bulletin 2517,
American Petroleum Institute, New York, New York, February
1962. 13 pp.
1} Evaporation Loss from Fixed Roof Tanks. Bulletin 2518,
American Petroleum Institute, New York, New York, June
1962. 38 pp.
*> Use of Variable Vapor Space Systems to Reduce Evaporation
Loss. Bulletin 2520, American Petroleum Institute, New
York, New York, September 1964. 14 pp.
* Petrochemical Loss from Storage Tanks. Bulletin 2523,
American Petroleum Institute, New York, New York, September
!969. 14 pp.
117
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The tank height was assumed to be 50 ft, 30 ft, 20 ft, or 15 ft
as appropriate. The average tank outage, i.e., freeboard, was
taken as one-half the height.
The average daily ambient temperature change, AT, was assumed
be 20°F, the national average value. The paint factor, Fp, al?ty/
adjustment factor for the paint type, was assumed equal to uni y
which is the value for white paint in good condition. The pal
factor can be as high as 14.6 for gray surfaces.
i s
The diameter factor, C, an adjustment factor for small tanks,
equal to unity for tanks 30 ft or larger in diameter. For tof
smaller tanks, the value is obtained from a graph given in R®1
ence 77 and is between 0.25 and 1.0.
Step 2. Calculate the equivalent gasoline working loss:
Fg ' TOTOOO PVNKT (A"5
where F = equivalent gasoline working loss, bbl/yr
V = tank capacity, bbl
N = number of turnovers per year
KT = turnover factor =1.0 for N £ 36
= MO + * for N > 36
6 N
Step 3. Compute total equivalent gasoline loss, L :
-------
LI = L(42)(W)
LI
CAP • U
E =
E1
2~
(A-8)
(A-9)
(A-10)
where
LI
CAP
E1
E
U
total petrochemical loss, Ib/yr
production capacity for the material, ton/yr
emission factor, Ib/ton phenol produced
emission factor, g/kg phenol produced
utilization, 0.80
sing the above procedure and the storage tank input data shown
n Table A-l, the emission data shown in Table A-2 were calcu-
lated for fixed-roof storage tanks.
TABLE A-l.
FIXED-ROOF STORAGE TANK INPUT DATA FOR A
REPRESENTATIVE SOURCE MANUFACTURING
ACETONE AND PHENOL FROM CUMENE
Input information
Number of tanks
Production capacity, tons/yr
Ambient temperature, °F
Average temperature change, °F
Molecular weight, Ib/lb-mole
Liquid density, Ib/gal
Vapor pressure, psia
Bulk temperature, °F
Tank .diameter, ft
Tank outage, ft
Paint factor (83)
Diameter factor (83)
Turnover factor (83)
Number of turnovers per year
Tank volume, bbl
Tank height, ft
Material stored
Acetophenone a-Methylstyrene
1
150,000
64
20
120.2
8.58
0.01
85
8
7.5
1.00
0.40
1.00
5
143
15
1
150,000
64
20
118.2
7.58
0.08
85
15
10
1.00
0.75
1.00
27
595
20
Phenol
4
150,000
64
20
94.1
8.83
0.10
140
33
25
1.00
1.00
1.00
15
7,619
50
TABLE A-2. FIXED-ROOF STORAGE TANK EMISSION SUMMARY
Material stored
Acetophenone
a-Methylstyrene
Phenol
Losses
gal/yr
1.55
63.10
455.6
Ib/yr
13.29
477.7
4,023
Emission factor,
g/kg phenol produced
0.000055
0.0020
0.017
All losses and emission factors are per tank.
119
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Procedure for Calculating Losses from Floating-roof Storage.
Tanks
Step 1. Calculate the equivalent gasoline evaporation loss:
'
where L = equivalent gasoline evaporation loss ,
K = tank factor = 0.045 for welded tanks
=0.13 for riveted tanks
D = tank diameter, ft
P = vapor pressure of material stored at bulk
_ temperature, psia
u = average wind speed, mph
K = seal factor =1.00 for tight fitting and post
1942 seals
=1.33 for loose fitting and pre
1942 seals
K = paint factor = 1.00 for aluminum color
p =0.90 for white
Tank diameters were computed using a height of 50 ft, 30 ft
20 ft, or 15 ft as appropriate.
Step 2. Calculate the equivalent gasoline withdrawal loss:
V
W = 0.000448 ~-
g D
where W = equivalent gasoline withdrawal loss, bbl/yr
V = volume of liquid withdrawn from tank, bbl/yr
Step 3. Compute total equivalent gasoline loss, L :
L = L + W
g y g
Step 4. Equation A- 13 determines the total equivalent gaso
loss, Lg. The petrochemical loss, L, can be determined &y tjrO"
assuming that the volume of vapor lost is the same f or t^ili^
chemical in question as for gasoline, by assuming aPPllcaM and
of the ideal gas law, and by using the molecular weight , n'^e
liquid density, W, of the petrochemical and of gasoline. gj.ty
ratio of the molecular weight of gasoline to its liquid ®ical
is 0.08. Therefore, the equation to compute the petrocnem
loss is:
...... L
120
-------
where L = total petrochemical loss, bbl/yr
M = molecular weight of the chemical, Ib/lb-mole
W = liquid density of stored chemical, Ib/gal
Calculate emission factors on the basis of phenol
production from:
L! = L(42(W)
LI
E' =
CAP
U
(A-15)
(A-16)
where
LI
CAP
E1
E
E = T~
total petrochemical loss, Ib/yr
production capacity, tons/yr
emission factor, Ib/ton phenol produced
emission factor, g/kg phenol produced
(A-17)
.Slng the above procedure and the storage tank input data shown
n Table A-3, the emission data shown in Table A-4 were calcu-
ated for floating-roof storage tanks.
TABLE A-3.
FLOATING-ROOF STORAGE TANK INPUT DATA FOR
REPRESENTATIVE SOURCE MANUFACTURING
ACETONE AND PHENOL FROM CUMENE
Tank identification
Input information
Number of tanks
Production capacity, tons/yr
Vapor pressure, psia (6)
Bulk temperature, °F
Average wind speed, mph
Volume liquid withdrawn, bbl/yr
Liquid density, Ib/gal
Molecular weight, Ib/lb-mole (6)
Tank factor, welded (80, 83}
Seal factor, tight (80, 83)
Paint factor, white (80, 83)
Tank diameter, ft
Tank height, ft
Acetone
4
150,000
3.87
76
10.07
132,335
6.585
58.1
0.045
1.00
0.9
30
50
Cumene
3
150,000
0.09
76
10.07
376,708
7.19
120.2
0.045
1.00
0.9
58
50
Heavy ends
1
150,000
0.0003
100
10.07
122,722
7.19
250
0.045
1.00
0.9
17
30
TABLE A-4. FLOATING-ROOF STORAGE TANK EMISSIONS SUMMARY
Material stored
Acetone
Cumene
Heavy ends
Losses
gal/yr
542.1
307.4
379.2
Ib/yr g/
3,569
2,207
2,723
Emission factor,
'kg phenol produced
-0.015
0.0092
0.011
All losses and emission factors are per tank.
121
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APPENDIX B
SPECIFICATIONS
Some commonly used specifications for acetone, phenol, cumene/
acetophenone, and ot-methyIstyrene (5, 7, 9, 11-13) are:
Acetone:
Acetone
Acidity
Water
Alcohols
Evaporative residue
Phenol, chlorination grade:
Phenol
Water
Carbonyls
Cumene:
Cumene
Butylbenzenes
n-Propylbenzenes
Ethylbenzene
Acetophenone, perfume grade:
Acetophenone
Chlorine
Other compounds
Acetophenone, technical grade:
Acetophenone
Other compounds
a-MethyIstyrene:
a-Methylstyrene
3-MethyIstyrene
Cumene
TBC (an oxidation inhibitor)
Aldehydes
Peroxides
Polymer
99.7 +%
10 ppm (as acetic acid)
0.3 wt % max.
15 ppm
10 ppm
99.9 +%
200 ppm .
50 ppm (as mesityl oxide;
99.99 +%
500 ppm, max.
1,000 ppm, max.
1,000 ppm, max.
99 +%
0
2 % max.
97 +%
3 %
99.3 %
0.5 %
0.2 %
15 ppm
10 ppm, as CHO
3 ppm, as HO
0 ppm
122
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APPENDIX C
SAMPLING PROCEDURES AND EQUIPMENT
TEST SITE PREPARATION
samPlin9 at plants manufacturing acetone and phenol from
did not require test site modifications. The emissions
6 organic vapors; therefore, isokinetic sampling was not
quired. Stainless steel sampling lines and valves were in
^ ace and accessible from platforms.
TEST
FREQUENCY AND DURATION
,mPling results are based on a field sampling effort which took
°Ver a tw° week Period- A total of 8 HVOSS samples, 24
r bag samples, and 17 formaldehyde and other aldehyde samples
collected at two plants.
HvN DIOXIDE/ OXYGEN, CARBON MONOXIDE, LOW MOLECULAR WEIGHT
UROCARBONS (LOWER THAN C6) , BENZENE, AND CUMENE
k Pies for analysis for these compounds were collected in Tedlar
Ana?" .Analytical procedures will be described in Appendix D.
f^ jytical Procedures, even though they were performed in the
M°LECULAR WEIGHT ORGANIC COMPOUNDS, TRACE ELEMENTS,
MOISTURE
sampling method used was a modification of the Source Assess-
Sampling System (SASS) described in the Level I Environmen-
Assessment Procedures (84). The modified train is the HVOSS.
Th
~
Hamersma, J. W., S. L. Reynolds, and R. F. Maddalene.
!ERL-RTP Procedures Manual: Level I Environmental Assess-
ment. EPA-600/2-76-160a, U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina, June 1976,
147 pp.
123
-------
The modifications consist of:
• The particulate collection and sizing devices were remove
• The sampling valves were used rather than a probe heated
to 200°C.
• The stack gas stream tested was controlled to approximate
5°C by using an equivalent condenser submerged in an ice
bath. The XAD-2 resin module was maintained at approxi-
mately 5°C.
• An explosion-proof pump was substituted for the vacuum
pump used in the SASS train.
A diagram of the sampling train is shown in Figure C-l.
Samples from the condenser and the XAD-2 module and the was"1 ^
of those and the sample lines were analyzed for organic compo
The HVOSS train utilized four impingers containing solutions
designed to trap volatile trace elements during testing at on ^
emission point. The impinger order, impinger contents, and P
poses of each impinger is shown in Table C-l.
TABLE C-l. HVOSS TRAIN IMPINGER SYSTEM REAGENTS
Impinger
Reagent
Quality
6M H2O2
0.2M (NH4)2S208
+ 0.02 M AgN03
0.2M (NHU)2S208
+ 0.02 M AgNO3
Silica gel
(color
indicating)
750 mS, Trap reducing gases
S02 to prevent
of oxidative capa
of trace element colJ-e
ing impingers 2 and
750 mi Collection of volatile
trace elements by °*1U
tive dissolution.
750 ma Collection of volatile
trace element by oxia*
tive dissolution.
750 g Prevent moisture from
reaching pump and dry
test meter.
The impinger solutions used to collect trace elements were
on one test at each plant. One test for trace elements at
plant was performed at the request of the EPA Project Officer*
124
-------
STACK
to
DRY GAS TEST METER ORIFICE PRESSURE READOUT
TEMPERATURE READOUTS
Figure C-l. High volume organic sampling system.
-------
The remainder of the tests were carried out using the impinger
system in Table C-2.
Moisture content of the stream was determined from the total
amount of water collected by the HVOSS train. The train was
cleaned up after each run following a modified Level I procedur
FORMALDEHYDE AND OTHER ALDEHYDES
No standard methods have been developed for the sampling of
in
aldehydes in stack gas emissions. The Intersociety Committee
Ambient Air Methods has developed a method for sampling aldehy
ALTERNATIVE HVOSS TRAIN IMPINGER SYSTEM
TABLE C-2.
Impinger Contents Quantity
Purpose
1, 2
3
Water
Empty
750 ml Cool the sample gas.
0 Spray trap, may be eliminated
Silica gel 1,000 g
low moisture content gas.
Prevent moisture from reaching
the pump and dry gas test met
in ambient air which was modified to sample for low levels of
aldehydes in stack gases. The method for ambient air involves
drawing the air stream through 2 midget impingers containing
10 mil of 1% NaHSO3 at a rate of 2 J,/min for 60 min and measuriny
the total volume of gas with a dry test meter. The minimum
detectable concentration of aldehydes is 0.02 ppm by volume
(85)
The method as modified for stack emissions including a
probe (glass) with a plug of glass wool for filtering out Par~"_n
ticulates, 2 midget impingers containing 10 m£ of 10% NaHSOa/
empty impinger, and an evacuated cylinder. As no upper limit
given for the method when used in ambient air sampling, stacK y
was collected at 2 8,/min for periods of 15 min and 30 min. A
diagram of the apparatus is shown in Figure C-2.
After sample collection, the impinger contents were transferee
to a 100 mi sample bottle. The glass wool plug was removed an g
discarded. All glassware from the probe to the dry impinger w ^
rinsed with 3 portions of 10% NaHSO3, and the rinsings were a°
to the sample bottle.
(85) Methods of Air Sampling and Analysis. American Public
Health Association, Washington, D.C., 1972. pp. 190-1'8
126
-------
LJ
r-^XZ^
CLASS WOOL
SIACK
f 1
1
1
/
SOLUTION
\
ICE BATH
PRESSURE
GAUGE
EVACUATED
CYCLINDER
Figure C-2. Diagram of sampling train for aldehydes.
127
-------
APPENDIX D
ANALYTICAL PROCEDURES
Parts of the analysis program were carried out at both the fie
locations and at the MRC Dayton Laboratory. Field analysis
included CO, CO2, and 02 by Orsat analysis; and GI to Cs ny^cu-
carbons, benzene, and cumene by portable GC/FID. Higher moie
lar weight organics (C7 and higher), aldehyde, and formalaeny
analysis were done in the laboratory. In addition to the Ci
C5 hydrocarbons, benzene, and cumene field analysis, integra
gas samples were analyzed for Ci to C5 hydrocarbons, benzene,
and cumene at the laboratory using qualitative GC/MS analysis.
CARBON DIOXIDE, CARBON MONOXIDE, AND OXYGEN
Analysis of these components was carried out in the field us^
the Orsat technique as specified in the Method 3 "Gas Analysi^
for Carbon Dioxide, Excess Air, and Dry Molecular Weight" Pr
cedure (86) and the FYRITE apparatus. Data were reported in
terms of volume % for CO, CO2, and O2•
LOW MOLECULAR WEIGHT HYDROCARBONS
The G! to C5 hydrocarbons, benzene, and cumene were sampled
analyzed at the plant site. Stack gases were collected in e
ated Tedlar bags and taken to the field laboratory. The
was performed using an AID portable chromatograph with a &
ionization detector (FID). The instrument was equipped witn ^
1.8 m by 6.4 mm stainless steel column packed with Poropak Q
was operated isothermally with a column temperature of 50°C.
Standard gas mixtures of the compounds were taken to quantify
data. The data were reported as alkenes (Ci to C5), benzene,
cumene vppm. Qualitative GC/MS analysis was performed to co
orate the field identification.
HIGHER MOLECULAR WEIGHT ORGANIC COMPOUNDS
• c
A flow diagram for the sample collection and preparation is
in Figure D-l.
(86) Method 3 - Gas Analysis for Carbon Dioxide, Oxygen,
Air, and Dry Molecular Weight. Federal Register, 41
23069-23070, 1976.
128
-------
SAMPLING LINE WASHES
MODULE WASH
ICE WATER BATH
ICE WATER BATH
EQUIVALENT CONDENSOR
CONTENTS (CUMENEI
AND WASH ICH2CI2I
REMOVE 100.0 mis
FOR SSMS ON
PLANT B/RUN 1
XAD-2 RESIN
&'
*ft REMOVE 7.0 g FOR
r^fl AA:(As.Hg,S.I
' AND SSMS.
IL.I PLANT B/RUN 1
COLLECT AND
RETAIN
CONTENTS AND CH30H * H# - RINSES
t
£3 *
WEIGH AND
DISCARD
DCTRACT VIA SEPARATORY
nJNNU THREE TIMES.
HWAl TO 15* OF SAMPLE
VOLUME EACH EXTRACTION
EXTRACT VIA SOXHIET
IN
DILUTE TO KNOWN VOLUME
ANALYZE FOR As, Hg, St. VIA AA
PLANT A RUN 2 AND PLANT B RUN 1.
ALL OTHER RUNS IMPINGED CONTENTS
WAS DISTILLED WATER (71. EMPTY
AND SILICA GEL. RESPECTIVELY.
(LAM.
C,?rl: * * "I FOR
u' Cw ANALYSIS VIA cc
FOLLOWING EXTRACTION. RECORD VOLUME
OF SOLVENT AND REMOVE ALIQUOT HAVING
VOLUME EQUAL TO THE PERCENT VOLUME
THAT "*A " IS OF THE COMBINED ORGANIC
VOLUME AND SUBMIT IT FOR C7 - C]6
ANALYSIS VIA GC
COMBINE ALL PORTIONS. REDUCE VOLUME VIA ROTOVAP
EXERCISE CAUTION TO RETAIN VOUTILES (CUMENE).
MAXIMUM CONDITIONS ARE 45'C AND 50 mm Hg. * •
T
REMOVE 0.5 mg. DISSOLVE
IN 10.0 mis OF HEXANE
NOTE;
TOhDv..r5;°mls AMBIENT EVAPORATE
WflriXNfSS: DESS'CATE. WEIGH. RECORD
TMDt I?ND VOLUM£ F0* '« ANALYSIS.
IABLE WEIGHT OF
WAS
•MEASURE VOLUME
• WEIGH
8 STEP LIQUID CHROMOTOGRAPHY
FRACTIONATION VIA SILICA GEl COLUMN
USING 2.0 flits. (100 mg. I OF THE HEXANE
SOLUTION.
NOTE: ELUATES WERE TO DRIED, WEIGHED AND
SUBMITTED FOR QUANTITATIVE ANALYSIS VIA
CC/MS. HOWEVER. THE ELUATES WERE QUITE
VOLATILE. DRIED WEIGHTS WERE NEGLIGIBLE.
RESULTANT GC/MS RESULTS INDICATED THE
LC - FRACTIONATION WAS NOT NECESSARY.
SAMPLE PREPARATION IS TERMINATED AT THIS
POINT ON ALL RUNS EXCEPT PLANT B/RUN 1.
PREPARATION OF THIS SAMPLE IS CONTINUED
AS INDICATED BELOW THE DOTTED LINE. WITH
THIS EXCEPTION. THE COMBINED, CONCENTRATED
ORGANIC SAMPLES ARE MEASURED AND SUB-
MITTED FOR QUANTITATIVE ANALYSIS VIA GC/MS
Figure D-l.
Flow diagram for sample collection and
preparation at plants manufacturing
acetone and phenol from cumene.
129
-------
The XAD-2 resin was Soxhlet extracted for 24 hr with pentane.
The volume was measured and a 1 mi to 10 mJl portion was removed
for GC analysis of the C7 to Ci6 hydrocarbons. The remaining
solution was stored for later combination with the other sampleS
from the run. For one run at each plant, 2 g of resin were
removed prior to extraction for elemental analysis.
The condensate and the sample line washes from the run were ex-
tracted with methylene chloride; this extract was then combined
with the methylene chloride rinse of the module. The volumes °r
these solutions were measured and a portion equal to the percen-
tage of the portion removed from the pentane extract of the XAD-*
resin extraction was removed for C7 to Cic analysis The remain
ing solution, representing the same percentage of the total as
iJ!1^ pentane solution of the extraction total, was com-
with the pentane extraction solution. The resulting sol*
rVS SS6d XS V°1Ume in a rotov*P with maximum conditions
t vs.? rv - arEsssr
infrared
sss is .
of the fractions were not required. Only two
J°nt?ined c°^POunds in the GC/MS analysis. No other
a basis for
TABLE D-l. SOLVENTS USED IN LIQUID CHROMATOGRAPHIC SEPARATION^
Solvent composition
1
2
3
4
5
6
7
8
Pentane
?n* MS^Y^ene chloride in pentane
50% Methylene chloride in pentane
Methylene chloride
in "wthylene chloride
mehfcylene chloride
o methylene chloride
Concentration HCl/methanol/methylene
FORMALDEHYDE
±n
a 10%
which was proposed by the Intersc nc
130
-------
Formaldehyde is measured in an aliquot of the collection medium
»y the chromatropic acid procedure. After reaction with chroma-
5RnPi° acid and sulfuric acid, the transmittance was read at
°0 nm. A blank containing 2 ml of 10% bisulfite was employed to
^et the 100% transmittance reading and a standard curve was gen-
rated employing known sodium formaldehyde bisulfite solutions
equivalent to 1 ug, 5 yg, and 7 yg f ormaldehyde/mfc .
OTHER ALDEHYDES
2 to C5 aldehydes were collected in impingers containing a 10%
S03 solution as described in Appendix C. The analysis method
patterned after Tentative Method 110 Appendix E as proposed
y the Interscience Committee (85) .
TK
e aldehydes were measured using GC/FID. The GC column was
w m x 3 nun stainless steel, packed with 15% by weight of carbo-
ax.20M on chromasorb, 60 to 80 mesh, followed by 1 . 7 m x 3 mm
ainless steel, packed with uncondinonylphthalate on firebrick.
tention times for the various species, under the conditions
in Appendix E are presented in Table D-2.
TABLE D-2. RETENTION TIMES FOR ALDEHYDES,
KETONES, ALCOHOLS, AND ESTERS
Reprinted from Methods of Air Sampling and Analysis by
permission of the American Public Health Association.
Compound
Acetaldehyde
Propionaldehyde
Acetone
Isobutylaldehyde
Methyl alcohol
Ethyl alcohol
Isopropyl alcohol
Ethyl acetate
n-Butylaldehyde
Methyl ethyl ketone
Isopentanol
Crotonaldehyde
Retention
time, min
3.5
4.6
5.1
5.5
6.1
6.7
6.7
7.0
7.1
7.7
12.0
14.0
ELEMENT ANALYSIS
of trace element composition was performed on the XAD-2
2 anj' tne XAD-2 resin module wash, and the contents of impingers
rnerc 3- Atomic absorption (AA) was used to analyze arsenic,
rv' ar*d selenium in the impingers while SSMS by CDM/Accu
uantif ie<3 69 elements including: uranium, thorium, bis-
a+. ' thallium, mercury, gold, platinum, iridium, osmium,
en» tantalum, hafnium, lutetium, ytterbium, thulium,
131
-------
erbium, holmium, dysprosium, terbium, gadolinium, europium,
samarium, neodymium, praseodymium, cerium, lanthanum, barium,
cesium, iodine, tellurium, antimony, tin, cadmium, silver, palla-
dium, rhodium, ruthenium, molybdenum, niobium, zirconium,
yttrium, strontium, rubidium, bromine, selenium, arsenic, ger-
manium, gallium, zinc, copper, nickel, cobalt, iron, manganese,
chromium, vanadium, titanium, scandium, calcium, potassium, chlo-
rine, sulfur, phosphorus, silicon, aluminum, magnesium, sodium,
and fluorine. SSMS is a semiquantitative method whose accuracy
in this use is +200%, -100%.
All solid samples were digested before analysis using the acid
digestion Parr bomb technique originally developed by Bernas and
modified by Hartstein for trace metal analysis of coal dust by
AA (87, 88). This method employs the Parr 4145 Teflon-lined bomb
and involves digestion of the samples in fuming nitric acid at
150°C. Sample solutions produced by acid digestion were first
diluted with distilled water to reduce acid concentration to
approximately 2% and then submitted for analysis.
(87) Bernas, B. A New Method for Decomposition and Comprehensive
Analysis of Silicates by Atomic Absorption Spectrometry.
Analytical Chemistry, 40(11):1682-1686, 1968.
(88) Hartstein, A. M., R. W. Freedman, and D. W. Platter. Novel
Wet-Digestion Procedure for Trace-Metal Analysis of Coal by
Atomic Absorption. Analytical Chemistry, 45(3);611-614,
1973.
132
-------
APPENDIX E
SAMPLING AND ANALYSIS METHODS FOR
FORMALDEHYDE AND ALDEHYDES (85)
Reprinted from Methods of Air Sampling and Analysir, by
permission of the American Public Health Association.
133
-------
INTERSOCIETY COMMITTEE
110
TENTATIVE METHOD OF ANALYSIS FOR LOW
MOLECULAR WEIGHT ALIPHATIC ALDEHYDES
IN THE ATMOSPHERE
4350I-OI-7IT
;. Principle
Formaldehyde, acrolein and low mole-
cular weight aldehydes are collected in
1 per cent NaHSO.i solution in midget
impingers. Formaldehyde is measured
in an aliquot of the collection medium
by the chromotropic acid procedure.
acrolein by a modified mercurio-
chloride-hexylresorcinol procedure, ami
C-j-Cj aldehydes by a gas chromalo-
graphic procedure. The method permits
the analysis of all C|-C.-, aldehyde? in a
sample (1).
The sampling procedure is not appli-
cable for the determination oF alcohols,
esters or ketones in atmospheric sam-
ples, since bisulfite does not efficiently
collect these materials. However, should
some of these compounds be present in
the atmosphere, their presence may be
indicated by the appearance of peaks
corresponding to their retention limes
in the chromatograms. The retention
times for several of these compounds are
shown along with the aldehydes in Table
1.
2. Range and Sensitivity
At sampling rates of 2 liters/min over
a 1 hr period, the following minimum
concentrations can be determined:
CH-0:
CH3CHO:
CHaCHoCHO:
(CH3).,CHCHO:
CH, = CHCHO:
0.02 ppm
0.02 ppm
0.03 ppm
0.03 ppm
0.01 ppm
Shorter sampling periods are permis-
sible for higher concentrations.
3. Interferences
3.1 Formaldehyde..
3.1.1 The chromotropic acid pro-
cedure has very little interference from
other aldehydes. Saturated aldehydes
give less than 0.01 per cent positive
interference, and the unsaturated alde-
hyde acrolein results in a few per cent
positive interference. Ethanol and
higher molecular weight alcohols and
olefins in mixtures with formaldehyde
are negative interferences. However,
concentrations of alcohols in air •re
usually much lower than formaldehyde
concentrations and, therefore, are not
a serious interference.
3.1.2 Phenols result in a 10-20
per cent negative interference when
present at an 8:1 excess over formalde-
hyde. They are, however, ordinarily
present in the atmosphere at lesser con-
centrations than formaldehyde and,
therefore, are not a serious interference.
3.1.3 Ethylene and propylene in •
10:1 excess over formaldehyde result
in a 5-10 per cent negative interference
and 2-methyl-l, 3-butadiene in a 15:1
excess over formaldehyde showed a 15
per cent negative interference. Aro-
matic hydrocarbons also constitute •
negative interference. It has recently
been found that cyclohexanone cau»e»
a bleaching of the final color.
3.2 Acrolein.
3.2.1 There is no interference in
the acrolein determination from ordi-
nary quantities of sulfur dioxide, nitro-
gen dioxide, ozone and most organic air
pollutants. A slight interference occurs
134
-------
ALIPHATIC ALDEHYDES
Table 1. Retention Timei Tor Aldehyde*,
Kelonea, Alcohol* and Eater* *
Compound
Acetaldehydr
Propionaldehyde
Acetone
Isobutylraldehyde
Methyl alrohol
Ethyl alcohol
Isopropyl alcohol
Ethyl acetate
n-Butyraldehydr
Methyl-ethyl Icelone
Isopentanal
Crotonaldehydr
Time,
Retention
minutes
3.5
4.6
5.1
5.5
6.1
6.7
6.7
7.0
7.1
7.7
12.0
14.0
• Flow nl«, terancttlure »d condition* oWribrd in
toil.
from dienes: 1.5 per cent for 1,3-buta-
diene and 2 per cent for 1, 3-pentadiene.
The red color produced by some other
aldehydes and undetermined materials
does not interfere in specrropholometric
measurement.
4. Precision and Accuracy
Known standards can be determined
to within :t5 per cent of the true value.
No data are available on precision and
accuracy for atmospheric samples.
5. Apparatus
5.1 Absorbers—All glass standard
midget impingers are acceptable. A
train of 2 bubblers in series is used.
5.2 Air Pump—A pump capable of
drawing at least 2 liters of air/min
for 60 min through the sampling train
is required.
5.3 Air Metering Device—Either a
limiting orifice of approximately 2
liters/min capacity or a glass flow
meter can be used. Cleaning and fre-
quent calibration are required if a limit-
ing orifice is used.
5.4 S\H'rlTH\tholometer—This instru-
ment should lie capable of measuring
the dr\ doped colors al 605 nni and
580 nm. The absorption bands are
rather narrow, and thus a lower absorp-
tivity may be expected in a broad-band
instrument.
5.5 Gas Chromalograph with hydro-
gen flame detector and injection port
sleeve (Varian 1200 or equivalent).
5.6 Boiling Water Bath.
6. Reagents
6.1 Determination of formaldehyde,
6.1.2 Sodium formaldehyde bi-
sulfite (E.K. P6450).
6.1.3 Cliromotropir acid sodium
salt, EK P230. 0.5 per cent in wa-
ter. Filter just before using. Stable
for one week if kept refrigerated.
6.1.4 Sulfuric acid. Concentrated
reagent grade.
6.2 Determination of Acrolein.
6.2.1 HgCl2*4«hexylreBorcinol.
0.30 g HgCJ2 and 2.5 g 4 hexylresorcinol
are dissolved in 50 ml 95 per cent
ethano]. (Stable at least 3 weeks if kept
refrigerated.)
6.2.2 TCAA. To a 1 Ib bottle of
trichloracetic acid add 23 ml distilled
water and 25 ml 95 per cent ethanol.
Mix until all the TCAA has dissolved.
6.3 Collection Medium—Sodium bi-
sulfite, 1 per cent in water.
7. Procedure
7.1 Collection of Samples—Two
midget impingers, each containing 10
ml of 1 per cent NaHSOj are connected
in series with Tygon tubing. These are
followed by and connected to an empty
impinger (for meter protection I and
a dry test meter and a source of suction.
During sampling the impingers are im-
mersed in an ice bath. Sampling rate
of 2 liters/min should be maintained.
Sampling duration will dej>end on the
concentration of aldehydes in the air.
Om» hour sampling time al 2 liters/min
i« adrqualr for ambient concentrations.
After sampling i* complete, the im
135
-------
pingers are disconnected from the tuin.
the inlet and oullfl lulir* an- capped,
and (he impmgrrs stored in an ice hath
or at 6 C in a refrigerator until analyses
are performed. Cold storage is neces-
sary only if the acrolein determination
cannot be performed within 4 hr of
sampling.
7.2 Analysis of Samples (each im-
pinger is analyzed separately).
7.2.1 Formaldehyde (1) (2).
Transfer a 2-ml aliquot of the absorb-
ing solution to a 25-ml graduated tube.
Add 0.2 ml chromotropic acid, and then.
cautiously, 5.0 ml concentrated sulfurir
acid. Mix well. Transfer to a boiling
water bath and heat for 15 minutes
Cool the samples and add distilled water
to the 10-ml mark. Cool, mix and trans.
fer to a 16-mm cuvette, reading the
transmittance at 580 nin. A blank con-
taining 2 ml of 1 per cent sodium hi-
sulfite should be run along with the
samples and used for 100 per cent T
setting. From a standard curve read
micrograms of formaldehyde.
7.2.2 Acrolein (1) (3).
To a 25-mI graduated tube add an
aliquot of the collected sample in bi-
sulfite containing no more than 30 /*g
acrolein. Add 1 per cent sodium bisul-
fite (if necessary) to a volume of 4.0
ml. Add 1.0 ml of the HgCI-4-hexylre-
sorcinol reagent and mix. Add 5.0 ml
of TCAA reagent and mix again. Insert
in a boiling water bath for 5-6 min.
remove, and set aside until tubes reach
room temperature. Centrifuge samples
at 1500 rpm for 5 min to clear slight
turbidity. One hour after heating, read
in a spectrophotometer at 605 nm
against a bisulfite blank prepared in
the same fashion as the samples
7.2.3 C,-C5 Aldehydes (1).
7.2.3.1 Analytical column—12' x
Vs" stainless steel packed with 15 per
cent w/w Carbowax 20 M on Chromo-
sorb, 60-80 mesh, followed by 5' x y8"
stainless steel Uncondinonylphthalate
on firebrick, 100-200 mesh, prepared as
follows: Ucon 50.HB-2(H), 1.5 g,
1.4 g of dinonylphthalale are dissolved
in chloroform and added to 13 g of
firebrick. The solvent is evaporated
at room temperature and the column
packed in the usual manner.
7.2.3.2 Injection port sleeve—
The inlet of the injection port contains
a glass sleeve packed with solid Na2CO.v
The Na2CO3 is held in place with glass
wool plugs.
7.2.3.3 Conditions—
Injection port temperature, 160-170 C
Column temperature, 105 C
Detector temperature, 200 C
Nitrogen carrier gas flow rate,
14 ml/min
Hydrogen flow rate, 20 ml/min
Combustion air flow rate, 400/min
7.2.3.4 Procedure—A 4 ^1 sample
of the bisulfite collection solution is
injected into the packed sleeve at the
injection port and the chromatogram
is recorded. Table 1 shows the relative
retention times for a series of aldehydes
and ketones in the Co-Cj range.
8. Calibration
8.1 Formaldehyde.
8.1.1 Preparation of standard
curve. To a 1 liter volumetric flask
add 0.4466 g sodium formaldehyde bi-
sulfite and dilute to volume. This solu-
tion contains 0.1 rng formaldehyde per
milliliter. Dilute to obtain standard
solutions containing 1, 3, 5 and 7 pg
formaldehyde per milliliter. Treat 2-ml
aliquots as described in the procedure
for color development. Read each at
580 nm after setting instrument at
100 per cent T with the blank. Using
semi log paper, graph the respective con-
centrations vs. transmittance.
8.2 Acrolein,
8.2.1 Preparation of standard
curve. To 250 ml of 1 per cent sodium
bisulfite add 4.0 *J freshly distilled acro-
lein. This yields a standard containing
13.4 /ig/ml. To a series of tubes add
136
-------
ALIPHATIC ALDEHYDES
0.5, 1.0, 1.5, and 2.0 ml of standard.
Adjust the volumes to 4.0 nil with 1
per cent bisulfite and develop color as
described above. Plot data on semi-tog
paper.
8.3 Ct-Cs Aldehydes.
8.3.1 Calibration. A mixed stan-
dard of Cr-Cs aldehydes and ketones is
prepared as follows:
a. Acetaldehyde-bisulfite solution: 0.336
g CH3 CHO-NaHS03 (EK 791) is
dissolved in 1 liter of 1 per cent
NaHS03. This gives a solution con-
taining 100 fig/ml acetaldehyde.
b. To 10.0 ml of the above solution are
added 40.0 ml of 1 per cent NaHSOs,
and 8 ftl of a mixture of equal volumes
of propanal, isobutanal, butanal, iso-
pentanal, pentanal crotonaldehyde,
acetone and butanone.
The final solution contains 20 /xg/ml
acetaldehyde and 0.02 pi of each of the
Cz-C-, aldehydes and ketones per milli-
liter. Four microliters of the standard
are injected into the glass sleeve in the
injection port of the chromatograph as
described in the procedure, and the
chromatogram is recorded.
°. Calculations
(1.23 jig formaldehyde = M (vol) at
25 C and 760 Torr I
9.1 Formaldehyde—ppm formalde-
hyde (CH20) =
total micrograms of CHjO in sample
1.23 X sample volume in liters
9.2 Acrolein—
(2.3 /<# acrolein = 1.0 pi (vol) acrulein)
total fig of acrolein in sample
~~ 2.3 X sample volume in liter*
9.3 Aldehydes—Calculation of un-
known sample concentration if made on
the basis of comparative peak heights
between standards and unknowns.
10. Effect of Storage
After sampling is complete, collection
media are stored in an ice bath or re-
frigerator at 6 C. Cold storage is neces-
sary only if acrolein is to be determined.
Under cold storage conditions, analyses
can be performed within 48 hr with
no deterioration of collected samples.
11. References
1. Levigji. D. A.. »d Frldilrin. M. The Dtltimttt
lion of Fornuldthrde, Aerolein »nd Low Molecular
Vei(hl Aldehydei in Industrial Emiwinnt on a Smile
Collected Simple. JAPCA. 20:312. 1«70.
I. Tentative Method lor thr Determination ol Formalae-
brdc io Ihr Alraoiphete, H.L.S. 7:87, 1970.
(S« Part II: hem 1)1. p. l»4).
3. Tentltfrt Method lor the Aiulvtii of Acrolein Conlrnt
of Ike Atraoiphere, H. L. S. 7:179. 1970.
(Srr r.rl II: (l«-m )09. p. I«7).
Subcommittee 4
R. C. SMITH. Chairman
K. J. BRYAN
.M. FELDSTEIN
B. LEVADIF.
F. A. MILLEH
E. K. STCPHENS
N. C. WHITE
137
-------
APPENDIX F
AVERAGE EMISSION FACTORS UNCONTROLLED AND CONTROLLED
FROM THE PEROXIDATION VENT AT A PLANT
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Table F-l lists the average emission factors uncontrolled and
controlled from the peroxidation vent at a plant manufacturing
acetone and phenol from cumene.
138
-------
TABLE F-I. AVERAGE EMISSION FACTORS UNCONTROLLED AND CONTROLLED
FROM THE PEROXIDATION VENT AT A PLANT MANUFACTURING
ACETONE AND PHENOL FROM CUMENE
Emission factor, g/kg phenol produced,
±95% confidence level bound3 'B
Material emitted
Criteria pollutants:0
Total nonmethane hydrocarbons
Chemical substances:
Acetaldehyde
Acetone
Acetophenone
Benzene6
2-Butanone
2-Butenal
t-Butylbenzene
Cumene
Dimethylstyrene
Ethylbenzene
formaldehyde
2-Hydroxy-2-phenylpropane
a-Methylstyrenef
Naphthalene
Propanal
1 •!
Arsenic
Barium
Calcium
Chlorine
Pi
^•uorij^Q
M
agnesium
Inlet to control
device
9.6
<0'0013 ! 10?%
, . + 840%
- 100%
<0.0014
0.22 ± 16%
n nflQ + 200%
u'uoy - 100%
<0.0029 + J20%
<0.0085
t. Q + 240%
b'y - 100%
<0.0005
0.027
n _,B + 460%
U-UJO _ 100%
<0.0019
<0.0005
<0.0005
<0.0017 + "0%
- 100%
<0. 0000006 ± 71%g
<0.0002 * 350%
<0.0006 __ ^QQ%
<0.ooo2 : jjjf
n ftrtAO + 400%x
0.0002 lrtria.
- 100%
•f 280%^"
<0. 00007 t 110Q1
Outlet from control
device
1.8
- 100%
n fin + 860%
°'60 - 100%
<0.0086
0.20 ± 9.4%
0-^0 ! ^
<0-0055 - JoS%%
<0.0022
-------
TABLE F-l (continued)
Material emitted
Emission factor, g/kg phenol produced,
±95% confidence level bound3'"
Inlet to control
device
Outlet from control
device
Manganese
Phosphorus
Potassium
0.000005
.0.0002
Sodium
Sulfur
Titanium
<°-°02 : 100%
<0.0006 * ^0*
<0. 00005 + JJO*
ii
_h
_h
Note.—Values given as less (<) are the amount in the sample only, because
the amount in the in the blank was either greater than the amount in the
sample, or not detected.
The percent error bound for the average emission factor is the root
mean square of the 95% confidence level error bounds at Plant A and
Plant B, It is calculated by
,..
s*t
100
and
Materials without the 95% confidence level error bound were tested once;
therefore, no error bound can be determined.
cNo particulates, nitrogen oxides (NOX), sulfur oxides (SOx)i or carbon
monoxide are emitted.
The total nonmethane hydrocarbon emission factor is the sum of the meth-
ane equivalent emission factors, based on carbon content, for the C2
through Ci6 materials determined by gas chromatographic (GC) analysis.
The total nonmethane hydrocarbon emission factor is not the sum of emis-
sion factors for all nonmethane organic materials.
The benzene emission factors are not representative. A process upset at
one of the two plants sampled resulted in a high level of benzene emissions.
The GC/MS analysis does not distinguish among forms. It was assumed to
be the a form.
The error bound determined from the accuracy for atomic absorption (AA).
wat sampled.
xThe error bound determined from the accuracy for spark source mass
spectrometry (SSMS).
140
-------
APPENDIX G
AVERAGE EMISSION FACTORS FOR THE CLEAVAGE SECTION VENTS
(COMBINED) AT A PLANT MANUFACTURING ACETONE
AND PHENOL FROM CUMENE, 1976 AND 1977
Table G-l lists the average emission factors for the cleavage
section vents (combined) at a plant manufacturing acetone and
Phenol from cumene in 1976 and 1977.
141
-------
TABLE G-l. AVERAGE EMISSION FACTORS FOR THE CLEAVAGE SECTION
VENTS (COMBINED) AT A PLANT MANUFACTURING ACETONE
AND PHENOL FROM CUMENE, 1976 and 1977
Emission factor,
Material emitted g/kg phenol produced^
Criteria pollutants:
Total nonmethane hydrocarbons 0.17
Chemical substances:
Acetone 0.0000060
Acetophenone 0.0000044
Benzene° 0.000031
2-Butanone 0.0000018
2-Butenal 0.000000085
t-Butylbenzene 0.000023
Cumene 0.14
Ethylbenzene 0.0000050
Formaldehyde <0.00000026
2-Hydroxy-2-phenylpropane 0.0000034
Isopentanal 0.00000085
Note.—Values given as less than are the amount in the
sample only, because the amount in the blank was either
greater than the amount in the sample or not detected.
Calculation of the 95% confidence level error bounds is
not possible because some materials were tested once and
because data obtained from industry and used to form the
average emission factors do not have error bounds.
No particulates, NOX, SOX, or carbon monoxide are emitted
£
The total nonmethane hydrocarbon emission factor is the
sum of the methane equivalent emission factors, based on
carbon content, for all nonmethane organic materials.
dThe benzene emission factors are not representative.
A process upset at one of the two plants sampled
resulted in a high level of benzene emissions.
142
-------
APPENDIX H
REPORTED EMISSIONS INFORMATION
Responses to the Air Products and Chemicals, Inc., Houdry Divi-
sion survey (in support of EPA Contract 68-02-0255) have been
analyzed and are presented in Tables H-l to H-8, (personal
communication with L. B. Evans, 9 February 1976). These emission
factors were not used in this report. The reported information
1s, in some instances, out of date because of plant shutdowns,
Codifications, and expansions since the data were reported in
•1-972. The accuracy and precision of the results are also limited
by wide variations in the amount of data reported and the methods
°f determination. The methods of determination reported in the
survey responses are material balances or engineering estimates
(56%), non EPA approved sampling methods (28%), and unknown
sampling methods (16%) . The emission factors determined from the
survey responses are higher than the emission factors determined
ffom sampling and recent industry contact.
More recent emission information was obtained from EPA on two
Plants. Table H-9 presents the information obtained on the
Georgia Pacific Corp., plant at Plaquemine, Louisiana (personal
communication with Vernon C. Parker, 10 March 1976). Emission
factors from this source were used in this report. Also, infor-
!?ation was obtained on the Clark Oil and Refining plant at Blue
jsland, Illinois, (personal communication with Philip J. Mole,
10 March 1976). There are no reported pollutant emissions. All
vents are connected to an afterburner.
143
-------
TABLE H-l. REPORTED EMISSIONS INFORMATION FOR PLANT 1
Emission factor,
g/k? phenol
Emission point Emission produced
Peroxidation vent
Cumene . 3.6
Hydrocarbons 4 . 3
Steam jet vent
Vent
Steam jet vent
Vent
Vent
Steam jet vent
Vent
Vent
Storage tank vents
Fugitive emissions Undetermined
Emission
Determination Emission height.
method control m
Cumene Carbon
condensed. adsorbers.
15.2
21.3
22.9
22.9
22.9
15.2
15.2
22.9
Conservation
vents or none.
Note. — Blanks indicate no information reported.
Hydrocarbon emission factor is based on the nonmethane equivalent i
MEET - . CcMm
where MEEF - methane equivalent emission factor, gAg phenol produced
E - material emission factor, gAg phenol produced
H • material molecular weight, g/g-mole
C • g moles of carbon that a gram of material contains
M - molecular weight of methane, 16.04 g/g-mole
TABLE H-2. REPORTED EMISSIONS INFORMATION FOR PLANT 2
Emission point Emission
Incineration stack .
N0x
Storage tank vents
Emission factor, Emission
gAg phenol Determination Emission height,
produced method control »
Sampled. Incinerator.
2.3
Floating roofs
and none.
16.8
Fugitive emissions None but minor
leakages may
occur.
Note.—Blanks indicate no information reported.
Incinerator not operating when reported) absorbers emit 0.26 gAg phenol of cumene (or
0.32 gAg phenol of total nonmethane hydrocarbons). Nonmethane hydrocarbon emission fac-
tors are the sum of the nonmethane equivalnet emission factor, based on carbon content for
all nonmethane organic materials.
144
-------
TABLE H-3. REPORTED EMISSIONS INFORMATION FOR PLANT 3
Emission ooint
Spent off gas vent
Concentration vent
Emission factor,
gAg phenol Determination Emission
Emission produced method control
Cumene
Formaldehyde.
Hydrocarbons
Cumene
Formaldehyde
Benzene
Toluene
Ethylbenzene
Hydrocarbons
12
1.9
15
0.089
0.0083
0.0043
0.0043
0.0010
0.12
a
GLC analysis Carbon
of acetone adsorbers.
used to
scrub gas
sample.
Gas chromato- Condenser.
graph
analysis.
Emission
height,
26.2
23.2
Cleavage vent
Acetone topping
vent
Acetone tower vent
O-Methylstyrene
vent
Acetone
Hydrocarbons
Acetone
Acetaldehyde
Hydrocarbons
0.28
0.23
6.0
0.31
5.2
Storage tank vents
Cumene
Toluene
Ethylbenzene
Mesityl oxide
Hydrocarbons
0.21
0.043
0.31
0.069
0.75
Material
balance.
Condenser.
None.
GLC analysis
of liquid
used to es-
timate vapor
composition.
Material None.
balance.
GLC analysis None.
of liquid
used to es-
timate vapor
composition.
23.2
26.2
26.2
21.3
Fugitive emissions Minor.
Condensers, con-
servation vents,
and none.
Note.—Blanks indicate no information reported.
a
Gas/liquid chromatography.
Hydrocarbon emission factor is the sum of the methane equivalent emission factors, based on
carbon content, for all nonmethane organic materials.
145
-------
TABLE H-4. REPORTED EMISSIONS INFORMATION FOR PLANT 4
Emission factor. *****??
gAg phenol Determination Emission height,
Emission point Emission produced method control E •
Peroxidation vent
Cumene
Formaldehyde
Benzene .
Hydrocarbons
Cumene hydroper-
oxide wash and
surge tank vent
Cumene
Hydrocarbons
Cumene stripper
vent
Cleavage vent Minor
Wash vent Minor
Phenol-acetone
still Minor
Acetone topping
column vent
Acetone
Acetaldehyde
Hydrocarbons
Acetone column Minor
Separation col-
umn vent Minor
Dewatering
column vent Minor
Storage tank
vents
Engineering Condenser. 21.3
1.6 estimate.
2.6
1.2
4.8
Engineering Condenser. 9'
0.27 estimate.
0.32
i o 0
Vent condenser. *•*•*
Condenser.
None.
Condenser.
94 4
Condenser **'
0.97
0.75
1.35
Condenser.
None.
None.
Floating roofs.
N2 blankets,
conservation
vents, and
none.
Fugitive emissions None.
Note.—Blanks indicate no data reported.
Hydrocarbon emission factors are the sum of the nonmethane equivalent emission factors,
based on carbon content, for all nonmethane organic materials.
146
-------
TABLE H-5. REPORTED EMISSIONS INFORMATION FOR PLANT 5
Emission factor,
gAg phenol
Emission point Emission produced
Peroxidation vent
Concentration and
cleavage vent
Acetone fractions-
tion vent
Cumene column
vent
a-Methylstyrene
column vent
Phenol column
vent
Residue stripping
column vent
Acetone vent
Acetone concen-
tration vent
Batch still vent
Storage tank
vents
Fugitive emissions Total unknown.
Emission
Determination Emission height.
method control B
Recovery system. 13.7
14.4
24.4
32.0
29.0
19.8
19.8
24.4
26.3
29.0
Hone.
Note.—Blanks indicate no information reported.
TABLE n-e. REPORTED EMISSIONS INFORMATION FOR PLANT 6
Emission factor,
g/kg phenol
Emission point Emission produced
Peed purification vent
Peroxidation off gas
scrubber vent
Cumene 2.7
Hydrocarbons 3.2
Cumene hydroper-
oxide concentra-
tion vent
Cunene 0.33
Hydrocarbons 0. 40
Cleavage condenser
vent
Acetone section
scrubber vent
Residual oil
sump vent
Phenolic water
sump vent
Pump drain
sump vent
Water scrubber
stack
Storage tank
vents
Fugitive emissions Hydrocarbons 0.63
Determination Emission
method control
Liquid trap.
Sampled. Scrubber and
condenser.
Sampled. Condenser.
Condenser.
Scrubber.
None.
None.
None.
Scrubber.
Floating roofs,
sealed roofs.
and none.
Emission
height ,
m
34.1
38.1
12.2
6.1
36.6
9.1
7.3
21.3
26.4
Mote.—Blanks indicate no information reported.
Hydrocarbon emission factors are total nonmethane hydorcarbons determined by summing the
"•ethane equivalent (based on carbon content] emission factors for all nonmethane organic
material*.
147
-------
TABLE H-7. REPORTED EMISSIONS INFORMATION FOR PLANT 7
Emission factor. Emission
g/kg phenol Determination Emission height,
Emission point Emission produced method control m
Spent air vent
Cumene 1.9
Hydrocarbons 2 . 3
Storage tank
vents
Fugitive emissions Minor
Material Condensers 26.2
balance!.
Floating roofs.
conservation
vents , con-
densers , and
none.
Note.—Blanks indicate no information reported.
Hydrocarbon emission factor is the cumene emission factor in methane equivalents, based
on carbon content.
TABLE H-8. REPORTED EMISSIONS INFORMATION FOR PLANT 8*
Emission point
Peroxidation vent
Cleavage vent
Finishing vent
Recovery section
Flare
Storage tank vents
Fugitive emissions
Emission factor,
g/kg phenol
Emission produced
Cumene ^
Hydrocarbons
Cumene
Acetone
Hydrocarbons
Acetone
Aldehydes
Hydrocarbons
Cumene
Hydrocarbons
Carbon dioxide
No estimate.
5.4
6.5
0.071
0.042
0.12
3.3
2.4
4.3
0.00089
0.0011
1,500
Determination
method
Engineering
estimate.
Engineering
estimate
Engineering
estimate.
Engineering
estimate.
Engineering
estimate.
Emission
Emission height,
control m
15.2
4.6
15.2
20.4
4.6
18.3
26.3
0.6
4.6
28.3
1.2
Condensers and
none.
Note.—Blanks indicate no information reported.
Not in operation.
Hydrocarbon emission factors are the sum of the methane equivalent emission factors,
based on carbon content for all nonmethane organic materials.
148
-------
TABLE H-9.
REPORTED EMISSION INFORMATION FOR THE GEORGIA-PACIFIC
CORPORATION PLANT AT PLACQUEMINE, LOUISIANA, 1975
Emission point
Peroxidation carbon adsorption vent
Oxidizer vent condenser
Cumene recovery condenser vent
Oxidizer feed drum vent
Recycle cumene tank vent
Cumene storage tank vent
Cleavage ejector condenser vent
Preflash ejector condneser vent
Cleavage tank condenser vent'1
Spent caustic drum
Acetone tower jet condenser vent
Tower reflux drum vent
a-Methylstyrene tower reflux drum vent
a-Methylstyrene tower overhead vent'3
Tower purge separator vent
Phenolic water reflux vent
Acetone tank scrubber vent
Acetone storage tank vent
Phenolic water tank vent
Phenol rundown tank vent
Phenol storage tank vent
Heavy end tower feed tank vent
a-Methylstyrene tower feed tank vent
a-Methylstyrene tower rundown tank vent
a-Methylstyrene day tank vent
Acetone loading area
Phenol loading area
Phenol shipping area
Fugitive: pumps and sewers
Emission factor, g/kg phenol produced
Total nonmethane a-Methyl-
hydrocarbons Cumene Acetone Aromatics Phenol styrene
0.011 0.0088
0.073 0.061
0.020 0.016
0.0020 0.0017
0.0085 0.0071
0.17 0.14
0.011 0.013
0.0012 0.0010
0.0020 _C
0.0077 0.0093
< 0.00004
<0. 00004
0.0033 0.0032
< 0.00004
0.030 0.036
2.5 3.0
0.0020 0.0020
0-0065 0.0064
0.065
0.0053 0.0052
0.011
0.0022 Q 0002
u.uuu^
0.0006 0.0004
0.061 0 0.074
0.073 o.072
°-l3 0.12
0.022
Height,
*>C "5
2b. J
^1 1
£• J • ^
^c o
26.2
6 A
m *t
9Q
• O
o^ o
Zj« 2
01 o
*J. t.
23,2
4 5
^ • j
24 7
**t . /
1C
. j
13 1
X
-------
APPENDIX I
DERIVATION OF SOURCE SEVERITY EQUATIONS
SUMMARY OF SEVERITY EQUATIONS
The severity of pollutants may be calculated using the mass
sion rate, Q, the height of the emissions, H, and the threshold
limit value, TLV. The equations summarized in Table 1-1 are
developed in detail in this appendix.
TABLE 1-1. POLLUTANT SEVERITY EQUATIONS
FOR ELEVATED POINT SOURCES
Pollutants _ Severity equation
Particulate S - ?Q
s -
Hydrocarbon S =
Carbon monoxide S = „,
H*-
S '
DERIVATION OF X FOR USE WITH U.S. AVERAGE CONDITIONS
max
The most widely accepted formula for predicting downwind groun
level concentrations from a point source is (89):
x- Q
(89) Turner, D. B. Workbook of Atmospheric Dispersion Estimat
Public Health Service Publication No. 999-AP-26, U.S.
Department of Health, Education, and Welfare, Cincinnati/
Ohio, May 1970. 84 pp.
150
-------
where x = downwind ground level concentration at reference
coordinate x and y with emission height of H, g/m3
Q = mass emission rate, g/s
7T = 3.14
a = standard deviation of horizontal dispersion, m
o = standard deviation of vertical dispersion, m
u = wind speed, m/s
y = horizontal distance from centerline of dispersion, m
H = height of emission release, m
x = downwind dispersion distance from source of emission
release, m
y ,
Amax xs assumed to occur when x is much greater than 0 and when
V equals 0. For a given stability class, standard deviations
of horizontal and vertical dispersion have often been expressed
as a function of downwind distance by power law relationships
as follows (90):
oy = axb (1-2)
c = cxd + f (1-3)
z
for a, b, c, d, and f1 are given in Tables 1-2 (91) and
". Substituting these general equations into Equation 1-1
Yields:
X = xTTi-^ VT expf -^ ] (1-4)
+ arruf'xb L 2 (cxd + f')2J
Assuming that Xmax occurs at x less than 100 m or the stability
class is C, then f equals 0 and Equation 1-4 becomes:
Q f -H2 n *\
X = u-i./i exP J d-5)
acTruxb+d [2c2x2d.
°r convenience, let:
AR = -S— and BR " ^
R acnu R 2c2
So +-^ = 4. Equation 1-5 reduces to:
Martin, D. O., and J. A. Tikvart. A General Atmospheric
Diffusion Model for Estimating the Effects on Air Quality
of One or More Sources. Presented at the 61st Annual
Meeting of the Air Pollution Control Association, St. Paul,
Minnesota, June 23-27, 1968. 18 pp.
•*-) Tadmor, J. , and Y. Gur. Analytical Expressions for the
Vertical and Lateral Dispersion Coefficients in Atmospheric
Diffusion. Atmospheric Environment, 3 (6):688-689, 1969.
151
-------
TABLE 1-2. VALUES OF a FOR THE
COMPUTATION OF a a (91)
Stability class
A
B
C
D
E
F
0.3658
0.2751
0.2089
0.1471
0.1046
0.0722
For the equation
= ax
where x = downwind distance
b = 0.9031 (from
Reference 46)
TABLE 1-3.
VALUES OF THE CONSTANTS USED TO
ESTIMATE VERTICAL DISPERSION3 (90)
Stability
Usable range, m class
>1,000 A
B
C
D
E
F
100 to 1,000 A
B
C
D
E
F
Coefficient
GI
0.00024
0.055
0.113
1.26
6.73
18.05
c2
0.0015
0.028
0.113
0.222
0.211
0.086
di
2.094
1.098
0.911
0.516
0.305
0.18
d2
1.941
1.149
0.911
0.725
0.678
0.74
fi'
-9.6
2.0
0.0
-13
-34
-48.6
fa1
9.27
3.3
0.0
-1.7
-1.3
-0.35
<100
A
B
C
D
E
F
0.192
0.156
0.116
0.079
0.063
0.053
0.936
0.922
0.905
0.881
0.871
0.814
0
0
0
0
0
0
For the equation
° * cx
f1
152
-------
X = ARx
-(brf-d)
exp
'B,
(1-6)
waking the first derivative of Equation 1-6
- 2dBRx
+ exp
- b - d x
-b-d-1
(1-7)
and setting this equal to zero (to determine the roots which
9ive the minimum and maximum conditions of X with respect to x)
yields:
.*p[v"d])[-
*»Rx
-'d
- a]
(1-8)
Since we define that x ? 0 or » at Xmax, the following expres-
sion must be equal to 0:
- 2dBx"2d - d - b = 0
d-9)
or
or
or
(b + d)x2d = - 2dB.
x
2d _ " 2dBR
2d
b + d 2c2(b + d)
x
2d
d H:
c2(b + d)
(1-10)
(1-12)
= /_AJl!_\
\c2(b + d)/
V2d
at x
max
s Equations 1-2 and 1-3 become:
/ d ;
b/2d
-
o =
b)
(1-13)
(1-14)
153
-------
°2
- J d H2 \ G/2d /d_H2 \ '* (I.
- c( 2/. , .. ) =lb-T-d (
\c "'(b + d) / \ /
The maximum will be determined for U.S. average conditions of
stability. According to Gifford (92), this is when o =
-------
or
For U.S. average conditions, u = 4.47 m/s so that Equation 1-20
reduces to:
DEVELOPMENT OF SOURCE SEVERITY EQUATIONS
The general source severity, S, relationship has been defined as
follows:
S = (1-22)
where Xmax = maximum time-averaged ground level concentration
F = hazard factor defined as the ambient air quality
standard for criteria pollutants and a modified
TLV (i.e., TLV • 8/24 • 1/100) for noncriteria
pollutants
Emissions
The value of Xmax may t>e derived from Xmax, an undefined "short-
term" (to) concentration. An approximation for longer term con-
Centration (ti) may be made as follows (89):
a 24-hr time period,
0.17
X = X r2 (1-23)
Amax Amax * *• - '
or
0.17
- _ I 3 min
^max ~ xmax \1,440 min
= Y (0.35) (1-25)
max Amax
155
-------
Since the hazard factor is defined and derived from TLV values
as follows:
P = (3.33 x 10~3) TLV (1-27)
then the severity factor, S, is defined as:
S =
((K35)X
max
F (3.33 x ID" 3) TLV
105 X
•max
TLV
If a weekly averaging period is used, then:
- - ( 3 V'17
xmax xmax \10,0807
or
' <°-25>Xmax
and
40
156
(1-28)
(1-29)
F -
F ~
F 8 x 10~3)TLV (1-33)
and the severity factor, S, is:
S =
F (2.38 x 10"3)TLV
or
ax (1-3^)
TLV
-------
which is entirely consistent, since the TLV is being corrected
ror a different exposure period.
Therefore, the severity can be derived from Xraax directly without
regard to averaging time for noncriteria emissions. Thus, com-
bining Equations 1-35 and 1-21, for elevated sources, gives:
S =
5.5 Q
TLV • H2
(1-36)
Criteria Emissions
For the criteria pollutants, established standards may be used
as F values in Equation 1-22. These are given in Table 1-4.
However, Equation 1-23 must be used to give the appropriate aver-
aging period. These equations are developed for elevated sources
using Equation 1-21.
TABLE 1-4.
SUMMARY OF NATIONAL AMBIENT
AIR QUALITY STANDARDS (93)
Pollutant
Particulate
matter
so
X
Carbon
monoxide
Nitrogen
dioxide
Photochemical
oxidants
Hydrocarbons
(nonme thane)
Averaging
time
Annual (geometric
mean)
2 4 -hour b
Annual (arith-
metic mean)
24-hourb
3-hourb
8 -hour b
l-hourb
Annual (arith-
metic mean)
l-hourb
3 -hour
(6 a.m. to 9 a.m.)
Primary
standards
75 ug/m3
260 ug/m3
80 ug/m3
365 ug/m3
-
10,000 ug/m3
40,000 ug/m3
100 vg/m3
160 ug/mj
160 ug/m3d
Secondary
standards
60* ug/m3
160 pg/m'
60 ug/m}
260C ug/m3
1,300 ug/m3
(Same as
primary)
(Same as
primary)
(Same as
primary)
(Same as
primary)
*The secondary annual standard (60 ug/m3) is a guide for assess-
ing implementation plans to achieve the 24-hour secondary
standard.
Not to be exceeded more than once per year.
cThe secondary annual standard (260 ug/m3) is a guide for assess-
ing implementation plans to achieve the annual standard.
dThere is no primary ambient air quality standard for hydro-
carbons. The value of 160 ug/m3 used for hydrocarbons in this
report is an EPA recommended guideline for meeting the primary
ambient air quality standard for oxidants.
(93) Code of Federal Regulations, Title 42 - Public Health,
Chapter IV - Environmental Protection Agency, Part 410 -
National Primary and Secondary Ambient Air Quality
Standards, April 28, 1971. 16 pp.
157
-------
carbon Monoxide Severity— .
The primary standard for CO is reported for a 1-hr averaging T-J-"
Therefore,
t = 60 min
t = 3 min
o
/ \ 0 . 1 7
( 3 ) (1-37)
V I — — / \ *^
Amax\60 /
0 . 1 7
= 2 Q _3
TieuH2 \60
(3.14) (2.72) (4.5)H2
Amax H2
(3.12 x 10~2)Q (1-41)
xmax 2
Y j. O ^
TTI3 V / T — •! ^ '
Severity, S = °ld* li
o
Setting F equal to the primary standard for CO, i.e., 0.04 g/
yields:
s = xmax = (3.12 x 10"2)Q (1-43)
F 0.04 H2
or
Q 0.78 Q (1-44)
sco —^r~
Hydrocarbon Severity—
The primary standard for hydrocarbon is reported for a 3-hr
averaging time.
ti = 180 min
158
-------
t = 3 min
o
xmax xmax \1807 (1-45)
= 0.5x_ax (1-46)
max y
(0.5) (0.052) Q
H2
= °'°26 Q
(
(1-48
v
For hydrocarbons, the concentration of 1.6 x 10~4 g/m3 has been
Issued as a guideline for achieving oxidant standards. Therefore,
s = xmax _ 0.026 Q
F 1.6 x 10-4 H2
or
s = 162.5 0 (1-50)
;gj-—^—^u.^i.c Severity—
rhe primary standard for particulate is reported for a 24-hr
averaging time.
/ \0.17
xmax = xmax \1,440/ (1-51)
_ (0.052) Q (0.35) (1-52)
H2
xmax
_ (0.0182) Q (1-53)
Particulates, F = 2.6 x lO"1* g/m3/ and
s = ^"iax = 0.0182 Q
F 2.6 x 10-" H2
159
-------
Q _ 70 Q (I-55)
p ~ 7~
* H2
SOv Severity—
SUx severity—
The primary standard for SOX is reported for a 24-hr averaging
time. Using t1 = 1,440 minutes and proceeding as before:
- _ (0.0182) Q (I
xmax
-56)
The primary standard is 3.65 x lO'1* g/m3,
and
s ^ xmax = (0.0182)0 I
F 3.65 x 10-14 H2
or
c _ 50 Q d-58)
SO ~ -,
x H2
NOX Severity—
Since NOX has a primary standard with a 1-yr averaging time*
Xmax correction equation cannot be used. As an alternative/
following equation was selected:
A difficulty arises, however, becaus^e a distance x, from emi i&
point to receptor, is included; hence, the following rational
used:
The equation x«,a« =
lUclX -- 9
neuH^
is valid for neutral conditions or when a s a . This maxim
occurs when z ^
/t-60)
H s /2~o
z
and since, under these conditions,
°9 - axb (l
Z
160
-------
then the distance, x , where the maximum concentration occurs is-
max
For class C conditions,
a
b
0.113
0.911
Simplifying Equation 1-59,
(1-62)
(1-63)
and
u = 4 . 5 m/s
Letting x =
where
x in Equation 1-59 ,
rricix
• 4° expf- \ (j
xn,ax'-911 L ^°
max
H \
.16/
1.098
(1-64)
(1-65)
(1-66)
and
4 Q
4 Q
x 1.911 /y 5 Hl .098) 1 .911
max
X =
H
(1-67)
(1-68)
o = 0.113x°-911
z
(1-69)
161
-------
(1-70)
o = 0.113 (7.5 H1-1)0'911
z
o = 0.71 H
z
Therefore,
- = 0.085 Q e F 1 / _H V I d-72)
H2-1 L
= °-085 Q (0.371)
H2.1
3.15 x 10~2 Q
Since the NO standard is 1.0 x lQ-k g/m3, the N0x severity
equation is:
= (3.15 x IP"2) Q (I
1 x 10-u H2-1
•75)
~'
315 Q (1-76)
AFFECTED POPULATION CALCULATION
Another form of the plume dispersion equation is needed to c
late the affected population since the population is assumed ^
be distributed uniformly around the source. If the wind <^1*i
tions are taken to 16 points and it is assumed that the wind
directions within each sector are distributed randomly overrfiu-
period of a month or a season, it can be assumed that the e£ Qf
ent is uniformly distributed in the horizontal within the se
The appropriate equation for average concentration, x» ^n \{.
is then (for 100 m <^ x _< 1,000 m and stability class C) (94) •
ozux
(94) Schwartz, W. A., et al. Engineering and Cost Study of J
Pollution Control for the Petrochemical Industry, voiun
Carbon Black Manufacturing by the Furnace Process
EPA-450/3-73-006a, U.S. Environmental Protection
Research Triangle Park, North Carolina, June 1974.
162
-------
° find the distances at which x/F = 0.1, roots are determined
Or the following equation:
2.03 Q
Fa ux
z
exp
[1 / «'
- —I—
o I
£ \ u
\ z,
= 0.1
(1-77)
in mind that:
a =
z
+ f
"ere a, b, and f' are functions of atmospheric stability and are
to be selected for stability Class C. Since Equation 1-77
a transcendental equation, the roots are found by an iterative
using the computer.
For
Distance might look as follows:
f specified emission from a typical source, x/F as a function
The
DISTANCE FROM SOURCE
7
Figure I-l. F as a function of distance from source.
affected population is contained in the area
A = Tr(x22 - X!2)
(1-78)
affected population density is Dp, the total affected popu-
P, is
P = DpA (persons)
(1-79)
163
-------
APPENDIX J
SIMULATED SOURCE SEVERITY DISTRIBUTIONS
Simulated source severity distributions for chemical substance
emitted from the cumene peroxidation vent are presented in
Figures J-l through J-9.
164
-------
LH
SflMPLE SIZE = 5000
MIN. VflLUE = 0.000001
MflX. VflLUE = 0.004224
MEflN = 0.000620
STD. OEV. = 0.000512
0.11 O'.U O'.IS 0.19
BCETBLOEHY0E SEVERITY
o.tt
o.«* o.rr
• ID*
0.30
O.K
O.W
o.n
Figure J-l. Simulated source severity for acetaldehyde
emitted from the cumene peroxidation vent.
-------
8
I
8
81
8
81
5*
581
&
en
81
8
SRMPLE SIZE = 5000
KIN. VflLUE = 0.000007
flflX. VflLUE = 0.087414
HERN = 0.011804
STO. OEV. = 0.011427
0,9*
t.fl«
.1C
.
flCETONE SEVERITY
D.M
I.4S
•.ii
Figure J-2.
Simulated source severity for acetone
emitted from the cumene peroxidation vent,
-------
(Ti
•-J
SflMPLE SIZE = 5000
MIN. VRLUE = 0.081986
MRX. VflLUE = 4.908799
HERN = 1.080967
STD. OEV. = 0.770110
Figure J-3. Simulated source severity for benzene emitted
from the cumene peroxidation vent.3
The benzene emission factors are not representative. A process upset at one of the
two plants sampled resulted in a high level of benzene emissions.
-------
00
SflflPLE SIZE = 5000
MIN. VflLUE = 0.000065
HflX. VflLUE = 0.029486
HERN = 0.004432
STD. DEV. = 0.003638
OM oIS JIw ?at
2-8UTflN8NE SEVERITY
n
.1*
• I0i
Figure J-4.
Simulated source severity for 2-butanone
emitted from the cumene peroxidation vent.
-------
8
*
&
en
vo
8
S
SflMPLE SIZE = 5000
MIN. VflLUE = 0.012927
MflX. VflLUE = 0.976905
MEflN = 0.186145
STD. DEV. = 0.138610
o.u
Figure J-5.
Simulated source severity for cumene
emitted from the cumene peroxidation vent.
-------
B
8,
8
8
8
ft
SflHPLE SIZE = 5000
MIN- VflLUE = 0.000000
flflX- VflLUE = 0.000686
HERN = 0-000064
STD. OEV. = 0-000067
.00 0.«
OJU
""" ET'HYLBENZENE
.i i
o'.ic
8.1*
P.W
10-.
t.n
o.u
too
Figure J-6.
Simulated source severity for ethylbenzene
emitted from the cumene peroxidation vent.
-------
SflMPLE SIZE = 5000
MIN. VflLUE = 0.000004
MflX. VflLUE = 0.341705
MEflN = 0.023366
STD. OEV. = 0.024323
O.K O.M O.J3
FWHWLDEHYDE SEVERITY
O.M
0.4*
0.10
o.re
• 10-.
D.M
O.M
0.11
O.TJ
Figure J-7.
Simulated source severity for formaldehyde
emitted from the cumene peroxidation vent.
-------
2*
NJ
SflMPLE SIZE = 5000
MIN. VflLUE = 0.000000
MflX. VflLUE = 0.000214
HERN = 0.000015
STO. OEV. = 0.000015
1.04
0.11
BLPHfl-nETHvLsTifREHE SEVERITY
O.M
.11
0.34
• 10-t
O.M
Figure J-8.
Simulated source severity for a-methylstyrene
emitted from the cumene peroxidation vent.
-------
O.M o.n o.is o.n
SflMPLE SIZE = 5000
MIN. VflLUE = 0.000000
MflX- VflLUE = 0-002010
MEflN = 0-000137
STD. DEV. = 0-OOOU3
NflPHTHflLEH*"
• 1(
o.n o.« o.*»
Figure J-9. Simulated source severity for naphthalene
emitted from the cumene peroxidation vent,
-------
APPENDIX K
AFFECTED POPULATION CALCULATIONS
Affected populations were calculated by the procedure outlined
in Section 4 and Appendix I. Input data and results for the
emission sources are shown in Tables K-l to K-7 When the source
severity is less than or equal to 0.1, the affected population is
reported as zero.
174
-------
TABLE K-l.
ESTIMATED AFFECTED POPULATIONS: CUMENE PEROXIDATION VENT EMISSIONS FROM
A REPRESENTATIVE SOURCE MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Material1"
Total nonmethane
hydrocarbons
Acetaldehyde
Acetone
Benzene9
2-Butanone
Cumene
Ethylbenzene
Formaldehyde
a-Methylstyrene
Naphthalene
Hazard factor =
Emission
rate,
Q/s
6.2
0.0072
2.1
0.69
0.17
3.0
0.0014
0.0034
0.00034
0.00034
TLV • 8/24
Emission
height,
m
17.1
17.1
17.1
17.1
17.1
17.1
17.1
17.1
17.1
17.1
• 1/100 for
Data
TLV,
q/B,3
NAf
0.180
2.400
0.030
0.590
0.245
0.435
0.003
0.480
0.050
input
Hazard
factor,
q/m3
160 x 10~6
6 x 10-"
0.0080
9.9 x 10-5
0.0020
0.00082
0.0015
1.0 x 10~5
0.0016
0.00017
Data output
Hind
speed,
ra/s
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
Population
density,
persons/km2
1,333
1,333
1,333
1,333
1,333
1,333
1,333
1,333
1,333
1,333
Root
xi, C
km
0.96
0
0
0.076
0
0.087
0
0
0
0
Root
*2.
1.7
0
0
0.68
0
0.46
0
0
0
0
Affected
area,"
tan2
6.2
0
0
0
0
0
0
0
0
0
Affected
population,6
8,300
0
0
0
0
0
0
0
0
0
noncriteria pollutants.
cThe distance to the plant boundary is used when xj is less than 0.96 tan.
The affected area is reported as 0 when both x, and x2 are less than 0.96 km, which is the distance to the plant
boundary.
The affected population is determined by multiplying the affected area by the capacity weighted mean county
population density. The population is, of course, not distributed uniformly throughout the county; therefore, in
the plant vicinity, the population density may be lower or higher than the county average.
Not applicable.
The benzene emission factors are not representative. A process upset at one of the two plants sampled resulted in
a high level of benzene emissions. '
-------
TABLE K-2.
ESTIMATED AFFECTED POPULATIONS: CLEAVAGE SECTION VENT EMISSIONS (COMBINED)
FROM A REPRESENTATIVE SOURCE MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Data input
Material
Total nonmethane
hydrocarbons
Acetone
Benzene'
2-Butanone
Curaene
Ethylbenzene
Formaldehyde
Emission
rate,
9/s
0.59
2.1 x 10-5
1.1 x 10-"
6.2 x 10~«
0.48
1.7 x lO"6
9.0 x 10-'
Emission
height, TLV,
B g/m3
12.8
12.8
12.8
12.8
12.8
12.8
12.8
NAB
2.400
0.030
0.590
0.245
0.435
0.003
Hazard Wind
factor, speed,
g/m3 m/s
160
0
9.9
0
0
0
1.0
x ID'6 4.5
.0080 4.5
x ID'5
.0020
.00082
.0015
x 10~s
.5
.5
.5
.5
.5
Population
density,
persons/km2
1,333
1,333
1,333
1,333
1,333
1,333
1,333
Root
xi, c
km
0.056
0
0
0
0
0
0
Data output
Root Affected
x2, area.d
km km2
0.49
0
0
0
0
0
0
0
0
0
0
0
0
0
Affected
population ,
persons
0
0
0
0
0
0
0
'Hazard factor - TLV • 8/24 • 1/100 for noncriteria pollutants.
bOnly materials which have TLV's or hazard factors are listed.
°The distance to the plant boundary is used when xi is less than 0.96 km.
dThe affected area is reported as 0 when both xi and x2 "» less than 0.96 km, which is the distance to the plant
boundary.
eThe affected population is determined by multiplying the affected area by the capacity weighted mean county
population density. The population is, of course, not distributed uniformly throughout the county? therefore, in
the plant vicinity, the population density may be lower or higher than the county average.
ftiot applicable.
9The benzene emission factors are not representative. A process upset at one of the two plants sampled resulted in
a high level of benzene emissions.
TABLE K-3.
ESTIMATED AFFECTED POPULATIONS: PRODUCT PURIFICATION VENT
EMISSIONS (COMBINED) FROM A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Data input
Material6
Total nonmethane
hydrocarbons
Emission
rate,
J/S
4.1
Emission
height,
m
26.5
TLV
g/m3
NAf
Hazard
factor
g/m3
160 x 10-'
Hind
speed ,
m/s
4.5
Population
density,
persons/km2
1,333
Rootc
X],
km
0.96
Root
*2-
km
1.4
Data output
Affected
area,d
km2
2.9
Affected
population,
persons
4,300
aHazard factor = TLV • 8/24 • 1/100 for noncriteria pollutants.
bOnly materials which have TLV's or hazard factors are listed.
cThe distance to the plant boundary is used when xi is less than 0.96 km.
''The affected area is reported as 0 when both X) and xz are less than 0.96 km, which is the distance to the plant
boundary.
£The affected population is determined by multiplying the affected area by the capacity weighted mean county popu-
lation density. The population is, of course, not distributed uniformly throughout the county; therefore, in the
plant vicinity the population density may be lower or higher than the county average.
Hot applicable.
-------
TABLE K-4.
ESTIMATED AFFECTED POPULATIONS: STORAGE TANK VENT EMISSIONS FROM A
REPRESENTATIVE SOURCE MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Material*
Emission
rate.
q/S
Emission
height,
m
TLV,
Hazard
factor,
g/m'
Wind
speed,
m/s
Population
density,
persons/km2
Root Root
X,.C X2,
km km
Affected Affected
area,** population,
tan* persons
Total nonmethane
hydrocarbons
Acetone
Total nonmethane
hydrocarbons
Cumene
Total nonmethane
hydrocarbons
o-Methylstyrene
Total nonmethane
hydrocarbons
Phenol9
Total nonmethane
hydrocarbons
h
Phenol"
0.17
0.21
0.12
0.097
0.0083
0.0069
0.047
0.047
0.1
0.1
15.2
15.2
15.2
15.2
6.1
6.1
9.1
9.1
15.2
15.2
NAT
2.400
NA
0.245
NA
0.480
NA
0.019
NA
0.019
160
0.
160
0.
160
x 10-*
0080
x 10~*
00082
x 10~6
0.0016
160
6.3
160
6.3
x 10-6
x 10- 5
x 10-6
x 10- 5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
1,333
1,333
1,333
1,333
1,333
1.333
1.333
1.333
1,333
1,333
0.12
0
0
0
0
0
0
0.047
0
0.081
0.19
0
0
0
0
0
0
0.20
0
0.35
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
o
0
0
0
Hao-ATH fan*-t\v = TTA7 • P /OA • 1 /I nft f*~. «n_>«_j «.A«i _ i i ._* *__
8/24 • 1/100 for noncriteria pollutants.
"Only materials which have TLV's or hazard factors are listed.
The distance to the plant boundary is used when X] is less than 0.96 km.
bo'und"y?ted aCea 1S rep°rted as ° wnen **>** x> and *2 are less than 0.96 km, which is the distance to the plant
etionadenlity.^TheaPipIllitiontiriSfdcourseltnolyi"9 ^ affect?d area b* the "F^city weighted mean county popula-
Not applicable.
9
Emission from heavy ends storage tank assumed to be phenol.
-------
TABLE K-5.
ESTIMATED AFFECTED POPULATIONS: PRODUCT TRANSPORT LOADING VENTS (COMBINED)
AT A REPRESENTATIVE SOURCE MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Data input
Material1"
Total nonmethane
hydrocarbons
Acetone
Phenol
Emission
rate,
g/s
0.59
0.26
0.389
Emission
height,
m
9.1
9.1
9.1
TLV
g/m3
NAf
2.400
0.019
Hazard
factor
g/m'
160 x 10~6
0.0080
6.3 X 10~5
Wind
speed,
m/s
4.5
4.5
4.5
Population
density,
persons/km2
1,333
1,333
1,333
Root
*l-c
km
0.034
0
0.032
Data output
Root
*2.
km
0.50
0
0.65
Affected
area , d
km2
0
0
0
Affected
population,
persons
0
0
0
Hazard factor = TLV • 8/24 • 1/100 for noncriteria pollutants.
Only materials which have TLV's or hazard factors are listed.
The distance to the plant boundary is used when Xi is less than 0.96 km.
The affected area is reported as 0 when both x, and x2 are less than 0.96 tan, which is the distance to the plant
boundary.
The affected population is determined by multiplying the affected area by the capacity weighted mean county popula-
lation density. The population is, of course, not distributed uniformly throughout the county; therefore, in the
plant vicinity the population density may be lower or higher than the county average.
Not applicable.
"The emission factor is an average of two estimates.
CO
TABLE K-6.
ESTIMATED AFFECTED POPULATIONS: FUGITIVE
EMISSIONS3 FROM A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
Data input
Material1*
Total nonmethane
hydrocarbons
Emission
rate,
?/s
0.076
Emission
height,
m
4.6
TLV,
g/m3
NA*
Hazard
factor,
^/m'
160 x 10-»
Hind
speed ,
m/s
4.5
Population
density,
persons/km2
1,333
Root
x,,
km
0.018
Data output
Root
Xa,
km
0.17
Affected
area,
km*
0
Affected ,
population,
persons
0
aThe fugitive emissions estimate includes those from pumps and sewers only. The other sources of fugitive emissions
are not included in this estimate.
Only materials which have TLV's or hazard factors are listed.
°Hazard factor - TLV • 8/24 • 1/100 for noncriteria pollutants.
The distance to the plant boundary is used when x, is less than 0.96 km.
eThe affected area is reported as 0 when both x, and x, are less than 0.96 km, which is the distance to the plant
boundary.
The affected population is determined by multiplying the affected area by the capacity weighted mean county popula-
tion density. The population is, of course, not distributed uniformly throughout the county! therefore, in the
plant vicinity the population density may be lower or higher than the county average.
g»ot applicable.
-------
APPENDIX L
PLUME RISE CORRECTION
Factors designed to quantify the potential hazard of manufacture
of acetone and phenol from cumene were generated in Section 4
using the Gaussian plume equation to predict ground level concen-
trations. These factors are source severity and affected
population. The Gaussian plume equation contains a factor called
the effective stack heigh, H. This is equal to the sum of the
physical stack height, h1, and the amount of plume rise, AH;
H = h1 + AH (L-l). An exhaust plume rises before dispersal due
to its exit velocity and temperature. This plume rise for plants
manufacturing acetone and phenol from cumene is not a significant
effect, that is:
AH/h1 <50%
(L-2)
In Section 4, source severity and affected population were there-
fore calculated assuming no plume rise; i.e., the effective
emission height was equated with the physical stack height.
DETERMINATION OF PLUME RISE
Plume rise can be estimated from the Holland formula (89):
AH =
V D.
s i
U
1.5 + (2.68 x 10~3)p
(L-3)
where AH = plume rise; m
Vs = stack gas exit velocity, m/s
Di = inside stack diameter, m
U = wind speed, m/s
p = atmospheric pressure, mb
Ts = stack gas temperature, °K
Ta = ambient temperature, °K.
Under Class C stability conditions AH is corrected by a factor
of 1.10.
Using values from the material balance given in Table 7, the
stack gas exit velocity can be found from
179
-------
• U • k, • ks • _2 (L-4)
\ *• /
where Es = g of stack gas per kg phenol produced
MS = molecular weight of stack gas, g/g mole
Cap = representative source phenol capacity, kg/yr
U = utilization factor
ki = conversion constant, yr/s
k5 = conversion constant, m3/g mole.
The conversion constant, k5, is determined using
R Tg
ks = ~P
s
where Ts = stack gas temperature, °K
R = universal gas constant, 8.31 x 10~3 mole °K
PS = stack gas pressure, kPa.
All gas streams are assumed to be ambient temperature (292°K)
and atmospheric pressure (101.33 kPa) based on observations at
the sampling sites. Therefore, k5 = 0.024 m3/g mole.
Table L-l presents the values of Vs, D-^, Es, and Ms used to
determine the estimated plume rise also shown in that table. Tn
following values were used for all cases:
u = 4.5 m/s
p = 1,013 mb
Ts = Ta = 292°K
Cap = 136 x 106 kg/yr
U = 0.80
k! = 3.169 x 10~8 yr/s
k5 = 0.024 m3/g mole.
If plume rise is taken into account the source severity should
be correct (multiplied) by the following factor:
h' + AH
k >
This is also presented in Table L-l. Table L-2 presents an
example of the usage of this factor on source severities for tn
cumene peroxidation vent.
180
-------
TABLE L-l. PLUME RISE ESTIMATES FOR A REPRESENTATIVE SOURCE
MANUFACTURING ACETONE AND PHENOL FROM CUMENE
oo
Cumene
Equation peroxidation
variables vent
Vg, m/s
D±b, m
E
s
Ms
AH, m
h* , m
AH/h1
( hl Vd
\h' + AH//
32.1
0.508
2.236
28.4
6.0
17.1
35%
0.55
Combined
cleavage
section vent3
0.00532
0.152
0.140
120
0.0003
12.8
0.4%
1.0
Combined
product
purification
section venta
0.342
0.152
1.20
16
0.02
26.5
0.08%
1.0
Combined
storage
tank venta
0.00765
0.152
0.141
84
0.0004
13.3°
0.003%
1.0
Combined
product
transport
loading vent
0.0105
0.152
0.184
80
0.0006
9.1
0.007%
1.0
All vents in that section are treated as one vent.
^Estimated.
"Average of all storage tank heights.
Plume rise correction factor for source severity where plume rise was treated as zero
corrections.
-------
TABLE L-2.
SOURCE SEVERITIES OF ATMOSPHERIC EMISSIONS FROM THE
CUMENE PEROXIDATION VENT WITH AND WITHOUT PLUME
AT A REPRESENTATIVE SOURCES MANUFACTURING ACETONE
AND PHENOL FROM CUMENE, 1977
Material emitted
Source severity5
No plume rise*3 With plume rise^j
Criteria pollutants
Total nonmethane
hydrocarbons^
Chemical substances:6
3.5
1.9
Acetaldehyde
Acetone
Benzene
2-Butanone
Cumene
Ethylbenzene
Formaldehyde
a-Methylstyrene^
Naphthalene
<0. 00076
0.0090
0.43
0.055
0.23
0.000063
0.022
0.000014
<0. 00013
<0. 00042
0.0050
0.24
0.030
0.13
0.000035
0.012
0.0000077
<0. 000072
Sampling performed.
""calculated with no plume rise, that is, H = h1 , where
h1 = 17.1 m.
'Calculated with plume rise, that is H = h1 + AH, where
h1 = 17.1 m and AH = 6.0, by multipling by the correction
factor, (h'/n1 + AH)2 = 0.55.
Source severity for total nonmethane organic materials
will not equal the source severity for total nonmethane
hydrocarbons. Source severities for the nonmethane
organic materials are based on the toxicity of the
chemicals. The source severity for total nonmethane
hydrocarbons is based on the guideline for meeting the
primary ambient air quality standard for photochemical
oxidants.
"Only substances which have a TLV are listed.
(continued)
182
-------
TABLE L-2 (continued)
The benzene emission factor is not representative. A
process upset at one of the two plants sampled resulted
in a high level of benzene emissions.
"Assumed to be the a form. The GC/MS analysis does not
distinguish among the forms.
183
-------
GLOSSARY
absorber: Carbon adsorption column used to remove hydrocarbons
from gaseous emissions.
affected population: Number of nonplant persons exposed to air-
borne materials which are present in concentrations greater
than a determined hazard potential factor.
afterburner: See incinerator.
Allied process: Process for the manufacture of phenol and ace-
tone from cumene licensed by Allied Chemical Corporation
to others.
atmospheric stability class: Class used to designate degree of
turbulent mixing in the atmosphere.
cleavage: Chemical reaction in which cumene hydroperoxide in tn
presence of a catalyst forms acetone and phenol.
criteria pollutant: Emission species for which ambient air
quality standards have been established; these include par-
ticulates, sulfur oxides/ nitrogen oxides, carbon monoxide,
and nonmethane hydrocarbons.a
emission factor: Weight of material emitted to the atmosphere
per unit of phenol produced; e.g., g material/kg product.
flare: Combustion device used for the ultimate disposal of smal
continuous flow hydrocarbon streams and intermittent hydro-
carbon streams.
Hercules process: Process for the manufacture of phenol and
acetone from cumene licensed by Hercules Corporation to
others.
incinerator: Thermal oxidizer used for ultimate disposal of
hydrocarbons.
aThere is no primary ambient air quality standard for hydrocar-
bons. The value, 160 yg/m3, used in this report is a guideline
for meeting the primary ambient air quality standard for photo-
chemical oxidants.
184
-------
methane equivalents: The amount of methane, based on carbon con-
tent, that an amount of organic material is equal to.
noncriteria pollutant: Emission species for which no ambient air
quality standards have been established.
product transport loading facility: Facility used at phenol
plants to load product phenol, acetone, and byproduct into
railroad tank cars and tank trucks.
source severity: Ratio of the maximum mean ground level concen-
tration of emitted species to the hazard factor for the
species.
tank outage: Distance from liquid surface to the top of a fixed
roof storage tank.
total nonmethane hydrocarbons: Total amount of all nonmethane
organic materials, in methane equivalents.
vent condensers: Heat exchanger system used to remove hydro-
carbons from gaseous streams by condensation.
185
-------
CONVERSION FACTORS AND METRIC PREFIXES (95)
CONVERSION FACTORS
To convert from
Degree Celsius (°C)
Gram/kilogram (g/kg)
Joule (J)
Kilogram (kg)
Kilogram/second (kg/s)
Kilojoule/kilogram
Kilometer2 (km2)
Meter (m)
Meter (m)
Meter3 (m3)
Meter3 (m3)
Meter3 (m3)
Meter3 (m3)
Meter3/second (m3/s)
Metric ton
Pascal (Pa)
Pascal (Pa)
Second (s)
Watt (w)
To
Degree Fahrenheit (°F)
Pound/ton
British thermal units
(Btu)
Pound-mass (avoirdupois)
Pound mass/hour (Ib/hr)
British thermal unit/
pound (Btu/lb)
Mile2 (mi2)
Foot
Mile
Barrel (42 gal)
Foot3
Gallon (U.S. liquid)
Liter
Gal/min
Ton (short, 2,000 Ib
mass)
Pounds-force/inch2 (psi)
Torr (mm Hg, 0°C)
Minute
Horsepower
Multiply by
I = 1-8 t£ +32
2.000
9.475 x 10"14
2.205 ,
7.937 x IO3
4.299 x ID"}
3.861 x 10"
3.281
6.215 x 10"
6.293 .
3.531 x I0j
2.642 x 10*
1.000 x 10^
1.585 x 10
102
450 x 10
501 x 10
667 x 10
1.340 x 10
Prefix
mega
kilo
milli
micro
nano
Symbol
M
k
m
u
n
PREFIXES
Multiplication
factor
106
103
io-3
10~6
io-7
Example
1 MPa = 1 x IO6 pascals
1 kj = 1 x 103 joules
1 mm = 1 x 10"3 meters
1 yg = 1 x IO"6 gram
1 ng = 1 x 10-7 gram
(95) Standard for Metric Practice. ANSI/ASTM Designation E
380-76e, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976
37 pp.
186
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TECHNICAL REPORT DATA
(Please read Instructions on the rtvtne before completing)
1. REPORT NO.
EPA-600/2-79-019d
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
SOURCE ASSESSMENT: Manufacture of Acetone and
Phenol from Cumene
5. REPORT DATE
May 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J.L. Delaney and T.W. Hughes
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-889
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-071
11. CONTRACT/GRANT NO.
68-02-1874
12. SPONSORING AGENCY NAME AND ADDRESS
PERIOD COVERED
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD CC
Task Final; 2/76 - 4/78
14. SPONSORING AGENCY CODE
EPA/600/13
15.SUPPLEMENTARY NOTES TJERL-RTP project officer is Bruce A. Tichenor, MD-62, 919/541-
2547. Other source assessment reports are in this series and in EPA-600/2-76-032,
-77-107, and -78-004 series.
ie. ABSTRACT rpne report describes a study of atmospheric emissions resulting from the
manufacture of acetone and phenol from cumene. The air emissions from such manu-
facture consist only of hydrocarbons (HC). Emission factors are given for each spe-
cies emitted to the atmosphere from each source within a typical plant. Emissions
data are used to calculate several factors designed to quantify the hazard potential
of the emissions. Industry contributions to atmospheric HC emissions from station-
ary sources are estimated to be: 0. 023% for the Nation, 0.0049% for California,
0. 013% for Illinois, 0.050% for Kansas , 0. 084% for Louisiana, 0.034% for New Jer-
sey, 0.049% for Ohio, 0.084% for Pennsylvania, and 0.081% for Texas. A variety of
HC emission control methods are used, depending on the emission and the emission
point. The two process technologies in use in the U.S. for oxidizing cumene to cu-
mene hydroperoxide and for cleavage of the cumene hydroperoxide to acetone and
phenol are discussed and compared. Process descriptions and flow sheets for these
technologies are presented. Economic and production trends in the phenol industry
and in the industries that use phenol, acetone, and the other byproducts are discus-
sed and analyzed.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Pollution
Assessments
Industrial Processes
Acetone
Phenols
Cumene
Hydrocarbons
Pollution Control
Stationary Sources
13B
14B
13H
07C
3. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
200
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
Form 2220-1 (9-73)
187
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