United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/3-88-002
Febuary 1985
Air
SODIUM
HYDROXIDE
PRELIMINARY
SOURCE
ASSESSMENT
-------
EPA-450/3-88-002
Sodium Hydroxide
Preliminary
Source Assessment
Emission Standards Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park NC 27711
February 1988
-------
This report has been reviewed by the Emission Standards Division of the Office of Air Quality Planning and
Standards, EPA, and approved for publication. Mention of trade names or commercial products is not
intended to constitute endorsement or recommendation for use. Copies of this report are available through
the Library Services Office (MD-35), U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina 27711; or, for a fee, from the National Technical Information Services, 5285 Port Royal Road,
Springfield, Virginia 22161.
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SODIUM HYDROXIDE
PRELIMINARY
SOURCE ASSESSMENT
Prepared by:
William J. Neuffer
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
September 1987
-------
TABLE OF CONTENTS
1.0 INTRODUCTION 1-1
2.0 SUMMARY 2-1
2.1. Sodium Hydroxide Properties 2-1
2.2. Uses of Sodium Hydroxide 2-2
2.3. NaOH Emissions 2-4
2.4. State Regulations 2-8
2.5. Worker Exposure 2-9
2.5.1. Worker Exposure Standards 2-9
2.5.2. Worker Exposure Data 2-11
2.6. Sodium Hydroxide Emissions - Short Term Releases 2-14
2.7. References 2-15
3.0 THE KRAFT PULPING INDUSTRY 3-1
3.1. Industry Description 3-1
3.2. Process Description 3-7
3.2.1. General 3-7
3.2.2. Specific Process of Interest 3-9
3.3. Emi ssions 3-11
3.3.1. Uncontrolled Emissions 3-11
3.3.2. Emission Control Equipment 3-11
3.3.3. Controlled Emissions 3-12
3.4. HEM Inputs 3-14
Append! x for Chapter 3 3-18
3.5. References 3-22
4.0 BEER MANUFACTURING 4-1
4.1. Industry Description 4-1
4.2. Process Description 4-6
4.2.1. General 4-6
4.2.2. Specific Process of Interest 4-6
4.3. Emi ssions 4-8
4.4. HEM Inputs 4-8
Appendix for Chapter 4 4-10
4.5. References 4-11
5.0 AUTOMOTIVE CARBURETOR MANUFACTURING 5-1
5.1. Industry Description 5-1
5.2. Process Description 5-1
5.3. Emissions 5-5
5.3.1. Uncontrolled Emissions 5-5
5.3.2. Emission Control Equipment 5-5
5.4. HEM Inputs 5-5
Appendix for Chapter 5 5-8
5.5. References 5-11
iii
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Page
6.0 METAL FINISHING 6-1
6.1. Industry Description 6-1
6.2. Process Description 6-1
6.2.1. General 6-1
6.2.2. Specific Processes of Interest 6-5
6.3. Emlsslons 6-10
6.4. HEM Inputs 6-10
6.5. References 6-15
7.0 INDUSTRIAL ORGANIC CHEMICALS 7-1
7.1. Industry Description 7-1
7.2. Process Description 7-1
7.3. Emissions 7-4
7.4. HEM Inputs 7-4
7.5. References 7-7
8.0 SOAP AND DETERGENT MANUFACTURING 8-1
8.1. Industry Description 8-1
8.2. Process Description 8-1
8.2.1. General - Soap 8-1
8.2.2. Specific Processes of Interest - Soap 8-5
8.2.3. General - Detergent 8-7
8.3. Em1 sslons/HEM Inputs 8-9
8.4. References 8-11
9.0 METAL PARTITIONS, SHELVING, RACKS 9-1
9.1. Industry Description 9-1
9.2. Process Description 9-1
9.3. Eml sslons/HEM Inputs 9-4
9.4. References 9-6
10.0 MISCELLANEOUS INDUSTRIES 10-1
10.1. Summary 10-1
11.0 NaOH INDUSTRY 11-1
11.1. Industry Description 11-1
11.2. Process Description 11-1
11.2.1. General 11-1
11.2.2. Diaphragm Cell Process 11-1
11.2.3. Mercury Cell Process 11-7
11.2.4. Membrane Cell Process 11-9
11.3. Emissions (Other Than NaOH) 11-11
11.4. NaOH Em1ss1ons/HEM Inputs 11-11
11.5. References 11-15
1v
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LIST OF FIGURES
Figure
2-1 Vapor Pressures of Various Caustic Soda Solutions 2-2
3-1 Kraft Pulping Process 3-8
3-2 Smelt Dissolving Tank With Water Sprays 3-10
4-1 Beer Manufacturing 4-7
5-1 Process Lines - Hoiley Automotive - Bowling Green, KY 5-3
5-4
6-1 Metal Finishing 6-3
6-2 Cut-Away View of Plating Tank 6-7
7-1 Production of Maple Flavoring - Elan Chemical, Newark, NJ 7-5
8-1 Continuous Process for Manufacture of Fatty Acids and Soap 8-6
8-2 Spray Dried Detergent Manufacturing 8-8
9-1 Plating Line-Ferro Merchandising Equipment - Union, NJ 9-3
11-1 NaOH Production by the Diaphragm Cell Process 11-4
11-2 Diaphragm Cell Used to Produce Sodium Hydroxide and Chlorine 11-6
11-3 NaOH Production by the Mercury Cell Process 11-8
11-4 NaOH Production by the Membrane Cell Process 11-10
11-5 Occidental Chemical - Niagara Falls, NY 11-13
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LIST OF TABLES
Table Page
2-1 1982 Caustic Soda Uses 2-3
2-2 Plants with Estimated Sodium Hydroxide Emissions Greater
than 10,000 Ib/yr 2-5
2-6
2-3 NaOH Workplace Standards 2-10
2-4 National Inspection Summary Report - OSHA 2-12
2-13
3-1 Summary of Kraft Pulp Mills 1n the United States 3-2-
3-6
3-2 Partlculate Emissions from Various Smelt Dissolving Tank
Control Systems 3-13
3-3 HEM Inputs for Sodium Hydroxide Emissions from Model
Size Smelt Dissolving Tanks 1n Kraft Pulp Plants 3-15
3-4 HEM Inputs for Sodium Hydroxide Emissions from Smelt
Dissolving Tanks at Certain Kraft Pulp Plants 3-16
3-17
4-1 Breweries Located in the United States - 1986 4-2-
4-5
4-2 HEM Inputs for Sodium Hydroxide Emissions from Beer
Manufacturing 4-9
5-1 U.S. Primary Automotive Carburetor Manufacturing Plants 5-2
5-2 Uncontrolled Emissions - Hoi ley Automotive -
Bowling Green, KY 5-6
5-3 HEM Inputs for Sodium Hydroxide Emissions from Carburetor
Manufacturing 5-7
6-1 Metal Finishing - U.S. Plants with Greater Than 500 Employees6-2
6-2 Electroless Plating 6-8
6-3 HEM Inputs for Sodium Hydroxide Emissions from
Metal Finishing 6-11
7-1 Industrial Organic Chemicals - U.S. Plants with Greater
Than 500 Employees 7-2
7-3
7-2 HEM Inputs for Sodium Hydroxide Emissions from Industrial
Organic Chemicals 7-6
8-1 Soap and Detergent Manufacturing - U.S. Plants with
Greater than 100 Employees 8-2
8-3
8-2 Spray-Dry Detergent Manufacturing, 1980 8-4
8-3 HEM Inputs for Sodium Hydroxide Emissions from Soap
Manufacturing 8-10
9-1 SIC 2542 - U.S. Plants with Greater than 500 Employees 9-2
9-2 HEM Inputs for Sodium Hydroxide Emissions from Metal
Partitions 9-5
10-1 Plants with Sodium Hydroxide Emissions Between 5,000 -
10,000 Ib/yr 10-2
10-2 Plants in Kentucky, New York and Texas with Sodium
Hydroxide Emissions Between 1,000 - 5,000 Ib/yr 10-3
10-4
vi
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LIST OF TABLES
(Continued)
Table
10-3 New Jersey Plants with Sodium Hydroxide Emissions Between
1,000 - 5,000 Ib/yr 10-5
10-6
11-1 NaOH Plants in the United States - 1986 11-2
11-2 Recent Changes 1n Capacity of Chior-Alkali Plants (1987-87) 11-3
11-3 NaOH Production in the U.S. 11-3
11-4 HEM Inputs For Sodium Hydroxide Emissions From Chlor-
Alkali Plants 11-14
vii
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1.0 INTRODUCTION
1.1 INTRODUCTION
The purpose of this project was to Identify and characterize the major
air emission sources of sodium hydroxide (NaOH) in a preliminary source
assessment (PSA). The stack parameters and NaOH emissions that are contained
in this PSA for various industries are used as inputs to the Human Exposure
Model (HEM) by EPA's Pollutant Assessment Branch to determine ambient
concentrations of sodium hydroxide. Details on HEM are contained in "User's
Manual for the Human Exposure Model," (EPA-450/5-86-001). Along with this
PSA and the resultant ambient HEM modelling, a preliminary health assessment
of sodium hydroxide was prepared by EPA's Environmental Criteria and Assessment
Office. This assessment is described in "Summary Review of Health Effects
Associated with Sodium Hydroxide," (ECAO-R-135). With the preliminary
source and health assessments and HEM modelling results, EPA determines if
air emissions of sodium hydroxide may pose a significant health risk. If
so, a much more detailed study is undertaken to further evaluate the emissions
and health risks to determine if sodium hydroxide should be regulated as a
hazardous air pollutant under Section 112 of the Clean Air Act.
To develop this preliminary source assessment, numerous sources were
used. A literature search provided some references that help identify
industries that use sodium hydroxide as well as descriptions of the manufacture
of sodium hydroxide (caustic soda). To identify States that presently
regulate sodium hydroxide, telephone calls were made to all EPA regional
air toxic contacts. Numerous State agencies were then contacted to obtain
information on their regulations. Also, the States of Kentucky, New Jersey,
New York, and Texas provided computer printouts on NaOH emission estimates.
These estimates were the basis of the inputs to the Human Exposure Model.
State agency and plant personnel in each industry were contacted to verify
these estimates and to obtain information on processes and emission control
equipment. At least one trade association in each industry was called to
determine how widely NaOH is used by the industry as well as for process
information. These associations, as well as the Duns Electronic Yellow
Pages help provide plant listings. Information was retrieved from the
1-1
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National Air Toxics Information Clearinghouse (NATICH) database to identify
any plant that is a major emission source of sodium hydroxide but was not
identified by printouts from the States. The National Environmental Data
System (NEDS) data base was used to determine stack parameters for various
kraft pulp mills. Information on sodium hydroxide spills is contained in
the Acute Hazardous Events Data Base and was obtained from EPA's Air and
Energy Research Laboratory. Also, a National Inspection Summary Report for
sodium hydroxide was received from the Occupational Safety and Health
Administration (OSHA).
This report contains eleven chapters. The next chapter describes uses
and properties of sodium hydroxide. Also, a summary of those plants that
are estimated to have sodium hydroxide emissions greater than 10,000 Ibs/yr
is presented. Information from the Acute Hazardous Events data base and
OSHA is also given. Regulations for those States with sodium hydroxide
emission limits are also given in Chapter 2. The next seven chapters sum-
marize each industry which has at least one plant with estimated annual
NaOH emissions to be greater than 10,000 pounds. A list of plants in each
industry along with process and emission information and the HEM inputs for
plants in the industries is given. Chapter 10 summarizes plants with
sodium hydroxide emissions greater than 1,000 Ib/yr but with no plants in
their SIC codes with emissions greater than 10,000 Ib/yr. Chapter 11
discusses sodium hydroxide (caustic soda) manufacturing plants, and the
processes used at these plants as well as estimates of sodium hydroxide
emissions from these plants.
1-2
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2.0 SUMMARY
2.1 SODIUM HYDROXIDE PROPERTIES
Sodium hydroxide (caustic soda) is a white, deliquescent, translucent
solid with a crystalline structure. It has a specific gravity of 2.13, a
melting point of 318°C and boiling point of 1390°C. It dissolves readily
in water evolving heat to form a colorless solution.1*2 Vapor pressures
of various caustic soda solutions are shown in Figure 2-1.
According to an article critiquing the U.S. occupational standard
for sodium hydroxide, caustic soda is highly reactive in the atmosphere.3
Properties of the sodium hydroxide aerosols, such as the chemical composition,
mass concentration, particle size distribution, and its phase, depend on
its reactions with carbon dioxide, water, and the relative humidity.
These interactions produce solid or liquid particles which may be entirely
one or several compounds. Whether caustic soda is a solid or liquid, the
following reaction takes place:
Depending on the size of the sodium hydroxide particle and the relative
humidity, the NaOH will convert to sodium carbonate within seconds to
minutes. More information on these reactions is contained in References
3-5.
2.2 USES OF SODIUM HYDROXIDE
As shown by the printouts on sodium hydroxide emission estimates
received from four State Agencies, sodium hydroxide (caustic soda) is
used in a wide variety of industries. In particular, caustic soda is used
for metal cleaning and electroplating in numerous SIC codes. Table 2-1
gives the end use by industry in 1982 for sodium hydroxide.
2-1
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Figure 2-1. Vapor Pressures of Various Caustic Soda Solutions'
2-2
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Industry
Chemicals
Pulp and Paper
Petroleum
Soap, Detergents
Cellulosic
Cotton Mercerizing
Other
TABLE 2-1. 1982 CAUSTIC SODA USES6
Percent
Amount
(103MT)
3,900
2,070
483-493
412-477
185
109
187-812
7,350-8,050
Some other uses of caustic soda are to neutralize acids and the
production of sodium salts in petroleum refining, in the production of
viscose rayon, cellophane, and plastics. Some uses of NaOH are further
described in Chapters 3-10.
In 1986, caustic production was estimated to be more than 11 million
tons as 100 percent NaOH with an operating capacity of 12.7 million tons.
In 1986, two large producers reduced their production capacity significantly
but the long term growth rate will probably continue to be 2-3 percent
per year.8 Information on the historical production of caustic soda and a
list of U.S. manufacturing plants is contained in Chapter 11 - NaOH Industry.
2-3
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Large consumers of caustic soda usually purchase and store caustic
soda at a NaOH concentration of 50 or 73 percent. Most users prefer the
50 percent product due to ease in handling. A rayon-grade caustic soda
is also produced as a higher quality, more uniform product. Solid caustic
is shipped in drums or is processed to produce a flake product.9
2.3 NaOH EMISSIONS
Table 2-2 shows those 15 plants in numerical order with sodium
hydroxide emissions greater than 10,000 Ib/yr as estimated by State
Agencies or in the case of the kraft pulp plants, by EPA. As shown in
the Table, 9 of these 15 plants are kraft pulp mills. As noted in
Chapter 3, HEM inputs were developed for 10 kraft mill plants that repre-
sent the range in capacity in these plants. All but 1 of the 10 plants
(one of the smallest capacities) exceeded 10,000 Ib/yr of emissions by a
wide margin. It is reasonable to assume that most of the 123 kraft pulp
mills exceed 10,000 Ib/yr of sodium hydroxide emissions by a sizeable
amount. Also, caustic soda emissions from some plants in the other SIC
codes mentioned in Table 2-2 should exceed 10,000 Ib/yr but the number of
these plants was not determined in this preliminary study.
Based on reviewing computer printouts submitted by State agencies and
discussions with plant and State agency personnel, sodium hydroxide emission
estimates were revised. In some cases, the revised estimates were much
lower. Initial emission estimates for 10 industries that were above
10,000 Ib/yr were revised to much lower amounts. These industries with
the original estimates and the rationale for the revised estimates follows.
1. SIC 2818 - Industrial Inorganic Chemicals. Monsanto-Logan
Township, NJ. Original estimate - 16,000 Ib/yr. Very little emissions
are expected as most estimated emissions come from storage tanks. The
revised estimate was supported by calculating emissions based on equations
in AP-42 for petroleum storage tanks and by conversations with State
Agency personnel.
2-4
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TABLE 2-2. PLANTS WITH ESTIMATED SODIUM HYDROXIDE EMISSIONS GREATER THAN 10,000 LB/YR.
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SIC
CODE
2611
2611
2611
2082
2611
3714
2611
2611
2611
2611
2611
3471
INDUSTRY
PLANT
Kraft Pulp Longview Fiber
Kraft Pulp Great Southern
Paper
Kraft Pulp Union Camp
Beer Manuf. Miller Brewing
Kraft Pulp International
Paper
Auto Rochester
Carburetor Products
Kraft Pulp Weyerhaeuser
Kraft Pulp Champion Int.
LOCATION
NaOH EMISSIONS
(Ib/yr)
Longvlew, WA 252,000
Cedar Springs, GA 154,000
Savannah, GA 119,000
Fulton, NY
Camden, AR
Rochester, NY
Plymouth, NC
Pensacola, FL
Kraft Pulp Georgia-Pacific Port Hudson, LA
Kraft Pulp James River Butler, AL
Kraft Pulp Crown Zellerbach Bogalosa, LA
Plating Monroe Plating Rochester, NY
106,000
102,000
67,000
65,000
53,000
52,000
42,000
33,000
22,000
PROCESS
CONTROL
EQUIPMENT
4 Smelt Dissolving M1st
Tanks Eliminator
3 Smelt Dissolving Wet Scrubber
Tanks
4 Smelt Dissolving Wet Scrubber
Tanks
2 Bottle Washing
Systems
None
3 Smelt Dissolving Spray Tower, 2
Tanks Water Curtains
Plating Tanks,
Caustic Cleaning
Tanks, other processes
None
2 Smelt Dissolving M1st
Tanks Eliminator
2 Smelt Dissolving Venturl
Tanks Scrubber
3 Smelt Dissolving Unknown
Tanks
3 Smelt Dissolving Wet Scrubber
Tanks
1 Smelt Dissolving M1st
Tank Eliminator
2 Plating Tanks,
3 Caustic Cleaning
Tanks
None
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TABLE 2-2. (Continued)
SIC
CODE
INDUSTRY
PLANT
LOCATION
NaOH EMISSIONS
(Ib/yr)
PROCESS
CONTROL
EQUIPMENT
2869 Industrial Organic Elan Chemical Newark, NJ
Chemicals
15,000
Preheater, Prenrfx
Tank
None
2841 Soap, Detergents Chemed
2542 Metal
Partitions
Ferro
Merchandising
E. Rutherford, NJ 14,000
Union, NJ 11,000
Storage, 3 Batch None
Kettles
5 Electroclean None
Tanks, 2 Soak
Clean Tanks
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2. SIC 2911 - Petroleum Refining. Exxon - Linden, NJ. Original
estimate - 88,000 Ib/yr of caustic solution emissions; Chevron - Perth Amboy,
NJ - 26,000 Ib/hr; Mobil - Greenwich Township, NJ - 12,000 Ib/yr. Nearly
all emissions came from storage tanks so emissions are now considered to be
minor. See rationale under 1.
3. SIC 3229 - Press and Blown Glass. Owens-Illinois - Vineland City,
NJ. Original estimate - 77,000 Ib/yr from borosilicate glass furnaces.
Plant personnel stated that caustic soda is not used and process descriptions
from the literature does not indicate any use of caustic soda in this
Industry. State personnel confirmed that no sodium hydroxide is used at
the plant.
4. SIC 3312 - Blast Furnaces. BSC Bar Products - Lackawanna, NY.
Original estimate - 20,000 Ib/yr based on 260 days/yr operating metal
cleaning process at a bar mill coil pickling facility. Plant personnel
stated the process only operates 8 hr/day; 20 days/yr so revised estimate
should be 1,500 Ib/yr.
5. SIC 3339 - 1° Non-Ferrous Metals. ASARCO - Newark, NJ. Original
estimate - 38,000 Ib/yr. Both State and company personnel stated that the
plant has been shut down for 2 years with no plans for reopening.
6. SIC 3463 - Nonferrous Forgings. Intercontinental Manufacturing -
Garland, TX. Original estimate - 25,000 Ib/yr. State agency personnel
checked and stated that this was the amount of caustic soda used as stated
in a 1980 Inventory Sheet. According to the State agency, NaOH emissions
should be 240 Ib/yr.
7. SIC 3544 - Tools and Special Dies. Alliance Metal - Gates, NY.
Original estimate - 12,000 Ib/yr. According to plant personnel, plant uses
60 Ib/yr of caustic soda so emissions will be less than 60 Ib/yr.
8. SIC 3572 - Typewriters. IBM - Lexington, KY. Original estimate -
19,000 Ib/yr from electro!ess nickel plating. State personnel stated that
this process discontinued operations In 1985 and was dismantled in 1986.
Emission estimates for each of four plants in SIC 357 are below 2,900 Ib/yr.
9. SIC 4231 - Trucking Terminal Facilities. P.O. Oil - Bayonne, NJ.
Original estimate - 32,000 Ib/yr. All emissions are from storage tanks.
Revised estimate is minor. See rationale under 1.
2-7
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10. SIC 5172 - Petroleum Products, NEC. Gordon Terminal - Bayonne,
NJ. Original estimate - 13,000 Ib/yr. All emissions are from storage
tanks. Revised emission estimate is minor. See rationale under 1.
2.4 STATE REGULATIONS
This section describes existing State regulations regarding industrial
processes that use sodium hydroxide. In general, these processes have to
comply with particulate emission standards which are based on process weight
equations. Two equations commonly used by State agencies are given below:
E = 4.2p °-67; P£ 30
E = 55p 0.11 _ 40; p>30
Where "p" is the tons of material processed per hour.
In addition, seven States have additional regulations specific to
sodium hydroxide. Ambient modelling is performed by these State Agencies
to verify that these regulations are met. A summary of these State
regulations follows. Allowable emission limits for sodium hydroxide vary
from 2 - 2,200 ug/m3 depending on the State and the corresponding time
period which varies from 30 minutes to a year.
Connecticut - (New and Existing Sources). Sodium hydroxide is
considered a Group III pollutant (slightly toxic).
- 40 ug/m3 (8 hr average)
- 200 ug/m3 (30 min average).
Kentucky - (New and Existing Sources)
EAL • EAC * Ifk
L
EAL = Allowable emission limit in pounds per hour.
E/\c = Actual emission rate in pounds per hour
TAL = Threshold ambient limit. For sodium hydroxide,
TAL = 8mg/m3
Operating hrs per wk
2-8
-------
C = Maximum ground level ambient air concentration estimated by modelling
in mg/m3.
If sodium hydroxide emissions for the source are less than 3.583 x 10-4 lbs/hr
then the source does not have to comply with these equations.
Nevada - (New and Existing Sources)
- 48 ug/m3 (8 hr. average)
Sodium hydroxide is considered a Level III pollutant (Toxic Hazardous
Ai r Contaminant).
New York - (New and Existing Sources)
- 40 ug/m3 (Annual Ambient Level). Sodium hydroxide is considered
a low toxic air pollutant.
South Carolina - (New Sources Only)
- 20 ug/m3 (24 hr. average). Sodium hydroxide is considered to
be moderately toxic.
Texas - (New and Existing Sources)
- 20 ug/m3 (30 min. average)
- 2 ug/m3 (annual average)
Virginia - (New Sources Only)
- 17 ug/m3 (24 hr. average)
2.5 WORKER EXPOSURE
2.5.1 Worker Exposure Standards
The current Federal standard for sodium hydroxide is 2 mg/m3 as a time
weighted average during an 8-hour period. This standard is much higher than some
of the ambient levels established by State agencies. This standard was recommended
by the Occupational Safety and Health Administration (OSHA) and is based on the
1968 American Conference of Governmental Industrial Hygienist's (ACGIH) Threshold
Limit Value. In 1986-87, ACGIH recommended that 2 mg/m3 not be exceeded at any
time.10 The National Institute for Occupational Safety and Health (NIOSH) recom-
mended this same level not be surpassed in a 15 minute period.11 Six other countries
have recommended standards for exposure to sodium hydroxide in the workplace.
These standards are shown on Table 2-3. All standards are ceilings, that is,
should not be exceeded at any time. More information on these standards is
contained in references 3 and 11.
2-9
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TABLE 2-3. NaOH WORKPLACE STANDARDS11
Country Pollutant Standard (mg/m3)
Finland NaOH 2
West Germany NaOH 2
Yugoslavia NaOH 2
Rumania Hydroxides (alkaline) 1
Bulgaria Alkalies 0.5
USSR " aersols (as NaOH) 0.5
2-10
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2.5.2 Worker Exposure Data
Table 2-4 summarizes data 1n descending numerical order received from
the Occupational Safety and Health Administration on a National Inspection
Summary Report of Sodium Hydroxide that Includes all Federal Inspections
between June 1, 1979, to October 31, 1986.12 Any sample value on this report
which Is greater than or equal to 0.5 mg/m3 Is Included 1n the Table. According
to the National Institute for Occupational Safety and Health, 150,000 workers
are estimated to be potentially exposed to NaOH.11
2-11
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TABLE 2-4. NATIONAL INSPECTION SUMMARY REPORT - OSHA12
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sic
CODE
3471
1541
3334
2842
2841
2869
2842
2810
2841
3471
3069
3621
INDUSTRY
Electroplating
Industrial
Building
Primary Aluminum
Speciality
Cleaning
Soap * Detergents
Industrial Organic
Chemicals
Speciality Cleaning
Industrial
Inorganic
Chemicals
Soap 4 Detergents
Electroplating
Fab. Rubber
Production
Motors 4 Generators
PLANT
Mycor Metal
Finishing
Ethyl Corp.
Kaiser A1
Chemix Corp.
Time Chemicals
Continental
Products
Can-Tol
Harshaw
Chemical
Time
Chemicals
Logan Finishing
Pioneer
Industrial Prod.
General Electric
NO. OF PEOPLE NO. OF VALUE
LOCATION! JOB TITLE EXPOSED SAMPLES tmg/m3)
Rochester, NY
Pasadena, TX
Ravenswood, WV
Berea, OH
Chicago, IL
Odessa, TX
Philadelphia, PA
Gloucester City,
NJ
Chicago, IL
Lakevlew, OH
Hlllard, OH
Tiffin, OH
Unknown
Burner
Operator
Bath M111
Operator
Unknown
Mixer
Warehouseman
Unknown
Process Man
Mixer
Anodlzer
Chlorlnator
Mold Repairman
1 1 8.0
4 TWA* 1.44-6.81
3 TWA 3.77
1 1 3.6
8 TWA 3.4
2 TWA 2.6
1 3 2.4
4 TWA 1.73
1 TWA 1.6
4 TWA 1.4
6 TWA 0.85
2 TWA 0.74
a Time Weighted Average
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TABLE 2-4. (Continued)
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SIC
CODE
2841
2842
2841
3561
2542
2841
3471
2841
INDUSTRY
Soap * Detergents
Speciality Cleaning
Soap A Detergents
Pumps
Metal
Partitions
Soap A Detergents
Electroplating
Soap A Detergents
PLANT
H. Kohnstamm
Can-Tol
H. Kohnstamm
Thompson
Pump
Ferro
Merchandising
Time
Chemicals
Poly Metal
Finishing
Time
Chemicals
LOCATION
Chicago, IL
Philadelphia, PA
Chicago, IL
Okmulgee, OK
Union, NJ
Chicago, IL
Springfield, MA
Chicago, IL
NO
JOB TITLE
Chemical Mixer
Mixer
Chemical Mixer
Dipper
Hoist Operator
Operator
Mixer
Loading Foreman
Filler Mixer
. OF PEOPLE
EXPOSED
2
2
2
1
1
1
29
3
NO. OF
SAMPLES
TWA
TWA
TWA
TWA
TWA
TWA
TWA
TWA
VALUE
(mg/m3)
0.71
0.64
0.63
0.63
0.61
0.60
0.56
0.50
-------
2.6 SODIUM HYDROXIDE EMISSIONS - SHORT TERM RELEASE
Three events are reported in the Acute Hazardous Events database for the
period 1980 - mid 1985 that relate to sodium hydroxide air emission releases.
All occurred during transit of solid caustic soda. No significant problems
resulted. There are numerous examples of spills of caustic soda solutions
but little if any resulting atmospheric emissions are reported in this
database.*3
2-14
-------
2.7 REFERENCES
1. Lowenheim, F.A., and M.K. Moran. In: Faith, Keyes and Clark's Industrial
Chemicals, Fourth Edition. New York, John Wiley and Sons, Inc. 1975.
pp. 737 - 745.
2. U.S. Environmental Protection Agency. Atmospheric Emissions from Chlor-Alfcall
Manufacture. Research Triangle Park, N.C. January 1971. pp. 79, 84.
3. Cooper, D.W., D.W. Underhill, and M.J. Ellenbecker. A Critique of the
U.S. Standard for Industrial Exposure to Sodium Hydroxide Aerosols. Mierfcan
Industrial Hygiene Association Journal. 40:365-371. May 1979.
4. Murata, M., M. Naritomi, Y. Yoshida, and M. Kobubu. Behavior of Sodium
Aerosol in Atmosphere. Journal of Nuclear Science and Technology. 11:65-71.
February 1974.
5. Clough, W.S., and J.A. Garland. The Behaviour in the Atmosphere of the
Aerosol from a Sodium Fire. Journal of Nuclear Energy. 25:425-435. 1971.
6. Chemical Economics Handbook. Stanford Research Institute. Menlo Parfc,
California. July 1984.
7. Greek, B.F. Chlor-Alkalies Profit from Plant Shutdowns. Chemical amd
Engineering News. 64:17-20. September 8, 1986.
8. U.S. Department of Commerce. 1987 U.S. Industrial Outloo*. Hashinfton.,
D.C. January 1987. p. 12-3.
9. Hopkins, H.S. Caustic Soda. In: Chemical and Process Technology
Encyclopedia, Volume 2. New York, McGraw Hill. 1974. pp. 229-234.
10. American Conference of Governmental and Industrial Hygienfsts. Threshold
Limit Values for Chemical Solutions in the Work Environment Adopted ty ACSIH,
with intended changes for 1986-87. Cincinnati, Ohio. p. 29.
11. National Institute for Occupational Safety and Health, U.S. Department
of Health, Education and Welfare. Criteria for a Recommended Standard ...
Occupational Exposure to Sodium Hydroxide. (NIOSH) 76-105. Washington, D.C.
1975.
12. Letter and attachment from Ratal1nas, J.A., Occupational Safety and
Health Administration (OSHA), U.S. Department of Labor, to Neuffer, W.J.,
EPA. December 24, 1986. 219 pp. OSHA National Summary Report for Sodium
Hydroxide.
13. Attachment from Crum, J.M., AEERL/EPA to Neuffer, W.J., EPA. tedated.
8 pp. Computer Printout - Acute Hazardous Events Data Base.
2-15
-------
3.0 THE KRAFT PULPING INDUSTRY
3.1 INDUSTRY DESCRIPTION
Table 3-1 shows the 123 kraft pulp mills operating 1n the United States.
These mills are concentrated In the Southeast, Pacific Northwest, and New England
regions. As shown 1n Table 3-1, the capacity of these plants ranges from 180 -
2,850 tons per day of pulp and they operate close to capacity.
3-1
-------
TABLE 3-1.
SUMMARY OF KRAFT MILLS IN THE UNITED STATES1.2
STATE
A1abama
CO
ro
Arizona
Arkansas
California
COMPANY
Container Corp.
James River Corp.
Alabama River Pulp Co.
Kimberly-Clark Corp.
Champion International Corp.
Gulf State Paper Corp.
Allied Paper, Inc.
International Paper Co.
Scott Paper Co.
Union Camp Corp.
Alabama Kraft Co.
MacMlllon Bloedel, Inc.
Hammermlll Papers Group
Nekoosa Papers Inc.
International Paper Co.
Georgia-Pacific Corp.
Potlatch Corp.
Arkansas Kraft Corp.
International Paper
Weyerhaeuser Co.
Simpson Paper Co.
Flberboard Corp.
Simpson Paper Co.
Louisiana-Pacific Corp.
LOCATION
Brewton
Butler
Clalborne
Coosa Pines
Courtland
Demopol 1s
Jackson
Mobile
Mobile
Montgomery
Phenix City
Pine H111
Selma
Southwest Forestry Industries,Inc. Snowflake
Ashdown
Camden
Crossett
Cypress Bend
Mow11 ton
Pine Bluff
Pine Bluff
Anderson
Antloch
Falrhaven
Samoa
Kraft Production
Capacity (tpd)
1334
1000
1000
850
1393
500
600
1072
1450
2050
1100
1100
1100
700
1400
801
1500
525
780
1193
300
225
750
640
600
Avg. Dally
Production (tpd)
1100
1000
1000
854
1300
500
600
1035
1400
2220
1000
1075
1100
700
1350
723
1400
450
800
1112
280
225
600
640
600
-------
TABLE 3-1.
SUMMARY OF KRAFT MILLS IN THE UNITED STATES (cont'd)
Georgla
CO
to
Idaho
Kentucky
COMPANY
Container Corp of Am.
Alton Packaging Corp.
Georgia-Pacific Corp.
Southwest Forest Industries,Inc.
Champion International Corp.
Buckeye Cellulose Corp.
St. Joe Paper Co.
Federal Paperboard
Brunswick Pulp 4 Paper Co.
Great Southern Paper Co.
ITT Rayonler, Inc.
Georgia Kraft Co.
Georgia Kraft Co.
Buckeye Cellulose Corp.
Stone Container Corp.
Interstate Paper Corp.
Oilman Paper Co.
Union Camp Corp.
Owens-Ill1no1s Inc.
Potlatch Corp.
Willamette Industries, Inc.
Westvaco Corp.
LOCATION
Jacksonville
Jacksonville
Palatka
Panama City
Pensacola
Perry
Port Saint Joe
Augusta
Brunswick
Cedar Springs
Jesup
Krammert
Macon
Oglethorpe
Port Wentworth
Riceboro
St. Marys
Savannah
Valdosta
Lewiston
Hawesvllle
W1ckl1ffe
Kraft Production
Capacity (tpd)
1400
1400
1085
1450
1560
1000
1700
1000
1760
1870
1400
2000
950
860
800
550
1200
2850
998
1100
660
722
Avg. Dally
Production (tpd)
1500
1470
1200
1400
1730
1100
1700
1000
1700
1870
1400
1700
900
750
800
525
1225
3000
900
1100
600
650
-------
TABLE 3-1.
SUMMARY OF KRAFT MILLS IN THE UNITED STATES (cont'd)
co
i
STATE COMPANY
Louisiana International Paper Co.
Crown Zellerbach Corp.
WIIHamette Industries, Inc.
Boise Cascade Corp.
Stone Container Corp.
International Paper Co.
International Paper Co.
Georgia-Pacific Corp.
Crown Zellerback Corp.
Manvllle Forest Products
Maine Warren Co., S.O.
International Paper Co.
Lincoln Pulp * Paper Co.,Inc.
James River Corp.
Boise Cascade Corp.
Warren Co., S.D.
Georgia-Pacific Corp.
Maryland Westvaco Corp.
Michigan Mead Corp.
Warren Co., S.D.
Minnesota Pot!aten Corp.
Boise Cascade Corp.
LOCATION
Bastrop
Bogalusa
Camptl
De Rldder
Hodge
Mansfield
P1nev1lle
Port Hudson
St. Frandsvllle
West Monroe
H1nekley
Jay
Lincoln
Old Town
Rumford
Westbrook
Woodland
Luke
Escanaba
Muskegon
Cloquet
International Falls
Kraft Production
Capacity (tpd)
1200
1300
800
1275
1400
2050
985
1285
495
1400
800
1200
350
600
950
295
800
Unk.
800
230
490
365
Avg. Dally
Production (tpd)
1200
1260
750
1210
1400
1430
975
1300
550
1728
900
1200
340
600
630
300
800
794
600
250
475
380
-------
TABLE 3-1.
SUMMARY OF KRAFT MILLS IN THE UNITED
STATE
Mississippi
Montana
New Hampshire
New York
North Carolina
CO
I
en
Ohio
Oklahoma
Oregon
COMPANY
Georgia-Pacific Corp.
International Paper Co.
International Paper Co.
International Paper Co.
Leaf River Forest Products,Inc.
Champion International Corp.
James River Corp.
International Paper Co.
Champion International Corp.
Weyerhaeuser
Weyerhaeuser
Federal Paper Board Co.
Champion International
Mead Corp.
Weyerhaeuser
Willamette Industries, Inc.
Crown Zellerbach Corp.
International Paper Co.
Pope A Talbot Pulp, Inc.
Boise Cascade Corp.
Weyerhaeuser Co.
Georgia-Pacific Corp.
LOCATION
Monti cello
Moss Point
Natchez
Vlcksburg
New Augusta
Mlssoula
Berlin
Tlconderoga
Canton
New Bern
Plymouth
Rlegelwood
Roanoke Rapids
ChllHcothe
ValHant
Albany
Clatskanle
Gardiner
Halsey
St. Helens
Springfield
Toledo
STATES (cont'd)
Kraft Production
Capacity (tpd)
1995
750
1104
1181
Unk.
1900
800
530
1440
700
1480
2000
1100
600
1600
580
775
850
400
1000
1090
1140
Avg. Dally
Production (tpd)
1700
661
1112
1200
1000
1900
800
530
1390
725
1405
2030
1050
600
1650
600
836
600
350
965
1090
1090
-------
TABLE 3-1.
SUMMARY OF KRAFT MILLS IN THE UNITED STATES (cont'd)
STATE
Pennsylvania
South Carolina
COMPANY
Tennessee
Texas
Virginia
Washington
Wisconsin
Penntech Papers Inc.
Appleton Papers Inc.
P.M. Glatfelter Co.
Westvaco Corp.
Stone Container Corp.
International Paper Co.
Bowater Carolina Co.
Union Camp Corp.
Bowater Southern Paper Co.
Tennessee River Pulp & Paper Co.
Temple - Eastex Inc.
Champion International Corp.
Champion International Corp.
Champion International Corp.
International Paper Co.
Owens-Illinois Inc.
Westvaco Corp.
Union Camp Corp.
Stone Container Corp.
Chesapeake Corp.
Crown Zellerbach Corp.
Weyerhaeuser Co.
Longview Fibre Co.
Weyerhaeuser Co.
Port Townsend Paper Corp.
Simpson Paper Co.
Boise Cascade Corp.
Thilmany Pulp & Paper Co.
Mosinee Paper Corp.
Nekoosa Papers Inc.
Consolidated Papers, Inc.
LOCATION
Johnsonburg
Roaring Springs
Spring Grove
Charleston
Florence
Georgetown
Catawba
Eastover
Calhoun
Counce
Evadale
Houston
Lufkin
Pasadena
Texarkana
Orange
Covington
Franklin
Hopewel1
West Point
Camas
Everett
Longview
Longview
Port Townsend
Tacoma
Wallula
Kaukauna
Mosinee
Nekoosa
Wisconsin Rapids
Kraft Production
Capacity (tpd)
220
180
575
2435
1400
1608
1050
700
690
1600
1550
650
400
850
1288
1200
1376
1950
1000
1400
810
395
2800
800
450
1040
776
430
195
335
577
Avg. Daily
Production (tpd)
180
190
500
2050
1400
n.a.
1150
600
700
1500
1520
630
400
750
1215
1150
1050
1950
900
1920
810
385
2000
750
445
1090
690
400
220
335
515
-------
3.2 PROCESS DESCRIPTION
3.2.1 General
Manufacturing of paper and paper products is a complex process which is
carried out in two distinct phases: the pulping of the wood and the manufacture
of the paper. Pulping is the conversion of fibrous wood into a "pulp" material
suitable for use in paper, paperboard, and building materials. Of the two
phases involved in paper-making, the pulping process is the largest source of
air pollution. The kraft or sulfate pulping process produces over 80 percent
of the chemical pulp produced annually in the United States. The remaining
20 percent of the chemical pulp is produced by the sulfite and neutral sulfite
semi-chemical (NSSC) processes.3
Pulp wood can be considered to have two basic components, cellulose and
lignin. The fibers of cellulose, which comprise the pulp, are bound together
in the wood by the lignin. To render cellulose usable for paper manufacture,
the pulping process must first remove the lignin.
The kraft pulping process is shown in Figure 3-1. In this process, wood
chips are cooked (digested) at an elevated temperature and pressure in "white
liquor", which is a water solution of sodium sulfide (Na2S) and sodium hydrox-
ide (NaOH). The white liquor chemically dissolves lignin from the wood. The
remaining cellulose (pulp) is filtered from the spent cooking liquor and
washed with water. Usually, the pulp then proceeds through various inter-
mittent stages of washing and possibly bleaching, after which it is pressed
and dried into the finished product (paper).
The balance of the kraft process is designed to recover the cooking
chemicals and heat. Spent cooking liquor and the pulp wash water are combined
to form a weak black liquor which is concentrated in a multiple-effect evapo-
rator system to about 55 percent solids. The black liquor is then further
concentrated to 65 percent solids in a direct-contact evaporator, which
evaporates water by bringing the liquor in contact with the flue gases from
the recovery furnace, or in an indirect-contact concentrator. The strong
black liquor is then fired in a recovery furnace. Combustion of the organics
dissolved in the black liquor provides heat for generating process steam and
converting sodium sulfate (Na2S04) to Na2$. To make up for chemicals lost in
3-7
-------
-RECOVERY-
-PULPING-
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the operating cycle, salt cake (sodium sulfate) is usually added to the
concentrated black liquor before it is sprayed into the furnace. Inorganic
chemicals present in the black liquor collect as a molten smelt at the
bottom of the furnace.
The smelt, consisting of sodium carbonate (N32C03) and sodium sulfide,
is dissolved in water to form green liquor which is transferred to a
causticizing tank where quicklime (CaO) is added to convert the sodium
carbonate to sodium hydroxide. Formation of the sodium hydroxide completes
the regeneration of white liquor, which is returned to the digester system.
A calcium carbonate mud precipitates from the causticizing tank and is
calcined in a lime kiln to regenerate quicklime.
3.2.2 Specific Process of Interest
As shown in the next section, the only process source estimated to
emit sodium hydroxide is the smelt dissolving tank (see Figure 3-2).
This cylindrical tank is approximately 10 feet in height and 20 feet in
diameter and is located below the recovery furnace hearth.
Molten smelt composed of sodium sulfide and sodium carbonate accumulates
on the floor of the recovery furnace and is drained from this furnace
through smelt spouts. The smelt is discharged into a water-filled vessel
referred to as the smelt dissolving tank. "Green liquor" is formed by the
incorporation of the smelt into water through quenching.
Green liquor levels are maintained several feet below the top of the
tank to allow for expansion and steam liberation. Contact of the molten
sroelt with water creates large volumes of steam, which must be vented.
High liquor levels result in carryover of liquor droplets and particulate
matter into the tank vent system. The tank is agitated with compressed
air or mechanical agitation to aid in mixing. The water-cooled smelt
spout enters the tank through a doghouse enclosure installed on the top of
the tank.
Steam or recirculated green liquor 1s used in the smelt spout to
shatter the smelt before it contacts the liquor surface. Incomplete
shattering can result in violent steam explosions as large droplets enter
the water and release large quantities of steam. The major causes of
3-9
-------
LIGENO
A — dissolving tonk
B — furnace
C — vent stock
D — green liquor
E — air line (01 agitation
F — dog house
G — smelt spout
H — circulated green liquor ihotter spray
Figure 3-2. Smelt dissolving tank with water sprays.1
3-10
-------
explosions 1n smelt tanks (which constitute a serious and potentially
dangerous problem) are smelt sulfidlty, lack of shatter efficiency, lack
of smelt reduction efficiency, sodium chloride content, and sodium
hydroxide. Temperatures in the smelt spout are between 1600 and 2000°F.6
3.3 EMISSIONS
3.3.1 Uncontrolled Emissions
Because of turbulence in the space above the liquor in the smelt
dissolving tank, significant amounts of partlculate are emitted with the
steam. The uncontrolled emission rate from the tank varies greatly
depending on quench rate, tank design, exhaust volume, and smelt chemistry.
Some data indicate that a strong relationship exists between steam shatter
flow and carryover.6 Uncontrolled emissions from a typical smelt dissolving
tank {1000 tons of pulp/day) may be as high as 380 Ib/hr [8.0 Ib/T Air
Dryed Pulp (ADP)].
According to a representative from the National Council of the Paper
Industry for Air and Stream Improvement, a trade association for the
kraft pulp industry, the only process with sodium hydroxide emissions is
the smelt dissolving tank. He estimated that 25 - 50* of the particulate
emitted from this tank is sodium hydroxide. The rest of the particulate
consists of sodium sulfide and sodium carbonate.8
3.3.2 Emission Control Equipment
By proper attention to tank design, steam shatter jet location,
steam flow, and vent control, many mills are able to operate with minimum
abatement equipment on the smelt dissolving tank stack. The gases from
most smelt tanks are vented through demister pads which are fine wire mesh
screens about one foot thick. Demister pads are basically low energy
scrubbers with collection efficiencies of about 80 percent. Droplets
condensing from the gas collect on the screen, and are backflushed with
water sprays to the dissolving tank. Several dissolving tanks are equipped
with more efficient water scrubbers, such as low pressure drop Venturis
(6-8 inches of water), packed towers, or cyclones with water sprays.
3-11
-------
Efficiencies of these systems are about 95 percent. A few mills combine
the dissolving tank gases with the recovery furnace gases, sending both
streams to an electrostatic precip1tator.4
3.3.3 Controlled Emissions
Emission data reported for 29 dissolving tanks range from 0.05 to
2.38 Ib/T ADP (equivalent to about 0.009-0.4 gr/dscf) with a median of
1.0 Ib/T ADP (equivalent to about 0.17 gr/dscf).9 Available data reported
from a previous survey by EPA are shown in Table 3-2.9 These data compare
the efficiencies of various scrubber systems.
3-12
-------
TABLE 3-2. PARTICULATE EMISSIONS FROM VARIOUS
SMELT DISSOLVING TANK CONTROL SYSTEMS9
Control System
Demister pad
Demister pad plus
shower
Demister pad plus
packed tower
Packed tower
Collection
Efficiency %
72
77
78
90
93
71
96
92
98
Emission Rate
Ib/T ADP
0.052
0.15
0.63
2.3
1.2
1.58
0.41
1.20
0.05
g/kg ADpa
0.03
0.08
0.32
1.15
0.60
0.79
0.21
0.60
0.03
gr/dscft>
0.009
0.03
0.1
0.4
0.2
0.3
0.07
0.2
0.009
a Calculated from emissions in Ib/T ADP on the basis of 1.0 Ib/T ADP =
0.5 g/kg ADP. ADP = Air Dryed Pulp
b Calculated from emissions in Ib/T ADP on the basis of 1.0 gr/dscf =
5.76 Ib/T ADP.
3-13
-------
3.4 HEM INPUTS
Two sets of HEM inputs were developed for the kraft pulp Industry.
The first set was based on model smelt tanks that were developed in
October 1975 to perform a modeling analysis of the ambient air impact of
kraft pulp mills. These HEM inputs are shown in Table 3-3. The units
were assumed to operate 360 days/year. The yearly production for each of
the three model sizes was multiplied by a typical State regulation of 0.5
pounds of particulate matter per ton of unbleached kraft pulp produced to
determine the total particulate emitted from each model size. Based on a
conversation with NCASI, 25-50 percent of the total particulate is estimated
to be sodium hydroxide.8 Under worst case assumption, 50 percent of the
particulate was assumed to be sodium hydroxide and therefore the total
particulate emissions were multiplied by 0.5. These calculations are
presented in an appendix to this chapter.
The other set of HEM inputs is shown on Table 3-4. These were
obtained by selecting plants with various capacity sizes in the kraft
pulp industry. Information on these plants was requested from National
Emission Data System (NEDS). Sodium hydroxide emissions for smelt tanks
in these plants were determined by multiplying the typical States regula-
tion (0.5 Ib/ton of pulp) by the yearly production and multiplying by
0.5. If the estimated emissions for these plants, as shown in NEDS, were
based on emission test results, these estimates were used and multiplied
by 0.5 to determine the amount of sodium hydroxide. These calculations
are presented in an appendix to this chapter.
3-14
-------
TABLE 3-3.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM MODEL SIZE SMELT DISSOLVING
TANKS IN KRAFT PULP PLANTS
co
i— »
en
SIZE
(Tons/Day)
500
1000
1500
EMISSION
TYPE
Stack
Stack
Stack
a Cross-sectional area 1s
b Raced nn "\t
in riaue nai» u<
STACK
HEIGHT
(m)
53.0
53.0
53.0
defined as
%a** /\i%Av»^ + 4 f
CROSS-SECT. STACK
AREA* DIAMETER
(m2) (m)
80
80
80
the stack
tn
1.5
1.5
1.5
height x stack
STACK
VELOCITY
(m/s)
14.6
14.6
14.6
diameter.
STACK
TEMP.
366
366
366
NaOH
EMISSIONS
(kg/yr)b
20,500
40,900
61,000
-------
TABLE 3-4.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM SMELT DISSOLVING TANKS AT
CERTAIN KRAF
TOTAL
PRODUCT.
PLANT LAT. LONG. CAPACITY EMISS.
NAME STATE (deg, mln, sec) (TPD) TYPE
James AL 321325 880107 1000 Stack
River
Int. AR 333733 924919 801 Stack
Paoer
i o r '
Simpson CA 402542 1221600 225 Stack
Paper
Champion FL 303622 871924 1560 Stack
Int.
Great GA 310949 850537 1870 Stack
Southern
«JUU Wild *'
Paper
Union GA 320612 810718 2850 Stack
pamn
VsQI*i|/
Georgia LA 303900 911641 1290 Stack
Pacific I
T PULP PLANTS
STACK CROSS-SECT. STACK
HEIGHT AREA DIAMETER
(m) (m2) (m)
37
37
38
68
46
46
41
52
52
49
49
76
70
70
93
61
61
61
41
41
42
129
35
35
25
62
62
59
88
441
105
105
223
67
85
85
1.1
1.1
1.1
1.9
0.76
0.76
0.6
1.2
1.2
1.2
1.8
5.8
1.5
1.5
2.4
1.1
1.4
1.4
STACK STACK
VELOCITY TEMP.
(m/s) (°K)
5.4
5.4
4.1
3.9
6.8
8.8
7.8
7.1
7.1
7.5
8.2
0.88
3.8
4.8
6.5
9.1
6.1
6.7
352
348
356
341
356
363
343
344
344
347
333
450
339
345
339
344
361
361
NaOH
EMISSIONS EMISSION CONTROL
(Kg/yr) SOURCE EQUIP.
5,900
6,400
6,800
14,000
18,000
14,500
1,400
7,700
16,400
25,000
24,100
20,900
8,600
10,900
34,500
14,500
4,500
4,500
Tank 1
Tank 2
Tank 3
Tank 1
Tank 2
Tank 3
Tank 1
Smelt
Tank
Tank 1
Tank 2
Tank 3
Tank 12
Tank 13
Tank 14A
14B
Tank 1
Tank 2A
Tank 2B
None
II
Wet
Scrubber
Spray Tower
Water Curt.
Water Curt.
Wet Scrub.
Venturl
Scrubber
Wet Scrub.
II II
M li
Unknown
n
n
-------
TABLE 3-4. (Continued)
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM SMELT DISSOLVING TANKS AT
CtRTAIN KRAFT PULP PLANTS
PLANT
NAME STATE
Crown LA
Zellerbach
Weyer- NC
haeuser
Longvlew WA
Fibre
LAT.
(deg,
304237
351246
402542
LONG.
m1n, sec)
911930
770653
1221600
TOTAL
PRODUCT.
CAPACITY
(TPD)
495
700
2800
EMISS.
TYPE
Stack
Stack
"
Stack
"
"
"
STACK
HEIGHT
(m)
41
69
69
38
48
58
57
CROSS-SECT. STACK
AREA
(m2)
74
97
97
42
58
70
80
DIAMETER
(m)
1.8
1.4
1.4
1.1
1.2
1.2
1.4
STACK
VELOCITY
(m/s)
3.7
5.8
5.8
7.3
21.1
10.8
14.6
STACK
TEMP.
336
336
336
324
326
335
329
NaOH
EMISSIONS
(Kg/yr)
15,000
14,800
14,800
14,600
38,900
11,600
49,500
EMISSION CONTROL
SOURCE EQUIP.
Tank 1 M1st EHm.
Tank 1 "
Tank 2 "
Tank 11 "
Tank 15 "
Tank 18 "
Tank 19 "
-------
APPENDIX - CHAPTER 3 - KRAFT PULP
Based on telephone conversation with Russ Blosser, NCASI, the only
emission sources of NaOH at kraft pulp mills are smelt dissolving tanks.
Mr. Blosser estimated that 25-50 percent of particulate Is NaOH. For worst
case analysis, use 50 percent.
Typical State Standard for PM at Smelt Dissolving Tanks - 0.5 Ib/T of
pulp produced.
MODEL PLANTS
A. Smelt Tank - 500 TPD
PM Emissions
500 TPD x 360 days/year x 0.5 Ib/T = 90,000 Ib/yr
NaOH Emissions
90,000 Ib/yr x 0.5 x 1 kg = 20,500 kg/yr
"ZTZlb
B. Smelt Tank - 1000 TPD
PM Emissions
1000 TPD x 360 days/year x 0.5 Ib/T = 180,000 Ib/yr
NaOH Emissions
180,000 Ib/yr x 0.5 x 1 kg = 40,900 kg/yr
T3T\b
C. Smelt Tank - 1500 TPD
PM Emissions
1500 TPD x 360 days/year x 0.5 Ib/T = 270,000 Ib/yr
NaOH Emissions
270,000 Ib/yr x 0.5 x 1 kg = 61,000 kg/yr
T^lb
Actual Plants
A. James River - Butler. Alabama
PM Emission Estimates from NEDS based on Emission Tests
Tank 1-13 T/yr; Tank 2-14 T/yr; Tank 3-15 T/yr
3-18
-------
NaOH Emission Estimates
Tank 1
13 T/yr x 0.5 x 2000 Ib/T x lkg/2.2 Ib = 5,900 kg/yr
Tank 2
14 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 6,400 kg/yr
Tank 3
15 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 6,800 kg/yr
B. International Paper - Camden. Arkansas
PM Emission Estimates from NEDS Based on Emission Tests
Tank 1 - 31 T/yr; Tank 2-40 T/yr; Tank 3-32 T/yr
NaOH Emission Estimates
Tank 1
31 T/yr x 0.5 x 2000 IbT x 1 kg/2.2 Ib = 14,000 kg/yr
Tank 2
40 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 18,000 kg/yr
Tank 3
32 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 14,500 kg/yr
C. Champion International - Pensacola, Florida
PM Emission Estimates from NEDS based on Emission Tests
Smelt Tank - General - 17 T/yr; Smelt Tank - General - 36 T/yr
NaOH Emission Estimates
Smelt Tank - General
17 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 7,700 kg/yr
Smelt Tank - General
36 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 16,400 kg/yr
3-19
-------
D. Great Southern Paper - Cedar Springs, Georgia
PM Emission Estimates from NEDS Based on Emission Tests
Tank 1 - 55 T/yr; Tank 2 - 53T/yr; Tank 3-46 T/yr
NaOH Emission Estimates
Tank 1
55 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 25,000 kg/yr
Tank 2
53 T/yr x 0.5 x 2000 Ib/T x lkg/2.2 Ib = 24,100 kg/yr
Tank 3
46 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib - 20,900 kg/yr
E. Union Camp - Savannah. Georgia
PM Emission Estimates from NEDS based on Emission Tests
Tank 12 - 19 T/yr; Tank 13 - 24 T/yr; Tank 14A/14B - 76 T/yr
NaOH Emission Estimates
Tank 12
19 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 8,600 kg/yr
Tank 13
24 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 10,900 kg/yr
Tank 14A/14B
76 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 34,500 kg/yr
F. Georgia-Padflc-Zachary. Louisiana
PM Emission Estimates from NEDS based on Emission Tests
Tank 1-32 T/yr; Tank 2A - 10 T/yr; Tank 2B - 10 T/yr
NaOH Emission Estimates
Tank 1
32 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 14,500 kg/yr
Tank 2A
10 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 4,500 kg/yr
3-20
-------
Tank 2B
10 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 4,500 kg/yr
G. Crown Zellerbach - St. Franclsvllle, Louisiana
PM Emission Estimates from NEDS based on Emission Tests
Tank 1 - 34 T/yr
NaOH Emission Estimate
34 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 15,000 kg/yr
H. Weyerhaeuser - New Bern, NC
PM Emissions from 2 Smelt Tanks
725 TPD x 360 D/yr x 0.5 Ib/T x 1 T/2000 Ib = 65 T/yr
NaOH Emission Estimate (2 Tanks)
65 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 29,500 kg/yr
I. Longvlew Fibre - Longvlew, Washington
PM Emissions from 4 Smelt Tanks
2,800 TPD x 360 D/yr x 0.5 Ib/T x 1 T/2000 Ib = 252 T/yr
NaOH Emission Estimates
Tank 11
Est. PM Emission Tank 11 (From NEDS) x 252 T/yr x 0.5 x 2000 Ib x 1 kg/2.2 Ib
Total PM Emissions - Smelt Tanks (From NEDS)
24 TPY x 252 T/yr x 0.5 x 2000 Ib/T x 1 kg/ 2.2 Ib = 14,600 kg/yr
188 TPY
Tank 15
64 TPY x 252 T/yr x 0.5 x 2000 Ib/T x 1 kg/ 2.2 Ib = 38,900 kg/yr
188 TPY
Tank 18
19 TPY x 252 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 11,600 kg/yr
188 TPY
Tank 19
81 TPY x 252 T/yr x 0.5 x 2000 Ib/T x 1 kg/2.2 Ib = 49,500 kg/yr
188 TPY
3-21
-------
3.5 REFERENCES
1. 1985 Lockwood's Directory of the Pulp and Allied Trades,
New York, Vance Publishing Corporation.
2. 1986 Post's Pulp and Paper Directory. San Francisco, Miller Freeman
Publications, Incorporated.
3. U.S. Environmental Protection Agency. Review of New Source Performance
Standards for Kraft Pulp Mills. Publication No. EPA-450/3-83-017.
Research Triangle Park, NC. September 1983.
4. U.S. Environmental Protection Agency. Standards Support and Environmental
Impact Statement, Volume 1: Proposed Standards of Performance for Kraft
Pulp Mills. Publication No. EPA-450/2-76-014a. Research Triangle
Park, NC. September 1976.
5. Sallack, J.A. An Investigation of Explosions in the Sode Smelt
Dissolving Operation. Canadian Pulp and Paper Association,
Technical Section, June 1955.
6. U.S. Environmental Protection Agency. Kraft Pulp Mill Inspection
Guide. Publication No. EPA-340/1-83-017. Research Triangle Park, NC.
January 1983.
7. Environmental Engineering Inc.; and J.E. Sirrine Company. Control of
Atmospheric Emissions in the Wood Pulping Industry. Contract No.
CPA 22-69-18. March 15, 1970.
8. Telecon. Blosser, Russ., National Council of the Paper Industry for Air
and Stream Improvement, with Neuffer, William, EPA. April 9, 1987.
Information on sodium hydroxide emissions from the kraft pulp industry.
9. U.S. Environmental Protection Agency. Atmospheric Emissions from the
Pulp and Paper Manufacturing Industry. Publication No. EPA-450/1-73-002.
Research Triangle Park, NC. September 1973.
3-22
-------
4.0 BEER MANUFACTURING
4.1 INDUSTRY DESCRIPTION
Table 4-1 shows the 112 breweries located In the United States.
4-1
-------
TABLE 4-1.
Breweries Located in the United States - 19861
Company
G. Heileman Brewing Co., Inc
Arkansas Brewing Co., Inc.
Anchor Brewing Co.
Anheuser-Busch, Inc.
Anheuser-Busch, Inc.
Buffalo Bill's Brewery
Golden Pacific Brewing Co.
Koryo Winery Co. (Sake Brewery)
Koryo Winery Co. (Sake Brewery)
Mendocino Brewing Co.
Miller Brewing Co.
Old Los Angeles Brewery
Ozeki San Benito
Palo Alto Brewing Co.
Redwood Brewing Company
Roaring Rock Brewery
The Saxton Brewery
Sierra Nevada Brewing Co.
Stanislaus Brewing Co., Inc.
The Stroh Brewery Company
Takara Sake USA, Inc.
Thousand Oaks Brewing Co.
Truckee Brewing Company
U C at Davis (Exp-Brewery)
Under the Oaks Brewery
Adolph Coors Co.
Boulder Brewing Co.
Anheuser-Busch, Inc.
Anheuser-Busch, Inc.
The Florida Brewery, Inc.
Pabst Brewing Co.
Miller Brewing Co.
G. Heileman Brewing Co,
Inc.
Location
Phoenix, AZ
Little Rock, AR
San Francisco, CA
Fairfield, CA
Los Angeles, CA
Hayward, CA
Emeryville, CA
Los Angeles, CA
Gardena, CA
Hopland, CA
Irwindale, CA
Los Angeles, CA
Hollister, CA
Menlo Park, CA
Petaluma, CA
Berkeley, CA
Chico, CA
Chico, CA
Modesto, CA
Los Angeles, CA
Berkeley, CA
Berkeley, CA
Truckee, CA
Davis, CA
Ojai, CA
Golden, CO
Boulder, CO
Jacksonville, FL
Tampa, FL
Auburndale, FL
Tampa, FL
Albany, GA
Perry, GA
4-2
-------
Table 4-1. (cont.)
Company
Honolulu Sake Brewery
Snake River Brewing Co.
G. Heileman Brewing Co., Inc.
Tae Hwa Brewing Co., Inc.
Falstaff Brewing Corp.
G. Heileman Brewing Co.
Dubuque Star Brewing Co.
Mi 11 stream Brewing Co.
Dixie Brewing Co., Inc.
G. Heileman Brewing Co., Inc.
G. Heileman Brewing Co., Inc.
Geyer Bros. Brewing Co.
Kalamazoo Brewing Co., Inc.
The Real Ale Company, Inc.
The Stroh Brewery Co.
Cold Spring Brewing Co.
G. Heileman Brewing Co., Inc.
The Stroh Brewery Co.
August Schell Brewing Co.
Anheuser-Busch, Inc.
Montana Beverages Ltd.
Anheuser-Busch, Inc.
Anheuser-Busch, Inc.
Champa!e, Inc.
Eastern Brewing Corp.
Pabst Brewing Co.
Vernon Valley Brewery, Inc.
Anheuser-Busch, Inc.
Genessee Brewing Co., Inc.
Miller Brewing Co.
West End Brewing Co. of Utica, N.Y.
William S. Newman Brewing Co. Inc.
Location
Honolulu, HI
Caldwell, ID
Belleville, IL
Waukegan, IL
Fort Wayne, IN
Evansville, IN
Dubuque, IA
Amana, IA
New Orleans, LA
Baltimore, MD
Frankenmuth, MI
Frankenmuth, MI
Kalamazoo, MI
Chelsea, MI
Detroit, MI
Cold Spring, MN
St. Paul, MN
St. Paul, MN
New Ulm, MN
St. Louis, MO
Helena, MT
Merrimack, NH
Newark, NJ
Trenton, NJ
Hammonton, NJ
Newark, NJ
Vernon, NJ
Baldwinsville, NY
Rochester, NY
Fulton, NY
Utica, NY
Albany, NY
4-3
-------
Table 4-1. (cont.)
Company
Miller Brewing Co.
The Stroh Brewery Co.
Anheuser-Busch, Inc.
The Hudepohl Brewing Co.
Miller Brewing Co.
The Schoenling Brewing Co.
Columbia River Brewery
6. Heileman Brewing Co., Inc.
Hillside Brewery & Public House
Portland Brewing Co.
Widmer Brewing Company
Jones Brewing Co.
Latrobe Brewing Co.
The Lion, Inc.
Pittsburgh Brewing Co.
The Stroh Brewing Co.
C. Schmidt & Sons, Inc.
Straub Brewery, Inc.
D.G. Yuengling & Sons, Inc.
The Stroh Brewing Company
Anheuser-Busch, Inc.
G. Heileman Brewing Co., Inc.
Miller Brewing Co.
Pearl Brewing Co.
Pearl Brewing Co.
Reinheitsgebot Brewing Co.
Spoetzl Brewery, Inc.
The Stroh Brewing Co.
Anheuser-Busch, Inc.
Chesapeake Bay Brewing Co.
General Brewing Co.
Hale's Ales, Ltd
Hart Brewing, Inc.
G. Heileman Brewing Co., Inc.
Independent Ale Brewing, Inc.
Kemper Brewing Co.
Kufnerbrau
Pabst Brewing Co.
Yakima Brewing & Malting Co.
G. Heileman Brewing Co. Inc.
Hibernia Brewing, Ltd.
Jos. Huber Brewing Co.
Location
Eden, NC
Winston-Salem, NC
Columbus, OH
Cincinnati, OH
Trenton, OH
Cincinnati, OH
Portland,
Portland,
Portland,
Portland,
Portland,
OR
OR
OR
OR
OR
Smithton, PA
Latrobe, PA
Wilkes-Barre, PA
Pittsburgh, PA
Allentown, PA
Philadelphia, PA
St. Marys, PA
Pottsville, PA
Memphis, TN
Houston, TX
San Antonio, TX
Fort Worth, TX
San Antonio, TX
Galveston, TX
Piano, TX
Shiner, TX
Longview, TX
Williamsburg, VA
Virginia Beach, VA
Vancouver, WA
Colville, WA
Kalama, WA
Seattle, WA
Seattle, WA
Rollingbay, WA
Monroe, WA
Olympia, WA
Yakima, WA
La Crosse, WI
Eau Claire, WI
Monroe, WI
4-4
-------
Table 4-1. (cont.)
Company Location
Jacob Lelnenkugel Brewing Co. Chippewa Falls, WI
Miller Brewing Co. Milwaukee, WI
Pabst Brewing Co. Milwaukee, WI
Sprecher Brewing Co., Inc. Milwaukee, WI
Stevens Point Beverage Co. Stevens Point, WI
4-5
-------
4.2 PROCESS DESCRIPTION
4.2.1 General
Between the ripe barley grain (a starchy raw material used in the form of
malt) and the cool, satisfying glass of beer, many production steps are involved.
A process flow diagram is given on Figure 4-1.
The four main steps in the production of beer are mashing, fermenting,
storage or layering, and bottling. Barley malt is the principal ingredient for
beer and is usually made by the malting industry. Essentially, malt is barley
which has been soaked 1n water and allowed to germinate after which it is
redryed and ground to a powder. Mashing is the process whereby, by help of
enzymes, starch, sugar and proteins are converted to simpler water soluble
fermentable compounds. Mashing occurs at temperatures of 140 - 160°F. The malt
extract is dissolved in water and the resulting liquid is known as wort (unfer-
mented beer). Hops are added to the wort in a brew kettle, where the wort is
boiled one-and-a-half to three hours. The wort is strained to remove hops, and
sludge is removed by a filter or centrifuge and is then cooled to 50°F. As
the wort cools, air that is necessary to begin fermentation is absorbed by the
wort. Yeast, usually obtained from an earlier brew, is mixed with the wort in
line to the fermentation starter tanks. Fermentation, the conversion of simple
sugars in the wort to ethanol and carbon dioxide, is completed in a closed
fermenter. Cooling is required to maintain the proper fermentation temperature.
After fermentation is completed, beer is stored to age for several weeks at
32°F in large closed tanks. The beer is then recarbonated, pumped through a
pulp filter, pasteurized at 140°F and packaged in bottles and cans. Draft beer
is not pasteurized and some breweries such as Coors do not pasteurize bottled
or canned beer.2-4
4.2.2 Specific Process of Interest
As shown in the next section, the only process sources estimated to emit
sodium hydroxide at breweries are bottle washing systems. Returnable and
nonreturnable bottles are first preheated and prerinsed. The bottles are then
soaked in a caustic soda solution that varies from 0.5 - 5% at temperatures
between 160 - 180°F. After soaking, the bottles in some machines are sprayed
internally and externally with a caustic soda solution before going to the after-
rinse. After-rinsing consists of spraying with hot water, lukewarm water and
4-6
-------
grits
malt
mills
_ refrigeration
'- compressor -
mixing^
tanks
can can Mlers
i washers .,
can closers pacKers
ftff « -I . ' IT.
:_L l
crowners ~^^ pasteurizer
'abe'ers packers
11 rm m
pasteurizer
tarrel
fillers
beer coolers
carbon dioxide
compressor
\
carbon / reducing
dioxide ;iquefier carbon dioxide valve
liquid storage
second
carbonation
Figure 4-1. Beer Manufacturing'
4-7
-------
finally cold water. Bottle washing machines in the U.S. are usually fitted with
3-5 compartments for soaking with varying strengths of caustic soda and
various temperatures. The strengths of the caustic soda solutions are set by
law not to be below certain levels. After cleaning, the bottles are filled,
closed with crown corks and then pasteurized.4
According to a representative of The Beer Institute, all breweries for the
major brewing companies (Anheuser-Busch, Miller, etc.) will have a bottle washing
process that uses sodium hydroxide. Also, all breweries in States such as New
York and Pennsylvania, which have deposits on glass bottles would have bottle
washing systems.5 According to an Anheuser-Busch employee, all returnable bottles
are washed with a sodium hydroxide solution to strip labels and for sterilization.
Sodium hydroxide solutions are not used for washing new glass bottles.6.7
Detailed information was obtained on the two bottle washing systems used
by Miller Brewing at their Fulton, New York brewery. The dimensions of each
bottle washing system are 75 feet in length, 16 feet wide and a height of 15
feet and was manufactured by Barry Wehmiller Company, St. Louis, Missouri.
Returnable bottles are placed on a rinsing conveyor which is initially treated
by a caustic wash using a 5 percent sodium hydroxide solution. The tank has 11
compartments each with a capacity of 4,000 gallons. The tank is heated to an
operating temperature of 120 - 175°F by steam indirect heating coils. The
retention time of bottles in this tank is 36 minutes and approximately 1,200
bottles are washed per minute. At any one time, approximately 44,000 bottles
are in each system. After the caustic wash tank, the bottles are rinsed in hot
water tanks. The 5 percent caustic solution is obtained by tank trucks and is
stored in a 10,000 gallon storage tank prior to bring pumped to various locations
in the brewery.7
4.3 EMISSIONS
Sodium hydroxide emission estimates were developed by the State of New
York for the Miller Brewing plant in Fulton, New York. These calculations are
contained in the appendix to this chapter.
4.4 HEM INPUTS
HEM inputs for bottle washing at Miller Brewing, Fulton, New York are
contained in Table 4-2.
4-8
-------
TABLE 4-2.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM BEER MANUFACTURING
PLANT LAT. LONG.
NAME STATE (deg. mln, sec)
STACK CROSS-SECT. STACK STACK STACK NaOH
EMISS. HEIGHT AREA DIAMETER VELOCITY TEMP. EMISSIONS EMISSION CONTROL
TYPE (m) (m2) (m) (m/s) (°K) (Kg/yr) SOURCE EQUIP.
MUler
Brewing NY 431804 762250
Stack 9.1 6.9
Stack 9.1 5.6
0.76 8.2 290 24,000 Bottle None
Washing
System
0.61 8.2 290 24,000 Bottle None
Washing
System
to
-------
APPENDIX - CHAPTER 4 - THE BEER INDUSTRY
Miller Brewing - Fulton. NY
- Bottle Washing System
Engineering estimate from Miller Brewing
- 0.008 Ib moisture/1b of air
- 23,085 Ib of air/hour
0.008 Ib moisture x 23,085 Ib of air _ 185 Ib moisture
Ib of air hour= hour
Solution for system in 5% sodium hydroxide
- Assume moisture is also 5% sodium hydroxide
185 Ib moisture x 0.05 _ 9 Ib NaOH
hour= hour
Hours of operation - 21.5 hours/day; 273 days/year
so yearly emissions of sodium hydroxide are:
9 Ib NaOH x 21.5 hours x 273 days/yr 52,800 Ib NaOH
hourday = year
52,800j^x 1 kg = 24,000 Jc£
yr 2.2 Ib yr
4-10
-------
4.5 REFERENCES
1. Bureau of Alcohol, Tobacco and Firearms. U.S. Department of the Treasury.
Breweries Authorized to Operate. Publication No. ATF P 5100.13. Washington,
DC. April 1986.
2. Mrak, E.M., H.J. Phaff. Malt Beverage. In: McGraw-Hill Encyclopedia of
Science and Technology, Volume 8. New York, McGraw-Hill Book Company.
1977. pp. 91-93.
3. Compilation of Air Pollutant Emission Factors, Fourth Edition. U.S.
Environmental Protection Agency. Research Triangle Park, NC. Publication
No. AP-42. September 1985.
4. Hoyrup, H.E. Beer and Brewing. In: Kirk-Othmer Encyclopedia of Chemical
Technology, Volume 3. New York, John Wiley and Sons, Inc. 1964. pp. 297-338.
5. Telecon. Nateman, Gary, The Beer Institute with Neuffer, William, U.S.
Environmental Protection Agency. May 12, 1987. Bottle washing at breweries.
6. Telecon. DeHart, Don, Anheuser-Busch with Neuffer, William, U.S.
Environmental Protection Agency. May 27, 1987. Bottle washing systems
at breweries.
7. Telecon. Warakomski, John, Miller Brewing with Neuffer, William, U.S.
EPA. June 16, 1987. Description of bottle washing system at Fulton, NY
plant.
4-11
-------
5.0 AUTOMOTIVE CARBURETOR MANUFACTURING INDUSTRY
5.1 INDUSTRY DESCRIPTION
Table 5-1 shows the primary automotive carburetor manufacturing plants fn
the United States. According to a printout from the Automotive Parts Rebuilders
Association, there are approximately 140 fuel system rebullders most of which
rebuild carburetors.1
5.2 PROCESS DESCRIPTION
Information was obtained from four primary carburetor manufacturing plants
and two rebuilt carburetor manufacturing plants. Sodium hydroxide solutions are
used very infrequently in rebuilt carburetor manufacturing and then only for
smaller installations. Three of the five primary carburetor manufacturing plants
use these solutions. One of the other primary carburetor manufacturing plants
(Ford - Ypsilanti, Michigan) uses potassium hydroxide for plating and metal
cleaning.
Process information was obtained from Holley Automotive, Bowling Green,
Kentucky. Figure 5-1 shows the process flow for the five lines at this plant
that use sodium hydroxide solutions. Those processes that use caustic soda
are identified with astericks. These lines are manual or automotive and are
operated 16 hours/day; 5 days/week. Maximum operating rates for each line
are: DMP Automatic - 500 Ib/hr; Udylite - 900 Ib/hr; DMP Manual - 400 Ib/hr and
Adjamatic and Deoxidize lines - 650 Ib/hr. The DMP Auto and Udylite lines
are zinc plating lines. DMP Manual is a black oxide and phosphate coating
process. The Adjamatic and Deoxidize lines put a chromate finish on carburetor
pieces. Each carburetor piece goes through only one of these lines. There are
approximately 20 - 100 metal pieces per batch. The concentrations of the
caustic soda solutions used vary from 5-10 percent. The operating temper-
atures for those processes that use these solutions vary from 135 - 140°F.
Tanks are directly heated by electrical heat elements. Metal pieces stay in
the bath for a maximum of 3 minutes, except the zinc electroplating tanks where
parts can stay up to 20 minutes. Tanks are dumped weekly to a pretreatment
system. The waste goes to one of three electrochemical treatment cells and
then to two rectangular clarifiers in series. The liquid discharge from the
5-1
-------
TABLE 5-1. U.S. Primary Automotive Carburetor Manufacturing Plants
COMPANY LOCATION
Holley Automotive Bowling Green, Kentucky
Ford Motor Company Ypsllanti, Michigan
Carter Carburetor St. Louis, Missouri
Rochester Products, Division of
General Motors Rochester, New York
Weber Carburetor Sanford, North Carolina
5-2
-------
DMP AUTOMATIC PLATING
1 1
1 WARM |
1 RINSE |
1 1
1 1
.1 SOAK |
"* 1 CLEAN |
1 * 1
1 III
. | ELECTRO- 1 . | COLD |
"* 1 CLEAN | ^ IRINSE |
1*11 1
1 1
^1 COLD |
"^ IRINSE |
1 1
1 1
_. 1 COLD |
•* 1 RINSE |~~
1 1
1 1
.1 ACID |
~*| HEAVY |
1 1
1
t
1 1
1 ZINC 1 .
(PLATING*^
1 * 1
1 1
1 COLD |
"(RINSE | *
1 1
III 1
I COLD | . ICHROMATEI .
— IRINSE n | |*
III 1
1 1
1 COLD |
~~|RINSE |*
1 1
1 1
1 COLD |
(RINSE | *
1 1
1 1
1 ACID |
ILIGHT I
1 I
DEOXIDIZE LINE
1 1
I SOAP |
1 * l~~~
1 1
1 1
. 1 CLEAR!
"^ 1 RINSEI
1 1
1 1
_.. 1 DART |
* 1 1st |~
1 ACID |
1 1
. 1 CLEAR |
* | RINSE |
1 1
1 1
_O WARM |
"^1 RINSEI
1 1
ADJAMATIC
1 1 1 1 1 1 1 1
1 SOAP | . I CAUSTIC ._ (CLEAR | . | CLEAR!
1 * 1 ^1 * 1 ^IRINSE | 7| RINSEI :
1 1 1 1 1 1 1 1
1 1
^| CLEAR |
1 1
1 1
. (CLEAR |
"^ IRINSE |
1 1
1 1
j^J DRIP |
"^1 1
1 1
1
III!
1 DRIP | , (CLEAR I y_
1 I \ IRINSE | v-
1 1 1 1
1 1
1 CLEAR | ,
~| RINSEI v-
1 1
1 1
1 CLEAR | .
I RINSEI ^
1 1
1 1
ICHROMATEI
~~l 1
1 1
* Sodium hydroxide solutions used 1n these processes
Figure 5-1. Process Lines - Holley Automotive - Bowling Green, Kentucky^
5-3
-------
UDYLITE PLATING
I 1
1 SOAP |
I CLEAN |
1 * 1
1 1
. I ELECTRO- 1
•^1 CLEAN |~
1 * 1
1 I
_. 1 COLD |
~^ | RINSEI —
1 1
I I
v. 1 COLD |
"^ 1 RINSEI
1 1
1 1 1 1 1 1
_. I ACID | ^ | COLD | >. | COLD |
^ 1 1 ^ 1 RINSEI ^ | RINSEI
1 1 1 1 1 1
i
1 1
1 COLD | ..
I RINSEI ^
1 1
1 1
I COLD | ^.
~| RINSEI^"
1 1
1 1
ICHROMATEI .
-, ,«•
1 1
1 1
1 COLD | ^_
1 RINSEI *
\ \
1 1 1 1 1 1
I DRIP | ^ | ZINC I . | DRIP I
1 | ^ IPLATING^ | |
1 1 1 1 1 1
DMP MANUAL PLATING
1 1
1 HOT |
1 OIL I"
1 1
1 1 1 1
. I RINSEI . | RINSEI v
^ 1 l~^ 1 l~~7
1 1 1 1
1 1
1 BLACK | v
1 OXIDE | ~?
\ \
1 H.W. |
| RINSEI v
' I PRE- |— ->
1 HEAT |
III!
1 ACID | ^ | RINSEI
1 l~^l 1
1 1 1 1
1
1 1
1 HOT | .
1 OIL |^
1 1
1 II 1
I ZINC I ^ \ ZINC I
(PHOSPHATE "^ (PHOSPHATE
1 III
\ \
^ I RINSEI
^~l 1
1 1
1 1
. I BLACK |
^ 1 OXIDEI
1 1
Till
^ I SOAK | ^ | RINSEI
^~| CLEAN) "^ | |
1*1 1 1
* Sodium hydroxide solutions used in these processes
Figure 5-1. Process Lines - Hoiley Automotive - Bowling Green, Kentucky2
(continued)
5-4
-------
final clarifier 1s discharged to the city sewer. The sludge collected by the
clarlflers passes to a filter press and then a sludge dryer. The dryer produces
a fine powder that is hauled to a hazardous waste landfill. All tanks have
stainless steel construction with a capacity for each tank of 160 gallons.
Tank dimensions are 36 inches in width, 40 inches long, and 30 inches high.3
Details on the purpose of these tanks and other information is contained
in Chapter 6 - Electroplating.
5.3 EMISSIONS
5.3.1 Uncontrolled Emissions.
Uncontrolled emission estimates for all processes at Rochester Products
are shown on Table 5-3 as none of these processes have emission control
equipment. The method that was used to determine some of these estimates is
contained in the appendix to this chapter. All estimates were developed by
plant personnel. Uncontrolled emissions for the various plating lines at
Holley Automotive are contained in a printout from the State of Kentucky and
are given in Table 5-2.
5.3.2. Emission Control Equipment
Only one automotive carburetor manufacturing plant, Holley Automotive,
is known to have emission control equipment. Each tank that uses caustic
soda including zinc electroplating bath tanks has a push/pull ventilation
system that is exhausted to a scrubber. There are four packed tower scrubbers
that use water as the scrubbing medium and the packing media is composed of
polypropylene. The operating pressure drop is 6 inches of pressure water gauge
and discharged water goes to a pretreatment system. The scrubbers are manu-
factured by KCH of Forest City, North Carolina. Emissions from tanks that do
not use caustic soda are ducted to other scrubbers.3
5.4 HEM INPUTS
HEM inputs for this industry are given in Table 5-3. These Inputs were
obtained from printouts obtained from the States of New York and Kentucky.
These estimates were discussed with plant personnel and changes were made
where appropriate. The methodology of determining some of these estimates
for Rochester Products is contained in the appendix to this chapter.
5-5
-------
TABLE 5-2. UNCONTROLLED EMISSIONS - HOLLEY AUTOMOTIVE -
BOWLING GREEN, KENTUCKY*
Process
Pollutant
Emissions (TPY)
Manual 4 Auto DMP Plating
Automatic DMP Plating
Adjamatic A Deoxidize
Udylite Plating
TSP
Nitric Acid
HC1
Sodium Hydroxide
HC1
Sodium Hydroxide
H3P04
Sodium Hydroxide
HC1
Sodium Hydroxide
0.027
0.003
0.015
0.056
0.104
0.016
0.180
0.016
0.004
0.120
0.220
5-6
-------
TABLE 5-3.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM CARBURETOR MANUFACTURING
PLANT
NAME STATE
Rochester NY
Products
n
j
Holley KY
Carburetor
LAT. LONG. EMISSION
(DEG, MIN, SEC) TYPE
431049 773923 Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
365837 855420 Stack
Stack
Stack
Stack
10
11
14
24
82
160
162
163
164
165
218
282
286
296
13
14
18
19
HEIGHT
(M)
12
12
12
11
11
12
12
12
12
12
9
11
10
10
9
9
9
9
VERTICAL
AREA
(SQ. M.)
6
7
6
3
4
7
7
7
7
7
5
4
6
9
10
10
7
8
.1
.3
.1
.3
.5
.3
.3
.9
.9
.3
.5
.5
.1
.5
.0
.0
.2
.1
DIAMETER
(M)
0.51
0.61
0.51
0.30
0.41
0.61
0.61
0.66
0.66
0.61
0.61
0.41
0.61
0.95
1.1
1.1
0.8
0.9
VELOCITY
(M/S)
11.2
21.3
10.9
3.0
9.1
11.6
10.7
12.2
12.2
10.7
10.4
6.7
4.0
12.2
20.0
20.0
20.0
17.0
TEMP.
297
297
297
311
297
297
297
297
297
297
319
333
297
303
299
299
299
299
EMISSIONS
(Kg/yr)
2990
450
1700
0.5
550
16100
710
1040
1040
710
3450
0.9
990
820
0.9
1.8
0.0
1.8
SOURCE
DESCR.
Manual Plating
Cleaning Tank
CONTROL
DEVICE
None
Z1nc Plating Tank None
Caustic Cleaning
Tanks
Automatic Tote
Pan Washer
Caustic Solution
Tanks
None
None
None
3 Ionic Z1nc Plating None
Tanks
Sodium Zlncate
Plating Bath
Ionic Z1nc Platl
Tank
None
ng None
Ionic Z1nc Plating None
Tank
Sodium Zlncate
Plating Bath
Caustic Cleaning
Drum-Type Washer
Caustic Cleaning
Carden Plater
Manual A Auto.
DMP Plating *
Manual A Auto.
DMP Plating**
Adjamatlc A
Deoxidize
UdylHe Plating
None
None
None
Tank None
None
Packed Tower
Scrubber
Packed Tower
Scrubber
Packed Tower
Scrubber
Packed Tower
Scrubber
Manual DMP - Ac1d,^z1nc phosphate tanks; Automatic DMP
**Manual DMP - Hot oil, soak clean, black oxide; Automatic
- Add (light and heavy), chromate.
DMP - soak clean, electroclean, zinc plating.
-------
APPENDIX - CHAPTER 5
Rochester Products - Rochester, NY
Sodium hydroxide emission estimates were developed by the company and
submitted to the State agency. Calculations for some of these processes were
sent by the State of New York and were discussed with plant personnel. These
processes are discussed below.
1. Emission Point -0010 (Four Manual Plating Cleaning Tanks)
From Industrial Ventilation; 18th Edition, p. 4-19
Q = 2.8 LVX (Slot on table or bench)
Q = Required exhaust volume; cfm
L = Length of hood, slot, table; feet
V = Capture velocity at distance X; fpm
X = Distance from hood face to furthest point of source; feet
V = Q = 1200 cfm/tank (four tanks)
Z.8LX 2.8 (1.5 ft)(8ft)
= 35.8 ft/min
From Buffalo Forge Fan Engineering, p. 95
W = ( 95 + 0.425V ) (ew - ea)
r
W = amount of water evaporated, Ib/ft^/hr
V = longitudinal velocity of air, ft/min
r = latent heat of vaporization
ew= vapor pressure that corresponds to water temp, of process,
(in Hg)
ea= vapor pressure of moisture in air (in Hg)
W = ( 95 + (0.425) ( 35.8) ) (5.881 - 0.436)
TUPf
= 0.59 Ibs/hr/ft2/tank
Sodium Hydroxide Emissions for all four tanks (5.7% NaOH in tank)
a. Hourly
(0.59 Ibs/hr/ft2/tank) (4 tanks) (12 ft2/tank)(.057) = 1.63 Ibs/hr
b. Yearly
(1.63 Ibs/hr) (16 hrs/day) (252 days/yr) = 6570 Ib/yr
6570 Ib/yr x ( 1kg } = 2990 kg/yr
2.21b
5-8
-------
2. Emission Point - 0014 (2 Caustic Cleaning Tanks)
Q = 3.7 LVX (Freely Suspended Slot)
Q = Required exhaust volume; cfm
L = Length of hood, slot, table; feet
V = Capture velocity at distance X; fpm
X = Distance from hood face to farthest point of source; feet
v = Q = 2300 cfm/tank = 38.8 ft/min
3.7(LX) 3.7 (BftHZft)
W = ( 95 + 0.425 V ) (ew - ea)
r
= ( 95 + 0.425 (38.8) ) (5.881 - 0.436)
TUT?
= 0.60 lbs/hr/ft2
Sodium Hydroxide Emissions from 2 tanks (4.3% NaOH in tank)
a. Hourly
(0.60 lbs/hr/ft2) (36ft2) (0.043) = 0.93 Ibs/hr
b. Yearly
(0.93 Ibs/hr) (16 hrs/day) (252 days/yr) = 3750 Ibs/yr
3,750 Ibs/yr x ( 1kg ) = 1700 kg/yr
3. Emission Point -0011 (1 Zinc Plating Tank)
Q = 960 cfm/section (4 sections in tank)
Q = 3.7 LVX
v = Q = 960
3./ (LMX) 6.1 (IHl./b)
= 37 ft/min
W = ( 95 + 0.425 V ) (ew - ea)
R
= ( 95 +0.425 (37) ) (0.875 - 0.436)
1051.4
= 0.046 Ibs/hr/ft2 of tank
5-9
-------
3
The tank is 4 ft deep x 16 ft long
Total Hourly Emissions
(0.046 Ibs/hr/ft*) (64 ft*) = 2.94 Ibs/hr
NaOH Yearly Emissions (Tank is 8.3% NaOH)
(2.94 Ib/hr) (16 hr/day) (252 day/yr) (0.083) = 980 Ib/yr
980 Ib/hr f Ikgj = 450 kg/yr
5-10
-------
5.5 REFERENCES
1. Letter and attachment from Kroell, K., Automobile Parts Rebuilders
Association, to Neuffer, W.J., EPA. May 14, 1987. List of fuel systems
rebuilders.
2. Letter and attachment from Wells, T., Holley Automotive Division, to
Neuffer, W.J., EPA. June 8, 1987. Process Flow Diagram.
3. Telecon. Wells, Ted, Holley Automotive Division with Neuffer, W.J.,
EPA. May 14, June 16, and June 17, 1987. Process and emission control
information on Bowling Green, Kentucky plant.
4. Letter and attachment from Parker, D.M., Division for Air Quality,
Commonwealth of Kentucky, to Neuffer, W.J., EPA. February 2, 1987.
Printout from the Kentucky Emissions Inventory System.
5-11
-------
6.0 METAL FINISHING
C
6.1 INDUSTRY DESCRIPTION
According to the 1982 Census of Manufacturers, SIC 3471 (Electroplating,
plating, polishing, anodozing, coloring, and finishing of metals and formed
products) has 3,367 companies and 3,450 establishments. Eight hundred and
ninety eight of these establishments employ more than 20 employees.1 One
hundred and sixty four plants have greater than 100 employees. A list of
plants In this SIC code with greater than 500 employees is shown on Table 6-1.
6.2 PROCESS DESCRIPTION
6.2.1 General
Electroplating is the main plating technique used and is the production
of a thin metal surface coating on another metal by electrodeposition. Other
plating methods are discussed later. This surface coating is applied to
provide corrosion protection, wear or erosion resistance, anti-frictional
characteristics or for decorative purposes.3 In electroplating, metal ions in
either acid, alkaline or neutral solutions are reduced on cathodic surfaces
which are the pieces being plated. The most common methods of plating are in
barrels, on racks or continuously from a spout or coil.3 The main processes
involved in metal finishing are shown on Figure 6-1.
Before a metal can be electroplated, the metal surface must be prepared
to ensure the desired bond. Cleaning is a term used to describe the preplating
treatments necessary to prepare the surface to accept a metal deposit. Cleaning
removes dirt, oils, grease and other foreign material from the metal surface.
Cleaning may range from a single dip in a mild detergent to a combination of
several treatments. A typical cleaning cycle includes the following steps:
(1) Pickling to remove gross scale (This is often done prior to the plating
department); (2) mechanical preparations such as polishing and grinding to
smooth metal surfaces; (3) cleaning (usually consisting of many operations)
to remove oils, grease, shop dirt, polishing and buffing compounds; (4)
rinsing; (5) acid dipping to remove oxide films; and (6) rinsing.*
6-1
-------
TABLE 6-1. METAL FINISHING - U.S. PLANTS WITH
GREATER THAN 500 EMPLOYEES*
Plant Name Location
American Industrial Chromium Pittsburgh, Pennsylvania
Bristol Corporation Newport Beach, California
Crown City Plating Company El Monte, California
Dynacraft Incorporated Santa Clara, California
Minnesota Mining A Manufacturing Company Nevada, Missouri
Providence Metallizing Company Pawtucket, Rhode Island
Stolle Corporation Sidney, Ohio
Summit Corporation of America Thomaston, Connecticut
Superior Industries International Van Nuys, California
Worldmark Corporation N. Palm Beach, Florida
6-2
-------
T I I I I I I III
(SOLVENT | | CLEANING | | RINSING! k | ELECTRO-1 . I RINSING!
IDEGREAS-I ? | | =* I I * I PLATING I * I I
I ING I I II II II I
i I
I CALIBRATE I
Figure 6-1. Metal FinishfngS
6-3
-------
Organic solvents are used to dissolve most oils and greases including
those used to bind buffing and polishing compounds. This may be done by
dipping, but is usually done by vapor degreasing in which solvent vapors
condense on the metal parts to be cleansed and flow back to a pool of liquid
solvent such as perchloroethylene or trichloroethylene.4
Following organic cleaning, alkaline cleaning removes surface soil and
prevents it from settling back into the metal. After rinsing, the metal
pieces are often dipped into a hydrochloric or sulfuric acid bath that removes
the tarnish or oxide films formed during alkaline cleaning and neutralizes the
alkaline film.4
Plating then occurs. There are four types of plating that can be used:
electroplating, electroless plating, immersion plating and anodizing.
Electroplating is the production of a thin surface coating of one metal upon
another by eletrodeposition. Electroless plating is a chemical reduction
process which depends upon the catalytic reduction of a metallic ion in a
aqueous solution and subsequent deposition of metal without using electricity.
Immersion plating is a chemical plating process in which a thin metal deposit
is obtained by chemical displacement of the base metal. Anodizing is an
electrolytic oxidation process which converts the metal surface to an insoluble
oxide.^
After rinsing, postplating treatments Include chromate conversion coatings
for zinc and cadmium and phosphate treatments for zinc. These processes
improve the corrosion protection for the deposit and inhibit the formation
of bulky corrosion products.4 Phosphate coating provides a good base for
paint as well as impacting corrosive resistance.
Metal coloring Involves chemical methods of coloring 1n which the metal
surface such as copper, steel, zinc and cadmium is converted to an oxide for
a decorative finish.
Next, the metal pieces that have been plated are fitted together into a
complete machine, unit of a machine, or structure. This product is then
tested by applying thermal, electrical or mechanical energy to determine the
suitability of the product. Finally, the product is calibrated by applying
thermal, electrical or mechanical energy to establish reference points.3
6-4
-------
6.2.2 Specific Processes of Interest
This section describes the various metal finishing processes that use
sodium hydroxide (caustic soda) solutions. As mentioned earlier, alkaline
cleaning is used to remove oily dirt or solid soils from metal workpieces.
Alkaline cleaners are used quite often as secondary cleaners after detergent
soaking. These cleaners are aqueous solutions of sodium compounds such as
carbonate, silicate, phosphate or hydroxide and usually contain a surfactant.4
Alkaline cleaning may be performed by one or combination of three techniques:
soak, spray or electroclean. This type of cleaning is operated at temperatures
between 120 - 200°F at sodium compound concentrations between 0.5 - 2 Ibs/gallon.5
Soak cleaning 1s used for metals with easily removed soils. The metal
part is immersed in a plain steel tank with some possible mild agitation.6
Conventional soak cleaning has alkaline cleaner concentrations of 8-12 oz/gal,
operating temperatures of 150-190°F and retention times of 1-15 minutes.6 Low
temperature soak cleaners have concentrations of 2-4 oz/gal, operating temp-
eratures of 70-90°F and similar retention times. Soak cleaning is less
efficient than spray or electrocleaning.
In spray cleaning, the impact force of the spray makes cleaning more
effective but limits the use of surfactants that are foamy. Operating parameters
vary as alkaline cleaners concentrations vary from 0.5-4 oz/gal, operating
temperatures from 120-160°F and retention times from 1-3 minutes.6
Electrolytic cleaning produces the cleanest surface available because of
the strong agitation of the solution by gas evolution and oxidation - reduction
reactions that occur during electrolysis. It is mostly used prior to electro-
plating and generally follows other cleaning procedures. Common operating
conditions are alkaline cleaner concentrations varying from 8-14 oz/gal,
operating temperatures from 130-200°F, retention times from 0.5-2 min. and
current densities from 20-150A/ft2.6 A dilute mineral oil dip usually follows
the final electrocleaner to neutralize the alkaline film on the metal surface.5
Electroplating consists essentially of connecting the parts to be plated
to the negative terminal (cathode) of a direct current and another metal piece to
the positive terminal (anode) and immersing both in a solution containing
ions of the metal to be deposited. Metals dissolve at the anode and are
plated at the cathode.7
6-5
-------
A typical plating tank is shown on Figure 6-2. Plating tanks are either
constructed of polyvinyl chloride or steel which requires no lining for alkaline
solutions. For neutral or acid solutions, steel tanks are lined with rubber
or plastic. Parts to be plated are hung in the tank on wires or on racks. DC
power is conveyed to plating tanks by bus bars. The anodes are hung into the
tanks from the positive bus bar usually along two sides, and work to be plated
is placed down the center. Most large plating operations are conducted on con-
veyor tanks. Small parts to be plated are contained in wire baskets or usually
barrels, with perforated plastic sides. Barrels rotate on a horizontal axis
in the tank.4. 7
It is usually helpful to agitate the solution such as by air agitation or
by stirring or pumping the plating solution. In addition to the metal ions con-
tained in this solution, relatively large quantities of various substances used
to increase the electrical conductivity and for buffering are added.7 Temperature
control is nearly always required because the characteristics of plating solutions,
and of the deposit depend to a large extent on the operating temperature.4
In addition to the basic equipment (power source, plating, cleaning and
rinsing tank, and bus bars), most plating installations require one or more of
the following: filters - for either continuous or intermittent solution purifi-
cation; drying facilities, racking stations where work may be hung and unracked
after plating, and stripping tanks for stripping faulty deposits or plating racks.
Sodium hydroxide solutions are used in the following electroplating
baths: cadmium cyanide, copper cyanide, stannate tin, zinc cyanide and brass
plating.3 The cadmium cyanide bath has the following compositions (oz/gal)
if barrels are used: NaCN - 11-19.5, Cd-1.5-2.6, NaOH-2-3, Na2C03-2.0. If
racks are used to hold the metal parts, the following concentrations are used
NaCN-8-16, Cd-2-4, NaOH-1.5-3 and N32C03-2.0. Operating temperatures vary from
80-100°F.8 For copper plating, caustic soda is required for good bath conduc-
tivity, and improved brightness. Typical bath composition (oz/gal) for high
efficiency copper cyanide baths is CuCN-10, NaCN-13.6, and NaOH-4.9 A tin
stannate plating system uses either sodium or potassium salts. Potassium
salts are favored for generally superior operating conditions. Operating
bath temperatures range from 150-190°F.4
6-6
-------
Anpq>bu»
Comwctmired
or hwtmi co.1
**• '*'" *«» motor
•» mow Norh bw m
IOM of own
mm work tar
Tank
Figure 6-2. Cut-away view of plating tank.4
6-?
-------
Zinc plating baths are composed (oz/gal) of In (CN)2 -4-8; NaCN-2.7-5.4,
and NaOH-8-15. Operating temperatures range from 85-130°F.8 Sodium hydroxide
is also used for white brass plating. White brass was substituted for nickel
when nickel was in short supply. It is still used for toys and tubular
furniture as well as by one major automobile manufacturer. Operating condi-
tions are NaOH-30-37.5g/liter and operating temperatures of 70-84°F.7
Electroless plating is a continuous chemical reduction process in which
metal ions are reduced by chemical agents in a plating solution and deposited
on the material to be plated. The process is similar to electroplating except
no outside current is needed. The components of the bath include an aqueous
solution of metal ions, catalysts, reducing agents, complexing agents and bath
stabilizers.
Electroless plating is most often used for coating non-metallic parts
such as printed circuit boards, as base plate for plating on plastics and as
a protective coating on metal parts. The following electro!ess plating
processes use sodium hydroxide: copper, nickel, gold over copper, nickel,
kovar; arsenic and silver.3 Table 6-2 shows the various baths and the
compounds used.
TABLE 6-2. Electroless Plating3,5
Metal Compound
Copper Copper sulfate ° 5H20
Sodium potassium tartrate °
Sodium hydroxide
Formaldehyde (37%)
Nickel Nickel chloride
Sodium hydroxide
Ethylenediamine, 9B%
Sodium borohydride
Thallium nitrate
Silver Sodium silver cyanide
Sodium cyanide
Sodium hydroxide
Dimethyl amine borane
Concentration (g/1)
4H20
5-13.8
25-69.2
7-20
10-38 ml/I
31
42
52
1.2
0.022
1.83
1.0
0.75
2.0
Temp (°F)
68-86
200-205
55
6-8
-------
Immersion plating is a chemical plating process in which a thin metal
deposit is obtained by chemical displacement of the base metal. A metal will
displace from solution any other metal that is below it in the electromotive
series of elements.3 Caustic soda solutions are used for the following plating
operations: brass on aluminum, cadmium on steel, lead on copper and tin on
copper alloys. The concentration of caustic soda in the plating bath and
operating temperatures are shown below.3.5
Process Concentration (oz/gal) Temperature (°F)
Brass on aluminum 42 110-115
Cadmium on steel 70 - 75 255
Lead on copper 14 Room Temp>
Tin on copper 3 Room . m
Etching and chemical milling are processes that produce a surface that
conceals imperfections, produces a decorative effect or roughens the surface.
The difference between etching and milling is that the rates and depths of
metal removal are usually much greater in milling. Processes that use caustic
soda are aluminum and tungsten etching and molybdenum alloys milling.3
Aluminum etching uses an aqueous caustic soda bath at concentrations of
3-8 oz/gal. Operating temperatures are 140-180°F for a period of 0.5-10 minutes.
Typically, a concentration of 5 oz/gal at 160°F for 5 minutes removes 0.001 inch
(1 mil) of metal. This amount of metal removed is sufficient to remove surface
imperfections and provides a satin or matte finish.6
Another use of caustic soda in the metal finishing industry is for the
coloring of metals. One of the most common is the alkaline blackening treatment
of steel. Various formulations are used for the treating baths from a number
of suppliers. One reference states that the bath solution is a 40 percent
aqueous solution of sodium hydroxide to which 5 percent each of sodium and
potassium nitrates are added.H Other formulations are caustic soda - 8 Ibs/gal;
sodium nitrate 1.5 oz/gal; sodium dichromate - 1.5 oz/gal; or caustic soda -
5 Ib/gal, potassium nitrite - 1.9 oz/gal, potassium nitrate 1.25 oz/gal.5
Processing bath temperatures range from 275 - 320°F and immersion times vary from
6-9
-------
5-30 minutes. The coatings formed on steel by these treatments are mostly
magnetic oxides and are 1n the order of 0.00003 - 0.00007 Inches thick.
Coating color and characteristics are a function of which type of alloy Is
treated, surface characteristic, bath concentration and temperature, and
retention time. These coatings are porous and not particularly corrosion
resistant.6 The colored metal articles are usually finished by Immersion 1n
hot greases, oils or waxes followed by wiping and polishing.11
Other metal colorings where caustic soda 1s used are flemish on brass and
blueing steel. The flemish finish on brass 1s produced by arsenic plating
having the following bath composition - white arsenic - 16 oz/gal, caustic
soda - 16 oz/gal and sodium cyanide - 1/2 oz/gal. The bath Is operated at
70-110°F with a current density of 3-20 amp/ft2. One of five bath types that
produces a blue color on steel uses caustic soda. The bath has concentrations
of caustic soda - 5 oz/gal, white arsenic - 5 oz/gal and sodium cyanide - 1 oz/gal,
The current density 1s 2 amp/ft2 and retention time varies from 2-4 minutes.5
6.3 EMISSIONS
As shown on Table 6-3, sodium hydroxide emission estimates were obtained
for 25 plants from the States of Kentucky, New Jersey and New York for SIC 3471.
As shown on this Table, only 3 of the 58 sources have emission control equipment
and these three have scrubbers. Sodium hydroxide emission estimates for entire
plants in this SIC code vary from 34 - 10,200 Kg/yr. Individual process units
vary from 1 - 8,900 kg/yr.
Emission test data was obtained from a plating shop at the Norfolk Naval
Shipyard. One ventilation line exhausted an electrocleaning tank (using
caustic soda), as well as nitric acid, and hydrogen chloride tanks. Emissions
are controlled by a spray scrubber that according to the emission test report
was not operating properly. Test results show sodium hydroxide emissions of
0.17 Ib/hr and hydrogen chloride emissions of 2.5 Ib/hr.
6.4 HEM INPUTS
i
The inputs used to access health risks from exposure to sodium hydroxide
emissions from 25 plants in SIC 3471 are given in Table 6-3. These data represent
all plants in this SIC code that were contained in computer printouts of sodium
hydroxide emissions from the States of Kentucky, New Jersey, New York, and Texas.
6-10
-------
TABLE 6-3.
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM METAL FINISHING
cr>
i
STACK VERTICAL
PLANT LAT. LONG. EMISSION HEIGHT AREA
NAME STATE (DEG, MIN, SEC) TYPE (M) (SQ. M.)
Central
Kentucky
Mid-South
Electric
Midway
Fabricating
N.I.
Industries
KY 380104 842653 Fug
Stack 1 0.5
Fug
Stack 3 0.9
Stack 3 0.9
KY 371857 834714 Fug
KY 363032 885333 Fug
Fug
Fug
Fug
Fug
Fug
Fug
KY 375248 843420 Stack 18 22
Stack 18 22
STACK STACK STACK
DIAMETER VELOCITY TEMP.
(M) (M/S) (°K)
311
0.5 1 311
311
0.3 1 311
0.3 1 311
298
298
298
298
298
298
298
298
1.2 12 298
1.2 15 298
NaOH
EMISSIONS SOURCE
(Kg/yr) DESCR.
37
41
14
1
53
130
16
34
35
16
36
110
160
33
3
2 Cleaning Tanks
Black Oxide Tank
Cleaning Tank
3 Cleaning Tanks
Cleaning Tank
3 Electroplating
Tanks
Alkaline Soak Clean
2 Electrocleaners
Alkaline Soak Clean
Electrocleaner
Electrocleaner
2 Electrocleaners
Electrocleaner
Plastic Product
Fabrication
Plastic Product
Fabrication
CONTROL
DEVICE
None
Wet
Scrubber
None
Wet
Scrubber
None
None
None
None
None
None
None
None
None
Wet
Scrubber
None
Cramer NJ 404023 750025 Stack 6.1 1.8
Plating Stack 6.1 1.8
Stack 6.1 1.8
Stack 6.1 1.8
Stack 3.0 0.9
0.3
0.3
0.3
0.3
0.3
14 327 570 Aluminum Etch Tank None
14 322 570 Anodizing Hoist Line None
23 294 180 Ultrasonic Cleaning None
23 294 90 Electrocleanlng None
17 293 2000 Z1nc Plating None
-------
TABLE 6-3. (continued)
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM METAL FINISHING
PLANT
NAME STATE
East Coast
Metal
Finishing NJ
Edmar
Creations NJ
Miller *
Son NJ
Moyer Plating NJ
Platronlcs NJ
Suffern
Plating NJ
Albert's
Plating NY
Curnow NY
General
Superplatlng NY
LAT. LONG.
(DEG, MIN, SEC)
404919
405441
404707
404359
403821
405249
404313
431046
430331
740733
741016
740905
740846
741431
740431
735608
773936
760410
EMISSION
TYPE
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
STACK
HEIGHT
(M)
3.0
15
8.5
8.5
6.1
8.5
4.3
4.3
4.3
6.1
6.7
7.6
7.6
7.6
VERTICAL
AREA
(SQ. M.)
2.7
9.0
5.1
5.1
1.8
5.1
3.4
3.9
5.6
17.7
18.8
5.3
6.9
6.9
STACK STACK
DIAMETER VELOCITY
(M) (M/S)
0.91
0.6
0.6
0.6
0.3
0.6
0.8
0.9
1.3
2.9
2.8
0.7
0.91
0.91
50
15
14
15
29
12
11
11
4
17
11
16
10
16
STACK
TEMP.
294
314
294
294
294
294
294
311
294
294
294
294
294
294
NaOH
EMISSIONS SOURCE
(Kg/yr) DESCR.
590
980
280
280
90
140
290
150
870
810
440
280
190
73
Electroplating
Alkaline Soak
Electroplating
Electroplating
Soak Tank
Spray Etching
Metal Cleaning
Metal Cleaning
Metal Cleaning;
Nickel Plating;
Brass Plating
Electroclean
Metal Cleaning
Etching
Alk. Cleaning;
Metal Plating
Zinc Plating
CONTROL
DEVICE
None
None
None
None
None
None
None
None
None
None
None
None
None
None
-------
TABLE 6-3 (continued)
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM METAL FINISHING
PLANT LAT. LONG. EMISSION
NAME STATE (PEG. MIN, SEC) TYPE
STACK VERTICAL STACK STACK STACK NaOH
HEIGHT AREA DIAMETER VELOCITY TEMP. EMISSIONS SOURCE CONTROL
(M) (SQ. M.) (M) (M/S) (°K) (Kg/yr) DESCR. DEVICE
JHT Plating NY 404849 735324 Stack
Keystone Corp.NY 425447 845357 Stack
Levco Metal
Finishers NY
McCauley Inc. NY
Marlette
Plating
Monroe
Plating
Nelkln
Plating
NY
NY
404526 735523 Stack
425605 844920 Stack
425644 845347 Stack
Stack
Stack
431056 773701 Stack
Stack
Stack
NY 404241 735604 Stack
10 51
10 9.1
7.6
20
5.1
0.91
2.6
4 297 110 Soak Clean, 2 None
Electroclean Tanks
13 297
11
297
64 Aluminum Etching None
5.5
10
4.2
9.1
0.76
0.91
8.5
13
311
297
140
150
7.3
9.1
4.6
8.8
8.3
1.4
1.2
0.91
0.3
11
7
18
333
342
417
40
130
95
12
12
7.9
7.3
7.3
4.8
0.61
0.61
0.61
13
11
6
294
294
339
660
660
8900
1100
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
Stack
7.3
10
9.7
8.5
8.5
7.9
7.6
8.8
9.4
14
8.0
24
12
20
16
14
26
27
1.9
0.8
2.5
1.4
2.3
2.0
1.9
3.0
2.9
8.2
4.0
4.9
9.1
6.1
8.5
8.5
8.8
30
297
297
297
297
297
297
297
297
297
220
560
170
120
680
310
290
340
680
Etching
None
Electroclean, Chrome None
Strip
Aluminum Etching None
Alkaline Cleaning None
Black Oxide Bath None
Zinc Plating None
Z1nc Plating None
3 Cleaning Tanks None
3 Caustic Tanks,
Electroclean None
2 Electroclean Tanks None
2 Electroclean Tanks None
2 Electroclean Tanks None
Zinc Plating None
2 Cleaning Tanks None
Caustic Soak Tanks None
Caustic Strike Tank None
Electroclean Tank None
Electroclean Tank None
-------
TABLE 6-3. (continued)
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM METAL FINISHING
PLANT
NAME STATE
S template,
Inc. NY
U.S. Electro-
plating NY
V1su-Craft NY
Yonkers
Plating NY
STACK VERTICAL STACK STACK STACK NaOH
LAT. LONG. EMISSION HEIGHT AREA DIAMETER VELOCITY TEMP. EMISSIONS SOURCE
(DEG, MIN, SEC) TYPE (M) (SQ. M.) (M) (M/S) (°K) (Kg/yr) DESCR.
413556 741849 Stack 2.4 1.5 0.61
405019 732022 Stack 6.1 4.3 0.71
425447 845357 Stack 6.4 22 3.5
405816 735207 Stack 0.6 0.18 0.3
2.3 308 55 Electroclean
6.7 294 73 Electroplating
7.3 294 2900 4 Electroclealng,
2 Soak Tanks
3.0 294 260 Electroplating
CONTROL
DEVICE
None
None
None
None
-------
6.5 REFERENCES
1. Bureau of Census, U.S. Department of Commerce. 1982 Census of Manufactures
General Summary. Part 1. Publication No. MC 82-5-1 (Part 1). Washington/
DC. March 1986. p. 1-14.
2. Duns Electronic Yellow Pages - Manufacturers. File 510. April 1987.
3. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines and Standards for the Metal Finishing Point
Source Category. Publication No. EPA 440/1-83/091. Washington, DC.
June 1983.
4. Lowenheim, F.A. Electroplating. In: Kirk-Othmer Encyclopedia of Chemical
Technology, Volume 8. New York, John Wiley and Sons, Inc. 1964. pp. 36-
/ T •
5. Metal Finishing - Guidebook Directory 1987. Hackensack, NJ, Metals and
Plastics Publications, Inc. January 1987.
6. Schwarzkopf, A.J. Metal Surface Treatments. In: Kirk-Othmer Encyclopedia
of Chemical Technology, Volume 13. New York, John Wiley and Sons, Inc.
1964. pp. 284-314.
7. Weil, R. Electroplating of Metals. In: McGraw-Hill Encyclopedia of
Science and Technology, Volume 4. New York, McGraw-Hill Book Company.
1977. pp. 601-606.
8. Swalheim, D.A., Zinc and Cadmium Plating. Winter Park, Florida, American
Electroplaters' Society. 1962.
9. Swalheim, D.A. and R.W. Mackey. Cyanide Copper Plating. Winter Park,
Florida, American Electroplaters1 Society. 1969.
10. Weil, R. Electroless Plating. In: McGraw-Hill Encyclopedia of Science
and Technology, Volume 4. New York, McGraw-Hill Book Company. 1977.
p. 544.
11. U.S. Steel Corporation. The Making, Shaping, and Treating of Steel.
8th Edition. Pittsburgh, PA. 1969. p. 942.
12. Source Emission Testing of the Building 195 Plating Shop at Norfolk
Naval Shipyard. Naval Energy and Environmental Support Activity. Port
Hueneme, California. NEESA 2-124. May 1985.
6-15
-------
7.0 INDUSTRIAL ORGANIC CHEMICALS
7.1 INDUSTRY DESCRIPTION
In 1982, the SIC code 2869 (Industrial Organic Chemicals, Not Elsewhere
Classified) had 488 companies and a total of 688 establishments. Three
hundred and seventy six plants had at least 20 employees.1 One hundred and
eighty six plants have greater than 100 employees and 62 plants have greater
than 500 employees. A list of these 62 plants Is given on Table 7-1. This
SIC code produces a multiple of products such as acetic, formic and tartaric
acids; solvents such as butyl and ethyl alcohol; methanol, synthetic perfumes,
artificial flavors, and esters.3 The only known products in which sodium
hydroxide is used are artificial maple flavorings and herbicides. A membership
list from The Flavor and Extract Manufacturers' Association of the United
States was also obtained.
7.2 PROCESS DESCRIPTION
This section describes the processes used at two plants that are the
only plants in this SIC code known to emit sodium hydroxide. One plant
uses sodium hydroxide in the production of artificial maple flavoring.
Figure 7-1 shows the processes used at Elan Chemical. The Flavoring and
Extract Manufacturer Association expects the number of plants that produce
this flavor to be small. Also, the Association did not know how frequent
caustic soda is used by its members to produce flavors and extracts.4
At this plant, a 25% caustic soda solution and corn cobs are the raw
materials used. All processes are batch processes. The raw materials are
preheated in a 1500 gallon container with approximately 8 percent by weight
of the reactor's content being sodium hydroxide. Caustic soda breaks down
the cellulose fibers in the corn cob similar to what Is done in paper
manufacturing. The preheater contents are then pumped to a 1500 gallon
reactor which oxidizes the corn cobs under pressure using compressed air.
Retention time in the reactor is 6-8 hours. After oxidizing the corn cobs,
the contents are pumped to one of three closed-top 6-7,000 gallon holding
tanks prior to shipment.5
7-1
-------
TABLE 7-1. INDUSTRIAL ORGANIC CHEMICALS - U.S. PLANTS
WITH GREATER THAN 500 EMPLOYEES?
Plant Name
Location
ASAG Incorporated
Advanced Nuclear Fuels Corp.
Advanced Nuclear Fuels Corp.
Akzo America Inc.
Akzona Incorporated
Aldrich Chemical Company Inc.
American Cynamid Co., Inc.
Amoco Performance Products In.
Angus Chemical Company
Angus Chemical Company
The Babcock & Wilcox Co.
BASF American Corp.
BASF American Corp.
Borg-Warner Chemical Inc.
Buckman Laboratories Inc.
Celanese Chemical Company Inc.
Celanese Construction Fabrics
Chemed Corporation
Chesebrough-Ponds Inc.
Degussa Corporation
Degussa Corporation - Alabama Group
Detrex Corporation
The Dow Chemical Co.
The Dow Chemical Co.
The Dow Chemical Co.
The Dow Chemical Co.
Dravo Corporation
Eastman Kodak Company
Ferro Corporation
Grain Processing Corporation
International Flavors/Fragrances
International Mineral Chemical
M & T Chemicals Inc.
Miles Laboratories
Monsanto Company
Monsanto Company
The Nutrasweet Company
Occidental Chemical Corp.
Occidental Chemical Holding
Oxy Chemical Corporation
PMC Inc.
PPG Industries Inc.
Sherex Chemical Company Inc.
Shipley Company Inc.
Harriman, NY
Bellevue, WA
Richland, WA
New York, NY
New York, NY
Milwaukee, WI
Westwego, LA
Ridgefield, CT
Sterlington, LA
Northbrook, IL
Holcombs Rock, VA
Parsippany, NJ (2 plants)
Clifton, NJ
Parkersburg, WV
Memphis, TN
Dallas, TX
New York, NY
Baltimore, MD
Adrian, MI
Teterboro, NJ
Theodore, AL
Southfield, MI
Freeport, TX (2 plants)
Lake Jackson, TX
Houston, TX
Indianapolis, IN
Pittsburgh, PA
Kingsport, TN
Cleveland, OH
Muscat!" ne, IA
Union Beach, NJ
Terre Haute, IN
Woodbridge, NJ
Elkhart, IN
St. Louis, MO
East St. Louis, IL
Skokie, IL
Niagara Falls, NY (2 plants)
Los Angeles, CA
Los Angeles, CA (2 plants)
Chicago, IL
New Martinsville, WV
Dublin, OH
Newton, MA
7-2
-------
TABLE 7-1,
Plant Name
INDUSTRIAL ORGANIC CHEMICALS - U.S. PLANTS
WITH GREATER THAN 500 EMPLOYEES?
(Continued)
Location
Signal Companies Inc.
Signal Companies Inc.
Standard Oil Chemical Company
Texaco Chemical Company
Texaco Inc.
Texas Petrochemicals Corp.
Union Carbide Corporation
Union Carbide Corporation
Union Carbide Corporation
Union Carbide Corporation
Union Carbide Corporation
Uniroyal Plastics Co. Inc.
Hacker Siltronic Corporation
Des Plaines, IL
La Grange, IL
Cleveland, OH
Bellaire, TX
Port Arthur, TX
Houston, TX
Institute, WY
S. Charleston, WV
Seadrift, TX
Danbury, CT
Charleston, WV
Middlebury, CT
Portland, OR
7-3
-------
Another plant in this SIC Code (Fermenta Plant Protection) uses a 30%
caustic soda solution in the production of sodium arsenite, an ingredient
used to produce the herbicide, monosodium methylarsenate. The solution is
produced at the plant from anhydrous caustic soda. The caustic soda solution
along with arsenic trioxide is charged to a reactor vessel, 8 feet in diameter
and 8 feet high with a capacity of 2500 gallons. The process produces sodium
arsenite and is operated at ambient conditions. The reaction is slightly
exothermic. The process is operated 8 hours per day, 5 days per week. Six
to eight batches are processed daily.6
7.3 EMISSIONS
At Elan Chemical, emissions from the preheater, premix tanks and holding
tanks are ducted to the atmosphere with no controls through separate stacks.
Air releases from the reactor are quenched by a 5000 gallon water tank that
condenses steam and caustic vapor as well as serving as a heat exchanger.
The tank contents are then transferred to the preheater tank. There are no
air releases to the atmosphere from this reactor. Also, air is exhausted
from the building to prevent vapor build-up.5
At Fermenta Plant Protection, emissions from the reactor result from the
violent spraying of caustic solutions. Emissions are controlled by a Brinks
mist eliminator that occasionally uses caustic soda or water as the scrubbing
medium. The mist eliminator is used to limit arsenic emissions as well as
for product recovery.6
7.4 HEM INPUTS
The HEM Inputs for Elan Chemical and Fermenta Plant Production are given
in Table 7-2. These inputs were obtained from printouts received from the
States of New Jersey and Texas.
7-4
-------
1
I STACK
* !!
1 1
Corn Cobs J 1
Caustic Soda *|PREHEATER| ^
1 1 :
1 1
STACK
1 1
1 1
1 1
1 1
k 1 PREMIX | a
* | TANK | '
1 1
COMPRESSED
1 1
1 WATER |
I TANKI
I 1
Itl
1 1
1 1
1 REACTOR |
>l l~
1 1
/N
1
I HOLDING)
I TANK f
I I
FINISHED
PRODUCT
AIR
Figure 7-1. Production of Maple Flavoring - Elan Chemical, Newark, NO5
7-5
-------
TABLE 7-2.
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM INDUSTRIAL ORGANIC CHEMICALS
PLANT
NAME
Elan
Chemical
Fermenta
Plant
Protection
Company
LAT. LONG. EMISSION
STATE (DEG, MIN, SEC) TYPE
NJ 404326 740725 Stack
Stack
Stack
Stack
TX 294549 951006 Stack
STACK VERTICAL STACK
HEIGHT AREA DIAMETER
(M) (SQ. M.) (M)
6.0 0.36 0.06
6.0 0.36 0.06
7.8 0.47 0.06
6.0 1.6 0.27
12.0 4.6 0.38
STACK STACK NaOH
VELOCITY TEMP. EMISSIONS SOURCE CONTROL
(M/S) (°K) (Kg/yr) DESCR. DEVICE
1.0 320 2050 Preheater
1.0 320 2050 Premlx Tank
1.6 300 2730 3 Holding Tanks
15.0 290 45 Building Exhaust
12.0 300 45 <^rUnm Arcon-H-o
None
None
None
None
Mie +
Reactor Eliminator
I
cr>
-------
7.5 REFERENCES
1. Bureau of the Census, U.S. Department of Commerce. 1982 Census of
Manufactures - General Summary Part 1. MC 82-S-l (Part 1). Washington,
DC. March 1986. p. 1-10.
2. Duns Electronic Yellow Pages - Manufacturers. File 510. April 1987.
3. The Statistical Policy Division, Office of Management and Budget. Standard
Industrial Classification Manual, 1972. Washington, DC. 1972. pp. 122-123,
4. Telecon. Klinger, E. Flavoring and Extract Manufacturing Association
with Neuffer, William. U.S. EPA. July 1, 1987. Information on sodium
hydroxide use by its members.
5. Telecon. Sulimirski, K. Elan Chemical with Neuffer, William. U.S. EPA.
June 30, July 1, 1987. Process and emission information on Newark,
New Jersey plant.
6. Telecon. Stansbury, J. Fermenta Plant Protection with Neuffer, William.
U.S. EPA. July 1,7, 1987. Process and emission information on Pasadena
Texas plant. '
7-7
-------
8.0 SOAP AND DETERGENT MANUFACTURING
8.1 INDUSTRY DESCRIPTION
This chapter covers SIC Code 2841 - Soap and other detergents, except
specialty cleaners. This category Includes plants primarily engaged In
manufacturing soap, synthetic organic detergents, Inorganic alkaline detergents,
or any combination thereof, and establishments producing crude and refined
glycerin from vegetable and animal fats and oils.1 In 1982, there were 642
companies 1n this category with 723 plants. Two hundred and thirty two plants
have 20 or more employees.2 A 11st of those plants with greater than 100
employees Is shown on Table 8-1. Table 8-2 shows the spray dry detergent
manufacturers that were operating in 1980.4
8.2 PROCESS DESCRIPTION
8.2.1 General - Soap
Soap consists of various mixtures of sodium or potassium salts of fatty
acids. Soap can be manufactured by either a batch or continuous process,
using either the alkaline saponification (converting fats to soap) using
natural fats and oils or the direct saponification of fatty acids.5
Much of the world production is still produced in batch processes that
use open steel kettles. Processing rates per batch vary from several thousand
to several hundred thousand pounds of soap. Fats and oils are converted to
soap by direct or indirect steam heating in a caustic solution. The end
product from the kettles is a completely saponified neutral soap containing
approximately 30% water. Dry salt 1s added to the boiling soap until a hard
grain 1s obtained. After a short boil, the kettle contents are allowed to
separate for several hours. The bottom layer, consisting primarily of caustic,
glycerol, and salt 1s pumped to storage tanks prior to recovering the glycerol
and salt in separate concentrating and refining operations. The upper soap
layer, is washed to remove colored and odorous Impurities as well as to
separate glycerol and salt from the soap.6
Continuous alkaline saponification of natural fats and oils as well as
fatty acids has the same processes as batch processes but process time is
shortened. Fatty acids obtained by continuous hydrolysis usually are
neutralized with caustic soda in a high speed mixer/neutralizer to form soap.5
8-1
-------
TABLE 8-1. SOAP AND DETERGENT MANUFACTURING - U.S. PLANTS
WITH GREATER THAN 100 EMPLOYEE$3
Plant Name
Location
Amerchol Corporation
American Hospital Supply Corp,
American Soap Company Inc.
Analytab Products
Armour and Company
Barcolene Company Inc.
Bonner W C Co. Inc.
Calgon Corp.
Calusa Chemical Company Inc.
Chemed Corporation
Colgate-Palmolive Company
Colgate-Palmolive Company
Colgate-Palmolive Company
Colgate-Palmolive Company
Desoto Inc.
Desoto Inc.
Dial Corporation
Dial Corporation
Dial Corporation
Dial Corporation
Dial Corporation
Dial Corporation
Diamond Chemical Co. Inc.
Ecolab Inc.
Emhart Corporation
Glissen Chemical Co. Inc.
Go-Jo Industries Inc.
Hewitt Soap Co.
Huish Chemical Co.
Industrial Chemical Labs
Andrew Jergens Company
Kleen Brite Laboratories Inc.
Knomark Inc.
Korex Company
Lever Brothers Company
Lever Brothers Company
Lever Brothers Company
Lever Brothers Company
Lever Brothers Company
Lever Brothers Company
Los Angeles Soap Company
Minnesota Mining and Mfg.
Minnestonka Inc. Soft Soap
Mo-Kan Manufacturing Company
Mohawk Supply Co.
Monsanto Chemical Company
Edison, NJ
El Paso, TX
Olive Branch, MS
Pla1nv1lle, NY
Phoenix, AZ
Hoi brook, MA
Watertown, MA
St. Louis, MO
Santa Fe Springs, CA
Cincinnati, OH
Piscataway, NJ
Kansas City, KS
New York, NY
Clarksville, IN
Fort Worth, TX
Union City, CA
St. Louis, Mo
Chicago, IL (2 plants)
Omaha, NE
Bristol, PA
Auburndale, FL
Montgomery, IL
Lyndhurst, NJ
St. Paul, MN
Middleton, MA
Brooklyn, NY
Cuyahoga Falls, OH
Dayton, OH
Salt Lake City, UT
Omaha, NE
Cincinnati, OH
Rochester, NY
Queens, NY
Wixom, MI
Los Angeles, CA
Hammond, IN
Whiting, IN
St. Louis, MO
New York, NY
Baltimore, MD
Los Angeles, CA
St. Paul, MN
Chaska, MN
Kansas City, MO
Sparta, NJ
Trenton, MI
8-2
-------
TABLE 8-1. SOAP AND DETERGENT MANUFACTURING - U.S. PLANTS
WITH GREATER THAN 100 EMPLOYEES3
(Continued)
Plant Name
Location
National Chemical Labs PA
National Distillers 4 Chemical
O'Brien Corporation
Original Bradford Soap Works
Pfanstlehl Detergent Chem.
Pilot Chemical Corp.
Procter & Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter & Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Procter 4 Gamble Company
Rlckert Ben Inc.
Philadelphia, PA
Los Angeles, CA
South Bend, IN
West Warwick, RI
Hlnsdale, IL
Santa Fe Springs, CA
Cincinnati, OH (3 plants)
Level land, TX
Sacramento, CA
Jacksonville, FL
Orange, CA
Dallas, TX
Qulncy, MA
Richmond, NY
Baltimore, MD
Augusta, GA
Kansas City, KS (2 plants)
Long Beach, CA
St. Louis, MO
Wayne, NJ
8-3
-------
TABLE 8-2. SPRAY-DRY DETERGENT MANUFACTURERS, 1980*
Company
Location
The Procter and Gamble Company
The Colgate-Palmolive Company
Lever Brothers
Astor Products
Chemithon
Custom Spray Products, Inc.
The Great Atlantic and Pacific
Tea Company, Inc.
Los Angeles Soap Company
Luseaux Labs
National Purity Soap and
Chemical Company
Pacific Soap
PI ex Chemicals
Purex
Safeway Stores, Inc.
Stepan Chemical
Witco Chemical Corporation
Long Beach, California
Sacramento, California
Augusta, Georgia
Kansas City, Kansas
Alexandria, Louisiana
Baltimore, Maryland
Quincy, Massachusetts
New York, New York
Cincinnati, Ohio
Dallas, Texas
Berkeley, California
Jeffersonville, Indiana
Kansas City, Kansas
Jersey City, New Jersey
Los Angeles, California
Baltimore, Maryland
St. Louis, Missouri
Jacksonville, Florida
Seattle, Washington
Atlanta, Georgia
Brockport, New York
Los Angeles, California
Gardena, California
Minneapolis, Minnesota
San Diego, California
Union City, California
Southgate, California
St. Louis, Missouri
Bristol, Pennsylvania
Oakland, California
Chicago, Illinois
Chicago, Illinois
Paterson, New Jersey
8-4
-------
A diagram of a continuous process Is shown on Figure 8-1. In this
process, a fat/oil mixture is pumped through a sprayer into the bottom of
closed hydrolyzer operating at 600 - 700 psi and 485°F. Hot water is intro-
duced near the top of the tower to produce fatty acids. These acids are then
refined by vacuum distillation. The fatty acids are continuously mixed in a
high speed blender with a 50% sodium or potassium hydroxide solution.7
The end product of both the kettle and continuous process is called "neat
soap" and contains approximately 30% moisture. The soap slurry is dryed in
either a cabinet, flash or vacuum dryer. For bar soaps, 10-15 percent moisture
is specified prior to cooling and extruding. Water content must be reduced
to 5-10% before cutting into flakes.6
8.2.2 Specific Processes of Interest - Soap
As shown on Table 8-3, the only processes known to emit sodium hydroxide
are kettles and material handling process units.
Kettles used in the soap manufacturing industry are circular or square
in cross section and are tapered to cones at the bottom. Kettle operation is
generally lagged to conserve heat. Open steam coils in the cone section
supply heat and agitation. Closed steam coils may also be present to supply
heat without adding steam.6
Information was obtained on Chemed Corporation's East Rutherford, New
Jersey plant that uses kettles to produce liquid soap. This plant has 11 batch
kettles that range in size from 500 - 5,000 gallons. Kettle dimensions vary
from 41/2-8 1/2 feet in diameter and 5-10 feet in depth. All kettles
have closed tops except for a 5 square foot bar grate area where material is
added to the kettle. The kettle initially begins operating at ambient temp-
erature and heat could be evolved during the mixture of certain products.
Cooling jackets surround the kettles and no external heat is added. The
average sodium hydroxide content of the batch for those liquid soap products
that require sodium hydroxide is 20 percent. In 1986, 368,000 gallons of
50 percent caustic soda was used by the company in the production of liquid
soaps. Products are made to order and retention time in the kettles vary
from 1 to 24 hours. In 1986, approximately 2,500 batches were produced.
8-5
-------
Noncondensibles
Hot -
Water
oo
i
Fat/Oil'
Mixture
CONDENSER
Steam and
Organic Vapors
Fatty Acids
FLASH
TANK
W
M
Q Noncondensibles
VL»
Q
04* ^C
3 o
^ t«
M
E-« 2
W O
M M
0 H
CONDENSER
..i..
CONDENSER • '
EVAPORATOR
I Heavy Fraction
* to Storage or
Recovery
Steam
& Vapors
Crude
Glycerin
i I
Steam
•Water
Caustic Solution
1
MIXER
Fatty Acid
Products
Crude Soap to
Final Processing
and Packaging
Figure 8-1. Continuous Process for Manufacture of Fatty Acids and Soaj/
-------
The kettle process generally begins when part of the weighed coconut-oil
fraction of the fat charge is first added to the kettle with a little water
and salt, and heated and agitated with live steam. Saponification is usually
started by the addition of 50% caustic soda solution and the slow addition of
the remaining coconut oil. A small amount of dry salt is usually added during
the process to maintain a slight excess of electrolyte. The last small
caustic soda additions are made slowly. As the pan expands by steaming, the
"closed grin" is tested for alkali consumption.6
At Chemed, dry soap powder is also produced. Caustic soda beads, soda
ash, sodium tripolyphosphate, sodium sulfate and tetrasodium pyprophosphate
are added in various amounts depending on the particular soap powder to be
produced. These materials are pneumatically conveyed to separate storage
silos. All material except the beads are placed into a blowpot (a pressurized
vessel) up to a maximum amount of 5,000 pounds. The caustic soda beads are
weighed and conveyed to one of four ribbon blenders which also receives the
blowpot product. The blenders are long troughs; 10 feet long and 4 feet
wide. The blended product is discharged to a hopper and then to a packaging
station where products are packaged in containers from 2 pound bags to
55 gallon drums.8
8.2.3 General-Detergent
The manufacture of spray dried detergents is shown on Figure 8-2.5 There
are three main processing steps: slurry preparation, spray drying and granule
handling. Detergent slurry is produced by blending a liquid surfactant with
powdered and liquid materials (builders and other additives) in a closed mixing
tank called a crutcher. The liquid surfactant used in making the detergent
slurry is produced by the sulfonation or sulfation by sulfuric acid of a
linear alkylate or a fatty acid, which is then neutralized with caustic
solution. The blended slurry is held in a surge vessel for continuous pumping
to the spray dryer. The slurry is sprayed at high pressure through a nozzle
into a vertical drying tower that operates at 315 - 400°C (600 - 750°F). The
detergent granules are mechanically or air conveyed from the tower to a mixer
to incorporate additional dry or liquid ingredients and finally sent to
packaging and storage.5
8-7
-------
RECEIVING,
STORAGE,
TRANSFER
SLURRY PREPARATION
SPRAY DRYING
BLENDING
AND
PACKING
00
I
CO
1
DRY DUST _
COLLECTORS
1
CONTROL
DEVICE
1 1
"flltH . [ MIXER |
SURFACTANTS:
SLURRY
ALCOHOLS
ETHOXYLATES
BUILDERS:
PHOSPHATES
SILICATES
CARBONATES
ADDITIVES:
PERFUMES
DYES
ANTICAKING AGENTS
1 r
CRUTCHER
f
SURI
VESS
TO CRUTCHER
•* AND POST-
ADDITION MIXEI
HIGH
—• yl PHbSSUHk
— - / PUMP
_ / rumr
ELf HOT AIR
i
FURNACE
1
SPRAY
DRYING
TOWER
Y
DRY DUST
COLLECTORS
POST-
ADDITION
MIXER
GRANULE
STORAGE
I CONVEYOR
PACKAGING
EQUIPMENT
FINISHED
DETERGENTS TO
WAREHOUSE
Figure 8-2. Spray Dried Detergent Manufacturing5
-------
8.3 EMISSIONS/HEM INPUTS
Shown on Table 8-3 are sodium hydroxide emissions that were estimated
for one soap manufacturing plant, Chemed in East Rutherford, New Jersey. As
noted in the Table, the first emission point (material handling and storage)
is controlled by a baghouse. All batch kettles are uncontrolled. There were
no sodium hydroxide emission data for spray-dry detergent manufacturing. The
Information in Table 8-3 was submitted as imputs to the Human Exposure Model
(HEM) for use by EPA's Pollutant Assessment Branch (PAB).
8-9
-------
TABLE 8-3.
HEM INPUTS - SODIUM HYDROXIDE EMISSIONS FROM SOAP MANUFACTURING
PLANT
NAME
STATE
LAT.
LONG.
EMISSION
TYPE
STACK VERTICAL
HEIGHT AREA
(M) (SQ. M.)
STACK
DIAMETER
(M)
STACK
VELOCITY
(M/S)
STACK
TEMP.
(°K)
NaOH
EMISSIONS
(Kg/yr)
SOURCE
DESCR.
CONTROL
DEVICE
Chemed Corp. NJ 404922 740547 Stack
9.9
6.8
0.69
9.8
294
3300
Stack
Stack
Stack
12
11
11
6.1
3.6
3.0
0.51
0.33
0.27
11.0
11.0
16.2
294
294
300
950
950
950
Storage S1lo, Baghouse
Tote bin,
Ribbon blenders,
product hoppers,
packaging stations
11 Batch Kettles None
3 Batch Kettles None
5 Batch Kettles None
-------
8.4 REFERENCES
1. The Statistical Policy Division, Office of Management and Budget.
Standard Industrial Classification Manual 1972. Washington, DC. 1972.
p. 118.
2. Bureau of the Census, U.S. Department of Commerce. 1982 Census of
Manufactures - General Summary Part 1. MC 82-S-l (Part 1). Washington,
DC. March 1986. p. 1-10.
3. Duns Electronic Yellow Pages - Manufacturers. File 510. April 1987.
4. U.S. Environmental Protection Agency. Source Category Survey: Detergent
Industry. Publication No. EPA-450/3-80-030. Research Triangle Park,
NC. June 1980. p. 11-12.
5. U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors, Fourth Edition. Publication No. AP-42. Research
Triangle Park, NC. September 1985. 5.15-1-5.15-4.
6. Ryder, F.V. Soap. In: Kirk-Othmer Encyclopedia of Chemical Technology,
Volume 18. New York, John Wiley and Sons, Inc. 1964. pp. 415-431.
7. Environmental Engineering, Inc. and PEDCO Environmental Specialists,
Inc. Draft Background Information for Establishment of National Standards
of Performance for New Sources - Soap and Detergent Industry. Prepared
for U.S. Environmental Protection Agency. Raleigh, North Carolina.
8. Telecon. Rice, V.W., DuBois Chemical with Neuffer, W.J., U.S. EPA.
May 29, and June 1, 1987. Process information on Chemed Corporation
plant in East Rutherford, New Jersey.
8-11
-------
9.0 METAL PARTITIONS, SHELVING, RACKS
9.1 INDUSTRY DESCRIPTION
This chapter discusses SIC Code 2542 - Metal Partitions, Shelving, Lockers,
and Office and Store Fixtures. Plants in this SIC code manufacture metal
products such as counters, display cases, gourmet racks, partitions, and
shelves.1 In 1982, this SIC had 533 companies with 568 plants. Two hundred
and ninety nine of these plants had at least 20 employees.2 One hundred and
sixty one plants have greater than 100 employees. A list of the 18 plants in
this SIC code with greater than 500 employees is shown on Table 9-1.
9.2 PROCESS DESCRIPTION
It is uncertain how many of the 568 plants in this SIC code use sodium
hydroxide at their facilities. According to one plant representative, many
plants would contract metal plating to job shops that are discussed in
Chapter 6 - Metal Finishing.4 Telephone calls were made to eight plants that
are members of the Rack Manufacturing Institute or the National Association
of Display Industries. Two plants use caustic soda and one uses it only to
regenerate resins from a water deionizer.
Specific process Information was obtained from three other plants that
use sodium hydroxide. Ferro Merchandizing Equipment, Union, New Jersey,
manufactures metal displays and racks that, for example, are used in department
stores for clothing displays. The plant has two plating lines; one that is
operated manually and the other automatic. A process flow diagram is shown
in Figure 9-1 for a plating line at this plant.
All tanks have approximately identical capacities of 800 gallons and
dimensions of 3 feet wide, 9 feet long, and 5 feet deep. The process is a
batch type with each metal batch weighing 75-100 pounds and a retention time
of 30 seconds per tank. More detailed descriptions of the soak cleaning and
electrocleaning processes are contained in Chapter 6.
The only tanks that use sodium hydroxide are the electroclean and
activator tanks. For the electroclean tanks, a 60% caustic soda powder is
used at a rate to produce a 6% total bath concentration of the powder in the
9-1
-------
TABLE 9-1.
SIC 2542 - U.<
500 EMPLOYEES*
PLANT NAME
PLANTS WITH GREATER THAN
LOCATION
American Desk Manufacturing Company
Ball Company
Forsyth International, Limited
Hauserman Incorporated
Hayworth Incorporated
Lozler Corporation
LTV Steel Company
Lyon Holding Company
Madix Incorporated
Reflector - Hardware Corporation
Republic Storage Systems Company
SPS Technologies Incorporated
Sunarhauserman Incorporated
Syndicate Systems Incorporated
Tab Products Company
U.S. Providence Corporation
Unarco Industries Incorporated
Vespar Corporation
Temple, TX
Winston-Sal em, NC
Gumming, GA
Cleveland, OH
Holland, MI
Omaha, NE (2 plants)
Salem, NH
Aurora, IL
Terrell, TX
Mel rose Park, IL
Canton, OH
Santa Ana, CA
Cleveland, OH
Indianapolis, IN
Palo Alto, CA
Providence, RI
Chicago, IL
Bala-Cynwyd, PA
9-2
-------
I CHROME I
IFINISHI
V
I I
I RINSE |
I |
I I
I ACTIVATOR|
I I
I I
FINAL
PRODUCT
l r .
I RINSEI /_
I |X
I I ,
INICKEL | /
"IPLATINGI V
I I
RINSEI
|
i r , \\
I ACID | / | RINSEI
I DIP |^ | |
I I I I
Figure 9-1. Plating Line - Ferro Merchandising Equipment - Union, New Jersey4
9-3
-------
tanks. Thus, 4% by weight of the electroclean tanks contents 1s sodium
hydroxide. The tanks operate at 150 - 170°F and are dumped approximately
every two weeks for one dally operating shift and every week If there are 2-3
dally operating shifts. The activator tank 1s used to assure chrome coverage
on metal parts. One percent of the tank contents 1s sodium hydroxide and the
tank 1s operated at ambient conditions.4
Another plant, Smith-McDonald Products In Buffalo, New York produces
metal fabrication products such as letter trays, ash trays, desk accessories
and mall sorting racks. Fifty percent caustic soda solutions are used 1n
copper plating and to blacken brass. Caustic soda Is added at rates of 1/2
and 12 oz/gallon, respectively.5
Republic Storage Systems, Canton, Ohio, has a small zinc plating operation,
using caustic soda, where latches and lock parts, contained 1n barrels, are
plated 2-3 days/week. Also, a ferric phosphate cleaning system that has
sodium hydroxide removes oil from coll metal products prior to metal
fabrication. Caustic soda Is also used to backflush resins used to delonize
water.6
9.3 EMISSIONS/HEM INPUTS
Based on printouts received from the States of Kentucky, New Jersey, New
York and Texas, only two metal partition/shelving rack plants located In
these States have sodium hydroxide air emission estimates. These estimates
and stack parameters for emission sources at these two plants are shown on
Table 9-2.
9-4
-------
TABLE 9-2.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM METAL PARTITIONS
PLANT
NAME STATE LAT. LONG.
Ferro
Merchan-
dising
Equipment
Corp. NJ 404007 741330
Smith-
McDonald
Products
Corp. NY 425433 844511
EMISSION
TYPE
STACK
STACK
STACK
STACK
HEIGHT
(M)
7.5
6.9
7.2
7.2
VERTICAL
AREA
(SQ. M.)
7.6
21.0
4.7
3.2
DIAMETER
(M)
0.75
3.1
0.65
0.45
VELOCITY
(M/S)
12
6.6
14
8.1
TEMP.
(°K)
300
300
330
290
EMISSIONS
(Kg/yr)
930 3
3,900 2
2
100
91
SOURCE
DESCR.
Electroclean Tanks
Electroclean Tanks
Soak Clean Tanks
Plating
Plating
CONTROL
DEVICE
None
, None
None
None
vo
i
en
-------
9.4 REFERENCES
1. The Statistical Policy Division, Office of Management and Budget. Standard
Industrial Classification Manual 1972. Washington, DC. 1972. p. 99.
2. Bureau of the Census, U.S. Department of Commerce. 1982 Census of
Manufactures - General Summary Part 1. MC-82-S-1 (Part 1). Washington,
DC. March 1986. p. 1-8.
3. Duns Electronic Yellow Pages - Manufacturers. File 510. April 1987.
4. Telecon. Dimattia, F., Ferro Mechandising Equipment with Neuffer, W.J.,
U.S. EPA. July 10, 1987. Process information on Union, New Jersey plant.
5. Telecon. Rotando, H. Smith-McDonald Products Company with Neuffer, W.J.,
U.S. EPA. July 24, 1987. Process information on Buffalo, New York
plant.
6. Telecon. Eshbach, B. Republic Storage Systems with Neuffer, W.J., U.S.
EPA. July 28, 1987. Process information on Canton, Ohio plant.
9-6
-------
10.0 MISCELLANEOUS INDUSTRIES
10.1 SUMMARY
Based on computer printouts received from the States of Kentucky,
New Jersey, New York, and Texas, there are numerous Industries with estimated
sodium hydroxide emissions less than 10,000 Ib/yr. Plants with sodium hydroxide
emissions between 1,000 - 10,000 Ib/yr and not 1n SIC codes discussed In
Chapters 3-9 are summarized 1n tables 1n this chapter. There are numerous
other plants 1n these States with emissions below 1,000 Ib/yr. Due to the
lower emissions from these sources, compared to plants In prior chapters,
little time was expended to verify these estimates. Some New Jersey plants
are not Included In tables for this chapter as most emissions are from NaOH
storage tanks which are now considered to be minor. Table 10-1 presents the
five plants in the four States with estimated sodium hydroxide emissions greater
than 5,000 Ib/yr (2,300 kg/yr) but less than 10,000 Ib/yr (4,500 kg/yr).
Table 10-2 shows the 25 plants in New York, Kentucky, and Texas that
have sodium hydroxide emissions between 1,000 - 5,000 Ib/yr. There are 22
different SIC codes in this table with SIC 3429 (Hardware) having three plants
and SIC 3811 (Engineering and Scientific Instruments) having 2 plants. Most
emission sources are electroplating, metal cleaning or etch tanks. Only
three plants have emission control equipment, two with wet scrubbers and one
with a mist eliminator.
Table 10-3 summarizes the 29 plants in New Jersey with sodium hydroxide
emissions between 1,000 - 5,000 Ib/yr. There are 22 different SIC codes with
the following SIC codes having more than one plant: 2816 (Inorganic Pigments)
- 3; 2819 (Industrial Inorganic Chemicals) - 4; 2821 (Plastic Materials) - 2;
and 3341 (2° Nonferrous Metals) - 2. Process units in these plants that
cause these emissions and any control equipment used were not identified in
the printout received from New Jersey.
10-1
-------
TABLE 10-1. PLANTS WITH SODIUM HYDROXIDE EMISSIONS BETWEEN 5,000 - 10,000 Ib/yr
o
i
ro
SIC
CODE
3325
2834
3911
INDUSTRY
Steel Foundries
Pharmaceutical
Preparations
Jewelry, Precious
Metals
COMPANY
General Electric
EM Diagnostic
PM Refining
LOCATION
Schenectady, NY
Greenwich Township,
NJ
Buffalo, NY
EMISSIONS
Ib/yr (kg/yr)
5,300 (2,400)
8,800 (4,000)
5,400 (2,500)
SOURCE CONTROL
DESCRIPTION EQUIPMENT
Rinse Tank
4 Filling Lines
2 Gold Melting
Furnaces
None
None
Packed
Tower
Scrubber
3542 Machine Tools
Chicago Pneumatic Frankfort, NY
Tools
3568 Power Transmission Bendlx Fluid Power Utlca, NY
Equipment
870 (400)
6,000 (2,700)
5,800 (2,600)
3 Gold Melting None
Furnaces
Rust Stripping None
Tank
Alkaline Cleaning None
-------
TABLE 10-2. PLANTS IN KENTUCKY, NEW YORK, AND TEXAS WITH SODIUM HYDROXIDE EMISSIONS
BETWEEN 1,000 - 5,000 Ib/yr
o
co
SIC
CODE
3200
2819
3572
3811
3714
3429
3574
3078
3452
3496
3442
6512
3429
INDUSTRY
Stone, Clay and
Glass
Industrial
Inorganic
Chemicals
Typewriters
Eng. and Sc1.
Instruments
Motor Vehicle
Parts
Hardware
Calculating
Machines
M1sc. Plastic
Partc
r a r Lo
Nuts * Bolts
Fabricated Wire
Metal Doors
Non-Resld. Bldg.
Hardware
COMPANY
Corning
American Chrome
and Chemical
SCM
Abbott Labs.
Sealed Power
Weber-Knapp
NCR
Owens-Illinois
Crest Products
Plymouth Tube
Hopes
Ideal Corp.
Chautauqua
LOCATION
Erwln, NY
Corpus Chrlstl, TX
Cortland, NY
Irving, TX
Franklin, KY
Jamestown, NY
Ithaca, NY
Bards town, KY
Lexington, KY
Hopk1nsv1lle, KY
Jamestown, NY
Brooklyn, NY
Jamestown, NY
EMISSIONS
Ib/yr (kg/yr)
4,500 (2,050)
4,400 (2,000)
4,200 (1,900)
4,000 (1,800)
3,500 (1,600)
3,200 (1,500)
3,100 (1,410)
3,000 (1,360)
2,500 (1,100)
2,200 (1,000)
2,100 (950)
1,900 (860)
1,800 (820)
SOURCE CONTROL
DESCRIPTION EQUIPMENT
Nickel Plating
Chromic Acid
Dl ant-
r 1 ant
Cleaning Tanks
Chemical Manu.
Rust Strip Tanks
Aluminum Etching
Plating
Industrial
Washing
Electrocleanlng
Electroplating
Caustic Dip Tank
Plating
Electrocleanlng
None
Wet Scrubber
None
None
None
None
None
None
None
Wet Scrubber
None
None
None
-------
TABLE 10-2. PLANTS IN KENTUCKY, NEW YORK, AND TEXAS WITH SODIUM HYDROXIDE EMISSIONS
(Continued)
o
SIC
CODE
3629
3717
3573
3811
3613
3429
3662
3679
3479
3497
3742
1950
INDUSTRY
Electrical
Industrial
Apparatus
Motor Vehicle
Electronic
Computing
Eng. and Sc1.
Instruments
Switch Gears
Hardware
Radio 4 TV Equip.
Electronic Comp.
Metal Coating
Metal Foil
Railroad Equip.
Wash & Clean
COMPANY
LRC Electronics
Ford Motor
IBM
Singer Col Ink
Square D
Union Fork 4 Hoe
IBM
Hadco Print
Universal
Fasteners
Park Nameplate
NY A1r Brake
C. 6. Phillips
LOCATION
Chemung Co. , NY
Green Island, NY
Endlcott, NY
Klrkwood, NY
Lexington, KY
Frankfort, NY
Owego, NY
Owe go, NY
Lawrenceburg, KY
Flushing, NY
Watertown, NY
Seneca Falls, NY
EMISSIONS
Ib/yr (kg/yr)
1,700 (770)
1,600 (730)
1,500 (680)
1,400 (640)
1,400 (640)
1,200 (550)
1,200 (550)
1,200 (550)
1,200 (550)
1,200 (550)
1,100 (500)
1,100 (500)
SOURCE CONTROL
DESCRIPTION EQUIPMENT
Etch Tank
Dip Tank
Stripping,
Etching
A1 um1 num
Deoxidize
Cadmium Plating
Wash Tanks,
Aluminum Etching
Copper Plating
Solder Stripping
Metal Plating
Curing Ovens
De-rusting
Dip Tanks
None
None
None
None
M1st El 1m
None
None
None
None
None
None
None
Minerals
-------
TABLE 10-3. NEW JERSEY PLANTS WITH SODIUM HYDROXIDE EMISSIONS
BETWEEN 1,000 - 5,000 Ib/yr
SIC
CODE
2823
2842
3562
2816
3341
2833
3544
2819
3429
2821
2819
2816
2816
3548
INDUSTRY
Cellulosic Man-Made
Fibers
Polishes, Cleaning &
Sanitation Goods
Ball & Roller
Bearing
Inorganic Pigments
2° Nonferrous Metals
Medicinal, Botanical
Products
Special Dies, Tools
Industrial Inorganic
Chemicals
Hardware
Plastics Material
Industrial Inorganic
Chemicals
Inorganic Pigments
Inorganic Pigments
Metal work ing
u. —u j -.
COMPANY
Hercules
Witco Chemical
Roller Bearing Co.
Ciba Geigy
Engelhard Minerals
Jame Fine Chemical
Crest Products
Pennwalt
General Motors
Graver Company
Old Bridge Chemical
Heubach
Nuodex
L-Tec
LOCATION
Sayreville
Paterson
Ewing
Dover
Newark
Bound Brook
Union
West Deptford
Ewi ng
Newark
Old Bridge
Newark
Piscataway
Piscataway
EMISSIONS
Ib/yr (kg/yr)
4,400 (2,000)
3,800 (1,700)
3,800 (1,700)
3,600 (1,600)
2,600 (1,200)
2,200 (1,000)
2,200 (1,000)
2,200 (1,000)
2,200 (1,000)
2,000 (910)
2,000 (910)
1,800 (820)
1,800 (820)
1,800 (820)
3842 Surgical Appliances
and Supplies
2819 Industrial Inorganic
Chemicals
2819 Industrial Inorganic
Chemicals
Howmedica
Kuehne Chemical
C. P. Chemicals
Rutherford
South Kearny
Woodbridge
1,400 (640)
1,400 (640)
1,400 (640)
10-5
-------
TABLE 10-3. NEW JERSEY PLANTS WITH SODIUM, HYDROXIDE
BETWEEN 1,000 - 5,000 Ib/yr
(Continued)
EMISSIONS
SIC
CODE
2899
2818
2840
3611
2821
2951
3352
3341
3255
2834
2810
INDUSTRY
Chemical Preparations
Industrial Inorganic
Chemicals
Soaps, Cleaners
Electrical Equipment
Plastics Materials
Paving Mixtures &
Blocks
Nonferrous Rolling
and Drawing
2° Nonferrous Metals
Clay Refractories
Pharmaceutical Prep.
Industrial Inorganic
COMPANY
Southland Corp.
Givaudan
Dow Consumer Products
RCA
B. F. Goodrich
W1tco Chemical
Easco Corp.
Johnson Matthey
Certech
Hoffman LaRoche
American Cyanamid
LOCATION
Great Meadows
Clifton
Piscataway
Camden
Oldmans
Perth Amboy
N. Brunswick
Winslow
Westwood
Nutley
Linden
EMISSIONS
Ib/yr (kg/yr)
1,400 (640)
1,300 (590)
1,200 (550)
1,200 (550)
1,200 (550)
1,200 (550)
1,100 (500)
1,100 (500)
1,000 (450)
1,000 (450)
1,000 (450)
Chemicals
3599 Machinery, Except
Electrical
GSM
Pennsauken
1,000 (450)
10-6
-------
11.0 NaOH INDUSTRY
11.1 INDUSTRY DESCRIPTION
Table 11-1 shows the 43 plants operating in the United States 1n 1986
that produce sodium hydroxide (caustic soda). Also, shown in this Table is
the process (diaphragm, mercury or membrane) used at each plant. Twenty-five
plants have diaphragm cells, 21 plants have mercury cells and 4 plants have
membrane cells. Also, some pulp and paper plants produce NaOH as a captive
operation. Table 11-2 shows recent changes in capacity for chlor-alkali plants
1n 1986-87. During this period, there were four expansions and two shut-downs.
Table 11-3 provides some historial production of caustic soda in the United
States. For the period 1970-85, production for each year was around 10 minion
short tons and as high as 12.8 million short tons. Most sodium hydroxide is
produced as a 50% solution.
11.2 PROCESS DESCRIPTION
11.2.1 General
Sodium hydroxide (caustic soda) is produced by the electrolysis of a
sodium chloride (salt) solution via the diaphragm, mercury, or membrane cell.
Chlorine and caustic soda are produced concurrently in the electrolytic cells.
Chlorine is produced at the anode and sodium hydroxide forms at the cathode
of the cell. In the diaphragm-cell plants, the caustic leaves the cells as
a dilute solution and is evaporated to either 50 or 73 percent solutions.
In mercury cell plants, high purity caustic can be produced in any desired
strength and requires no concentration.2 A description of the three
cell processes follows.
H.2.2 Diaphragm Cell Process
Diaphragm cells produce approximately three-fourths of the caustic
produced 1n the U.S.3 A process flow diagram Is shown on Figure 11-1. The
Input to these cells is normally saturated brine. Brine purification is necessary
to prevent plugging of the diaphragm by the precipitation of metal hydroxides.
11-1
-------
TABLE 11-1. NaOH PLANTS IN THE UNITED STATES -19861
Plant
Stauffer Chemical Company
01 in Corporation
Occidental Chemical Corp.
Occidental Chemical Corp.
Dow Chemical USA
Dow Chemical USA
01 in Corporation
LCP Chemicals 4 Plastics, Inc.
Brunswick Chemical Company
General Electric Company
Vulcan Chemicals
B.F. Goodrich Chemical
Formosa Plastics Corp. USA
Occidental Chemical Corp.
Vulcan Chemicals
Kaiser Aluminum & Chemical Corp.
PPG Industries, Inc.
Dow Chemical USA
Georgia Gulf Corporation
Stauffer Chemical Company
Occidental Chemical Corp.
LCP Chemicals A Plastics, Inc.
Stauffer Chemical Company
01 in Corporation
LCP Chemicals A Plastics, Inc.
LCP Chemicals * Plastics, Inc.
Fort Howard Paper Company
Pennwalt Corporation
01 in Corporation
E.I. duPont deNemours A Co., Inc.
Dow Chemical USA
Occidental Chemical Corp.
Occidental Chemical Corp.
Hercules, Inc.
Georgia-Pacific Corporation
Weyerhaeuser Company
Pennwalt Corporation
LCP Chemicals A Plastics, Inc.
PPG Industries, Inc.
Fort Howard Paper Company
PAG Paper Products Company
Vulcan Chemicals
Location
LeMoyne, AL
Mclntosh, AL
Mobile, AL
Muscle Shoals, AL
Pittsburg, CA
Delaware City, DE
Augusta, GA
Brunswick, GA
Brunswick, GA
Mt. Vernon, IN
Wichita, KS
Calvert City, KY
Baton Rouge, LA
Convent, LA
Geismar, LA
Gramercy, LA
Lake Charles, LA
Plaquemine, LA
n H
St. Gabriel, LA
Taft, LA
Orrington, ME
Henderson, NE
Niagara Falls, NY
Syracuse, NY
Acme, NC
Muskogee, OK
Portland, OR
Charleston, TN
Corpus Christi, TX
Freeport, TX
Deer Park, TX
LaPorte, TX
Hopewell, VA
Bellingham, WA
Tacoma, WA
Tacoma, WA
Moundsville, WV
New Martinsville, WV
Green Bay, WI
Green Bay, WI
Port Edwards, WI
Process
Mercury
Diaphragm
Mercury
Mercury
Diaphragm
Mercury
Mercury
Mercury
Diaphragm
Diaphragm
Diaphragm, Membrane
Mercury
Diaphragm
Diaphragm
Diaphragm
Diaphragm
2 Diaphragm, Mercury
Diaphragm
Diaphragm
Mercury
Diaphragm, Mercury
Mercury
Diaphragm
Diaphragm
Diaphragm, Mercury
Mercury
Membrane
Diaphragm
Mercury
Diaphragm
Diaphragm, Mercury
Diaphragm, Mercury
Diaphragm
Diaphragm
Mercury
Diaphragm
Membrane
Mercury
2 Diaphragm, Mercury
Diaphragm
Membrane
Mercury
11-2
-------
TABLE 11-2. RECENT CHANGES IN CAPACITY AT CHLOR-ALKALI PLANTS (1986-87)1
Plant
General Electric Company
Brunswick Chemical Company
Occidental Chemical Corp.
DuPont/OHn (joint venture)
DuPont
Dow Chemical USA
Location
Burkville, AL
Brunswick, GA
Taft, LA
Niagara Falls,
Corpus Chrlstl,
Freeport, TX
NY
TX
Project
New Plant - Diaphgram
Membrane cell added
Restart 2 cells
New Plant - Membrane
Shut-down entire plant
Partial shut-down
TABLE 11-3. NaOH PRODUCTION IN THE U.S.I
.Total
Year (103 Short Tons)
1970 10,100
1975 9,630
1976 10,500
1977 11,000
1978 11,300
1979 12,800
1980 11,600
1981 10,600
1982 9,380
1983 10,000
1984 10,900
1985 10,800
Liquid 68-74* Liquid - Others Dry
(10-3 Short Tons) (103 Short Tons) (103 Short Tons)
837
552
500
567
510
489
435
405
320
341
335
281
8,550
8,800
9,760
10,100
10,400
11,700
10,800
9,980
8,740
9,430
10,400
10,500
NA
393
376
353
393
470
441
375
292
325
308
255
11-3
-------
Brine
1 Treatment 1
1
1
1 f
I 1
f 1
1 1
1 I
j.
V
1 1
1 1 Recovery I
(Evaporation I
1 1
1 1
I i
1 1
IPnnrpnl" rati f\n 1 .....
I I
1 brying |
» — s 1 Pf\mnv*oc c i /\n !___
JLiquefactionj
I LOO i i ng i
1 rnmr»i*peei nn 1 — — — ~
1 1
___s Cni KlaHU
> TVL KlaHI-l
Liquid C12
Product
Caustic|
Fusion 4 j-
Flaking I
•> Anhydrous NaOH
Figure 11-1. NaOH Production by the Diaphragm Cell Process
11-4
-------
In the brine treatment process, soda ash and caustic are added to adjust
the pH to about 10 to precipitate insoluble metal hydroxides such as calcium
and magnesium. The brine is then filtered to remove these precipitates.4.5
A diagram of a typical diaphragm cell is shown on Figure 11-2. As many
as 200 cells are operated in series. In this cell hot (60-70°C), purified,
saturated brine is fed continuously to the anode and hot chlorine gas,
hydrogen and caustic soda are produced.5 The following reaction takes place:
2 NaCl+ 2H20 —> 2 NaOH + C12 + H2
Diaphragm cells consist essentially of three parts; the anode, the
cathode and the diaphragm separating the two. The cells are rectangular or
cylindrical steel shells supporting graphite or steel screen cathodes. The
anode section consists of a concrete bottom holding an assembly of closely
spaced graphite blades cast in lead. Extending through the side of the
bottom are copper bus bars that conduct current to the lead. The cathode
section rests on the concrete bottom and is constructed of a steel plate with
a wire screen coated on the anode side with an asbestos diaphragm. The
concrete top is sealed to the cathode section. The diaghragm permits the flow
of brine between the anode and cathode compartments while preventing contact
of the products of the electrolytic decomposition.5
The diaphragm cell produces a weak caustic liquor containing about 11
percent caustic and 15 percent sodium chloride. The caustic is concentrated
in evaporators to 50 percent and sometimes to 73 percent caustic. During
evaporation, excess salt precipitates out and is filtered, washed, and returned
to the brine system as a slurry.5
11-5
-------
CONCRETE
CELL TOP
ANOLYTE (BRINE)
CHLORINE
OUTLET
HYDROGEN
OUTLET
CATHODE
BUSBAR
GRAPHITE ANOD
CONCRETE
CELL BOTH*
LEAD POUR
JOINING ANODES
ASBESTOS-COVERED
CATHODE FINGER
BRINE INLET
(ORIFICE FEED)
•AMMETER
CATHODE
FRAME
CELL LIQUOR
OUTLET
•ASTIC SEALER
AND INSULATOR
ANODE BUS BAR
INSULATOR
Figure 11-2.
Diaphragm Cell Used to Produce
Sodium Hydroxide and Chlorine^
11-6
-------
11.2.3 Mercury Cell Process
In the mercury cell process, solid salt is required for makeup of the
electrolyte. The electrolyte Is a saturated (about 25%) salt solution, which
Is heated and passed Into purification tanks, where It is treated with sodium
carbonate and some caustic soda to precipitate calcium, magnesium and Iron
as hydroxides.6
A flow diagram for this process Is shown on Figure 11-3. Purified brine
Is fed from the main brine treatment section through the Inlet end box to the
electrolyzer, where It flows between a stationary graphite or metal anode and
a flowing mercury cathode. The spent brine Is recycled from the electrolyzer
to the main brine treatment section through a dechlorination step. Chlorine
gas is formed at the anode of the electrolyzer and is collected for further
treatment. The gas is cooled, dried by scrubbing with concentrated sulfuric
acid, and compressed. The dry chlorine gas may be used directly or may be
liquified.7
The sodium is collected at the cathode of the electrolyzer, forming an
amalgam. The sodium amalgam flows from the electrolyzer through the outlet
end box to the decomposer, where it is the anode to a short-circuited graphite
or metal cathode in an electrolyte of sodium hydroxide solution. Water is
fed to the decomposer and reacts with the sodium amalgam to produce elemental
mercury, sodium hydroxide solution, and by-product hydrogen gas.
The stripped mercury is returned to the cell. The caustic soda solution
generally leaves the decomposer at a concentration of 50 percent sodium
hydroxide by weight. This solution is usually filtered to remove impurities.
The filtered caustic solution may be further concentrated by evaporation.
The by-product hydrogen gas from the decomposer may be vented to the atmosphere,
burned as a fuel, or used as a feed material in other processes.7
11-7
-------
/ BASIC TREATMENT CHEMICALS
(SODA ASH, CAUSTIC I
ACID, CaCL2, ETC.)
CHLORINE
SOLI
NaCL Fl
OTHER
D
:EO
MAIN
STREAM
RECYCLE
MAIN BRINE
SATURATION,
PURIFICATION, AND
FILTRATION
[
J
I
•»»
f
BRINE
DECHLORINATOR
TREATED
SPENT BRINE
BRINE
i
1
INLET
*•* END-BOX
END-BOX
VENTILATION SYSTEM
AQUEOUS
LAYER
STRIPPED
AMALGAM
END-BOX
VENTILATION SYSTEM
H| PUMP
AQUEOUS LAYER
HATER COLLECTION
SYSTEM
PRODUCT
CHLORINE
COOLING,
DRYING,
COMPRESSION, AND
LIQUEFACTION
OUTLET END-BOX
END-BOX
VENTILATION SYSTEM
AQUEOUS LAYER
HYDROGEN GAS
BYPRODUCT
END-BOX
VENTILATION SYSTEM
DECOMPOSER
(DENUDER)
AMALGAM
CAUSTIC SODA
SOLUTION
FILTRATION.
CONCENTRA-
TION, AND «*CAUSTIC
MERCURY
RECOVERY
PRODUCT
SOOA
Figure 11-3.
NaOH Production by the Mercury
Cell Process7
11-8
-------
The Inlet end box Is a receptacle that Is placed on the Inlet end of the
electroylzer to provide a convenient connection for the stripped mercury as
it returns from the decomposer to the electrolyzer. Also, it keeps the
Incoming mercury covered with an aqueous layer. The outlet end box is a
receptacle that 1s placed on the outlet of the electrolyzer to provide a
convenient means for keeping the sodium amalgam covered with an aqueous layer
and for the removal of the thick mercury "butter" that is formed by impurities.7
11.2.4 Membrane Cell Process
There is a trend to build new chlor-alkali or replace existing diaphragm
or mercury cells with membrane cells. Compared to these cells, the membrane
cells are less expensive to build, consume less electricity per ton of product
and cost less to operate.8*9
A flow diagram for this process is shown 1n Figure 11-4. The membrane
cell can use salt or saturated brine as the raw material. Similar to the
other two processes, caustic and soda ash are used to precipitate calcium,
magnesium and other metallic ions. In order to maintain membrane life, a
second stage treatment is used with ion exchange resins. The treated solution
then enters electrolytic cells that produce a 29-33 percent NaOH solution.
In the membrane cell, a synthetic cation exchange membrane separates the
electrolytic reaction products. As in the diaphragm cell, chlorine gas is
generated at one side of the membrane, and caustic soda and hydrogen gas are
produced at the cathode side. The membrane allows passage of only the sodium
ions from the anode to cathode.7 This solution is then pumped to a vacuum
flash evaporator that raises the NaOH concentration to 40 percent. Vapors
from the evaporator are fed to a heat exchanger of the second effect to produce
50 percent caustic soda.8
11-9
-------
Salt or
Saturated Brine
Depleted Brine
Return to Well
-> ! Primary I
I Treatment I
six
(Ion Exchange)
(Treatment I
I
Dechlori nation | <•
I
I Electrolysis I
I
IDryingI
•> (Compression | --->
[Liquefaction!
I I
I Caustic |
I Circulation I
I"
-> I Cooling |
I Compression I
— >
I I
I Evaporationl
-> 50* NaOH
Figure 11-4. NaOH Production by the Membrane Cell Process.
11-10
-------
11.3 EMISSIONS (OTHER THAN NaOH)
Emissions from diaphragm and mercury cell processes Include chlorine
gas, mercury from mercury cells, and carbon dioxide.5 No Information was
readily available on emissions from membrane cells. Gaseous chlorine 1s pre-
sent In the blow gas from liquefaction and from vents In tank cars, ton con-
tainers and cylinders.5 Uncontrolled chlorine emissions vary from 20-100 Ibs/ton
of chlorine produced for diaphragm cells and 40-160 Ib/ton for mercury cells.
Storage and handling results In 33.5 Ib/ton for both processes.10 Control
equipment for blow gas from liquefaction Include water absorption (94 percent
efficiency) and carbon tetrachloride absorption or caustic scrubbing (99.9
percent efficiency).10
From the mercury cells, mercury 1s emitted from the hydrogen by-products
stream, the end-box ventilation system and the end-room ventilation air.7
Control techniques for these processes Include cooling, mist elimination,
chemical absorption, activated carbon adsorption and molecular sieve adsorption.7
Using controls, mercury emissions from the hydrogen gas stream ranged from
0.002-2.0 Ib/day. Lower emissions were controlled by molecular sieve or
carbon adsorption control systems. Highest values are controlled by using a
cooling system alone. For the end box ventilation system, mercury emissions
range from 0.002 - 0.94 Ib/day.7
Carbon dioxide is generated in both diaphragm and mercury cells by the
oxidation of the graphite anodes. Also, carbonates present in the cold feed
brine are decomposed during acidification. Uncontrolled carbon dioxide
emissions vary from 40 Ibs/ton of chlorine produced for diaphragm cells to
20 Ibs/ton for mercury cells.
11.4 NaOH EMISSIONS/HEM INPUTS
Information on sodium hydroxide emissions was obtained on three of the
eight chlor-alkali plants located in the four states (Kentucky, New Jersey,
New York, Texas) that sent printouts on NaOH emissions. No Information was
available from any other data source on sodium hydroxide emissions from this
industry. This Information is summarized on Table 11-4. As shown on this
table, sodium hydroxide emissions are minor as estimated by State personnel
for the chlor-alkali industry and range from 0-25 kg/yr per plant.
11-11
-------
A process flow diagram for the sodium hydroxide emission sources at
Occidental is shown in Figure 11-5. The plant is presently only operating
the diaphragm cells. The centrifuge and filter separate salt and other
impurities from the 50 percent caustic soda solution.1*
Sodium hydroxide emissions from Olin, Niagara Falls, NY, result from the
storage and handling of sodium methylate (NaOCH3). This compound is produced
using the same type of mercury cell used in the production of caustic soda but
is not part of the chlor-alkali plant. The sodium amalgam from the mercury
cell is fed to the decomposer with an electrolytic solution of NaOH. Methanol,
not water, is fed to the decomposer to produce sodium methylate. The chlorine
produced is collected and sent to the chlorine plant. Sodium methylate is
used in the production of Vitamin A and other Pharmaceuticals as well as
serving as a methyl precursor in the manufacture of pesticides and other
products.1^
11-12
-------
I
I—»
GO
u.ecuuijmc Caustic I Cell Liquor | \^T^t^ 1
i»6i is I > (Storaoe Tank^ 1 > iruannva+st* i
: _ , ^uv/iayc lanK.^ | ? tvaporator
1 Solution | (3)* | | | <
1
1 1st Step
>]/
1 Centrifuge* 1
iFeed Tanks(3)|
1
1
xl/
1 1
|Centrifuges*(2) l~
1 1 IProduct |
-> 1 Fllterl > | Storage I
ill 1
1
1
1
1
1 Ulter Cake |
(Storage Tanks*(3)l
To 2nd Step
— > Evaporator
"1
\U
Salt
Ffgure 11-5. Occidental Chemical - Niagara Falls,
* NaOH Emission Sources
-------
TABLE 11-4.
HEM INPUTS FOR SODIUM HYDROXIDE EMISSIONS FROM CHLOR-ALKALI PLANTS
Stack Cross- Stack
Plant Latitude/Longitude Emission Height Sect Area Dia.
Name State (deg, m1n. sec.) Type On) (m2) (m)
Stack Stack NaOH
Velocity Temp. Emissions Emission Control
(m/s) (°K) (Kg/yr) Source Equip.
Occidental NY 430502 850225
Chemical
Stack
Stack
Stack
Stack
25
10
0.30
29.1 289
3 Filter
Cake Tanks
Spray
Tower
Scrubber
SAME STACK AS ABOVE
SAME STACK AS ABOVE
23
10
0.25
13.0 289
8
12
1.7
3 Centrifuge Spray
Feed Tanks Tower
Scrubber
3 Cell Liquor Spray
Storage Tanks Tower
Scrubber
2 Centrifuges Spray
Tower
Scrubber
Olln
Corp.
NY 430451 850136 Stack
Stack
Stack
6
6
8
.7
.4
.2
10
10
10
0
0
0
.05
.05
.05
0.26
0.26
0.26
323
333
333
4.0
4.0
4.0
Sodium Me thy late
Storage Tank
Sodium Me thy late
Feed Tank
Sodium Methyl ate
Collection Tank
None
None
None
Occidental TX 294342 950643 Stack
Chemical
Stack
10.7 10 0.25 11.3 299 0.0 Anhydrous Caustic
Caustic Prod. Scrubber
9.4
10
0.51
12.8 294 0.0 Diaphragm Cell Scrubber
Fugitives
-------
11.5 REFERENCES
1. The Chlorine Institute, Inc. North American Chlor-Alkali Industry Plants
and Production Data Book. Pamphlet 10. Washington, D.C. January 1987.
pp. 1, 2, 10, 13.
2. Cuffe, S.T., R.T. Walsh and L.B. Evans. Chemical Industries. In- Air
P0ll784°n' Thl'rd Edition, Vol. IV. New York, Academic Press. 1977.
3. Shreve, R.W. Manufacture of Chlorine and Caustic Soda. In: Chemical
Process Industries, Third Edition. New York, McGraw-Hill. 1967.
pp. 231-240.
4. Hopkins, H.S. Caustic Soda. In: Chemical and Process Technology
Encyclopedia. New York, McGraw-Hill. 1974. pp. 229-234.
5. U.S. Environmental Protection Agency. Atmospheric Emissions from Chlor-
Alkali Manufacture. Research Triangle Park, NC. January 1971. 93 pp.
6. Lowenheim, F.A. and M.K. Moran. Sodium Hydroxide. In: Faith Keyes
and Clark s Industrial Chemicals, Fourth Edition. New York, John Wiley
and Sons. 1975. pp. 737-745. y
7. U.S. Environmental Protection Agency. Review of National Emission
Standards for Mercury. EPA-450/3-84-104. Research Triangle Park, NC.
August 1984.
8. Means, R.E. and T.R. Beck. A Techno/Economic Review of Chlor-Alkali
Technology. Chemical Engineering. 9H22):46-51. October 29, 1984.
9. Chowdhury, J. New Chlor-Alkali Methods Boost a Sagging Industry.
Chemical Engineering. 91J9):22-27. April 30, 1984.
10. U.S. Environmental Protection Agency. Preliminary Source Assessment for
Chlorine and Hydrogen Chloride. Research Triangle Park, NC. July 1986.
pp. 1-15-20; 3-1-5.
11. Telecon. Juszhiewicz, J. Occidental Chemical with Neuffer, W.J., U.S.
EPA. August 13, 1987. Process information on Niagara Falls, NY plant.
12. Telecon. Kapteina, A. 01 in Corporation with Neuffer, W.J. U.S. EPA
August 13, 1987. Process information on Niagara Falls, NY plant.
11-15
-------
TECHNICAL REPORT DATA
(f 'lease read Instructions on the reverse before completing)
EPA-450/3-88-002
3. RECIPIENT'S ACCESSION NO.
Sodium Hydroxide
Preliminary Source Assessment
5. REPORT DATE
6. PERFORMING
•
William J. Neuffer
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
1. CONTRACT/GRANT NO.
AME AND ADDRESS
DAA for Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park. NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/200/04
A preliminary source assessment of industries with sodium hydroxide emissions is
presented. Brief descriptions of these industries and processes that emit sodium
hydroxide are given. Sodium hydroxide emissions data that were used in the Human
Exposure Model (HEM) are contained in this report. This Model is used by EPA's
Pollutant Assessment Branch to evaluate health risks from various pollutants. Sodium
hydroxide emission data were primarily obtained from the States of Kentucky New
Jersey, New York and Texas.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Grc
Air Pollution
Pollution Control
Preliminary Source Assessment
Hazardous Air Pollutants
Sodium Hydroxide emissions
Air Pollution Control
13B
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
129
22. PRICE
EPA Form 2220-1 (R.v. 4-77) PREVIOUS EDITION is OBSOLETE
------- |