EPA-340/1 -88-004
A Guideline For
Graphic Arts Calculations
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Stationary Source Compliance Division
Washington, DC 20460
June 1988
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CONTENTS
Figures
Acknowledgment
Abstract
1. Introduction
1.1 Purpose
1.2 Process Description
1.2.1 Equipment
1.2.2 Ink Material -
1.3 Emissions
1.4 Regulations
1.5 Calculations
References
2. Basic Data Considerations
3. Basic Reformulation Calculations
4. Control Compliance Calculations
5. Reformulation and Control Compliance Calculations
6. Complex Calculations
7. Alternate Emission Limit
Appendix A - Procedures for Certifying Quantity of
Volatile Organic Compounds Emitted by
Paint. Ink, and Other Coatings. EPA-
450/3-84-019.
Appendix B - Reference Method 24
Reference Method 24A
c ~ Alternative Compliance for Graphic Arts RACT
Darryl Tyler Memo, September 9, 1987.
iii
iv
v
1
1
1
2
3
7
7
9
13
15
19
23
26
34
,46
A-l
B-l
C-l
ii
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FIGURES
Number
1 Flexographic Printing Unit
2 Rotogravure Printing Unit
3
5
ill
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ACKNOWLEDGMENT
Onis guideline was prepared for the U.S. Environmental Protection Agency
(EPA) by PEI Associates, Inc. (PEI) lander Contract No. 68-02-3963. PEI ' ....
appreciates the support and input given by Mr. Bwight HLustick, Mr. laxmi
Kesari, and Ms. Linda lay during the preparation of this guideline. The review
and comments provided by Messrs. James Berry, Robert Blaszczak, Richard Dalton,
William Johnson, Paul Kahn, Michael Pucci, David Satoan arid Dennis Santella are
also gratefully acknowledged.
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ABSTRACT
Hie calculation of volatile organic compound emissions from graphic arts
operations to determine compliance is often a complicated task, sometimes
creating confusion with compliance authorities and sources alike. In an
attempt to minimize this confusion, EPA (OAQPS) has periodically issued
guidance in this area, generally in the form of memoranda to the EPA Regional
Offices. EPA guidance for submitting data on ink formulations and performing
basic calculations is contained in the document entitled "Procedures for
certifying Quantity of Volatile Organic Compounds Emitted by Paint, Ink, and
Other Coatings," EPA 450/3-84-019, published in December 1984. On June 19,
1985, two pages, III-4 and III-9, were revised and issued.
"A Guideline for Graphic Arts Calculations" takes the above guidance
process one step further. Example calculations are included for basic emission
problems, compliance determinations, control strategy problems, and complex
emission problems.
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SECTION 1 .
INTRDEUCnON
1.1 PURPOSE
The purpose of this document is to provide background information, a
process description, emissions data, a regulatory description, and example
calculations for the graphic arts industry, ihis section covers the first four
of these topics to provide the reader with the necessary information for
calculating compliance problems. The remaining sections present sample
calculations typical of those used to determine compliance or to evaluate
control'strategies. These calculations include explanations that are useful to
persons familiar with graphic arts operations. Section 2 provides basic data
considerations that are required to perform these calculations. Section 3
provides basic reformulation calculations to introduce the basic mathematical
concepts involved in calculating volatile organic compound (VOC) emissions from
graphic arts sources. Section 4 illustrates calculation techniques to use when
a printer chooses to reduce emissions with add-on control systems. Section 5
presents reformulation and add-on control compliance calculations. These
problems introduce complicating factors such as multiple printing lines and
dilution solvent and are therefore more complicated than the problems in
Sections 3 and 4. Section 6 includes complex calculations, which incorporate
the techniques demonstrated in Sections 3, 4, and 5 plus multiple inks on
multiple printing presses. Section 7 demonstrates calculations using the newly
developed alternate emission limit which is available through a SIP revision.
1.2 PROCESS DESCRIPTION
The graphic arts industry includes five common types of printing:
rotogravure, flexography, silk screening, letterpress/ and lithography
(offset). The U.S. Environmental Protection Agency (EPA) issued Control
Techniques Guidelines (CIGs) to provide Information to state and local air
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pollution control agencies on the rotogravure and flexographic industries. (1)
Rotogravure and flexography are therefore commonly regulated by State Implemen-
tation Plans (SIPs) and are the subject of this document.
Rotogravure printing is considered by EPA to consist of two different
categories: publication rotogravure and packaging rotogravure. Publication
rotogravure is the printing of paper which is used in books, magazines,
catalogs, etc. (2) These facilities are usually very large in size. Packaging
rotogravure is the printing of paper, foil, and plastic film used to package
various products. It is done by a considerably larger number of companies
ranging from large facilities with many press units to very small captive
operations with only one or two press units. Many processes normally included
within the paper, fabric, or vinyl coating CTG categories may be regulated
under Graphic Arts Regulations if the coating line includes a rotogravure or
flexographic printing station. The State SIP should be checked to determine
which requirements are applicable for a specific source.
1.2.1 Fxauiranent
larger printing operations use presses which have a curved image carrier
mounted on a rotating cylinder, or an etched or engraved image directly on a
rotating cylinder. In direct printing, the image is transferred directly from
the cylinder to the print surface. In indirect printing, the image is
transferred to an intermediate roll called a "blanket" and then to the print
surface.(3)
Flexographic printing is the application of words, designs, and pictures
to a substrate by means of a roll printing technique. The applied pattern is
raised above the printing roll and the image carrier (plate) is made of rubber
or another elastomeric material. A feed cylinder rotates in a trough of ink,
called an ink fountain, and delivers the ink to the plate via distribution
rollers. The web passes between the inked plate and the impression cylinder.
As the impression cylinder presses the substrate against the inked plate, the
image is printed on the substrate. The ink dries by evaporation mainly.
Evaporation is achieved by moving the web through a dryer with temperatures
below 120'C. (See Figure 1.) Flexographic presses are usually rotary web in
design, i.e., roll-fed. However, presses that print corrugated paper board are
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PAPER
WEB
DISTRIBUTION
ROLLERS
TO NEXT
PRINTING UNIT
IMPRESSION
CYLINDER
Figure 1. Flexcxgraphic printing unit. (4)
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one exception. Flexography uses fluid inks (low viscosity), typically about 75
volume percent organic solvent. Obviously, any solvents used must be com-
patible with rubber and other plate materials. (5)
In rotogravure printing, a pattern is etched into the chrome- or copper-
plated gravure cylinder. Chrome-plated cylinders provide better wear resis-
tance. The image is in the form of cells or cups mechanically or chemically
etched in the surface. These cells are usually 0.0014 inches deep by 0.005 (
inches square with approximately 22,500 cells per square inch. The
gravure cylinder rotates in an ink trough or fountain, and the excess ink is
wiped by a steel doctor blade. Then, a rubber impression cylinder (blanket)
presses the web into the etched cylinder to transfer the ionage. Rotogravure
printing also requires very fluid inks with a solvent content ranging from 50
to 85 volume percent or higher. The solvent is evaporated in low-temperature
dryers, 38 to 93 °C. Dryers may be of the steam drum type or may be heated
indirectly by steam or hot air. (See Figure 2.) (6)
1.2.2 Ink Materials
Printing inks are composed of the same type of ingredients as surface
coatings: solids, VOC, negligibly photochemically reactive (exempt) solvent,
and water. Of course, they are tailored to have different properties than
coatings. The solids contained in an ink consist of pigments, resins, and
other materials that influence the consistency of the ink. In addition to
regulatory limitations required by EPA, OSHA, FDA, and USDA, the specifications
for an ink are governed by a number of considerations such as: printing
processes and methods; kind of press; paper or other substrate; drying process;
desired finish: matte, gloss, etc.; end use of the printed product; color;
fabrication method to which the printed stock will be subjected; and sequence
of ink application in multicolor printing. (7)
The VOC content of inks varies widely. Flexographic and gravure inks
contain 50 to 85 volume percent VOC and dry by solvent evaporation. Water-
borne inks contain a volatile mixture that is water plus 5 to 30 volume percent
VOC. (8) Some water-borne inks recently developed do not contain any VOC.
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ADJUSTABLE
COMPENSATING
ROLLER
TO NEXT
PRINTING UNIT
0)RECIRCULATION
FAN
DRYER «
EXHAUST
«- AMBIENT
AIR
INK FOUNTAIN
Figure 2. Rotogravure printing unit. (9)
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The following solvents are representative of those used in printing inks,
usually in combinations:(10)
Toluene
Xylene
Heptane
Isooctane
Mineral Spirits
Naphtha
Hexane
Propanol
Isopropanol
Methanol
Efchanol
Butanol
Glycols
Glycol ether esters
Glycol esters
Acetone
Methyl ethyl ketone
Isopropyl acetate
Normal propyl acetate
Ethyl acetate
A volatile organic compound is defined in 40 CER Subpart A, General
Provisions, §60.2, as any organic compound which participates in atmospheric
photochemical reactions; or which is measured by a reference method, an
equivalent method, or an alternative method; or which is determined by
procedures specified under any subpart. Negligibly photochemically reactive
solvents are used in inks to decrease drying time yet they do not contribute
to the total VOC emissions tally. These materials should not be counted as
VDCis if they are "exempt" from the applicable regulation. The method for
discounting these materials is described in Appendix A. The EPA considers the
following organic solvents to have negligible photochemical reactivity, and
therefore does not consider them to be VDCs.
Methane*
Ethane*
1,1,1-trichloroethane (methyl chloroform)*
Methylene chloride**
Trichlorofluoromethane (CFC-ll)***
Dichlorodifluoromethane (CFC-12)***
C3ilorodifluoromethane (CFC-22)***
Trifluoromethane (CFC-23)***
Trichlorotrifluoroethane (CFC-113)*
Dichlorotetrafluoroethane (CFC-114)***
Chloropentafluoroethane (CFC-115)***
Many states also do not consider some or all of these materials to be VOCs. (11)
* 42 ER 35314, July 8, 1977
** 45 ER 32042, June 4, 1979
***45 ER 48941, July 22, 1980
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1.3 EMISSIONS
Graphic arts operations are significant volatile organic conpound (VOC)
emission sources. Most inks contain VOCs which evaporate during the ink
application and curing processes, rather than becoming part of the dry film.
An EPA study states that the majority of VOC emissions from the f lexographic
printing industry are produced by large facilities/ each emitting more than
1,000 tons per year of VOCs. (12) This study did not include the publication
rotogravure industry, but the data listed below are considered to be represen-
tative of the regulated graphic arts industries since most publication
rotogravure facilities also emit more than .1,000 tons per year. (13)
Facilities with total VOC
emissions less than
50 tons per year
125 tons per year
250 tons per year
Percent of total
industry VOC emissions
<2.7
<7.6
Although the industry is quite diverse with many small facilities, the
regulated industries consist of several hundred large sources.
Ihe VOC emission points in graphic arts sources are the printing unit
where ink application and dilution solvent addition occur, the ovens where
solvent evaporates from the product, and the control device. Regulatory
requirements discussed in the next section limit emissions by specifying the
nonvolatile portion of the ink, the volatile fraction of the ink, or the
overall percent reduction by the control system.
1.4 REGULATIONS
The following is a summary of the RACT regulations which control volatile
organic ompound (VOC) emissions from a packaging rotogravure, publication
rotogravure, or flexographic printing facility that uses VOC-^ontaining ink
and emits a combined weight of VOCs greater than or equal to 100 tons per year.
The applicability cutoff of 100 tons per year is based upon either historical
ink and VOC use or annual potential emissions, depending on the applicable
regulations. Differences exist from state to state. The regulations are
enforced on an ink-by-ink basis when add-on controls are not used or process
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line basis if add-on controls are used unless the facility complies through a
bubble as defined in a specific SIP. Generally, the regulated facility may not
operate unless:
1. A carbon adsorption or incineration system is operated to reduce
the volatile organic compound emissions from an effective
capture system by at least 90 percent. Hie capture system must
ensure an overall reduction in volatile organic compound emissions of
at least the following percentages:
a. 75 percent for a publication rotogravure process; ,
b. 65 percent for a packaging rotogravure process;
c. 60 percent for a flexographic printing process; or
2. The volatile fraction of the ink, as it is applied to the
substrate, contains 25 percent by volume or less of VOC and 75
percent by volume or more of water; or
3. Ihe ink as it is applied to the substrate, less water, contains
60 percent by volume or more of nonvolatile material. (14)
4. Hie EPA has recently developed an equivalent alternate com-
pliance method for flexographic and packaging rotogravure
printing industries only. A SIP revision is required to use
this method. Please see Section 4 for more information.
Please note the following regarding Number 3 listed above. While the
"less water" applies in a majority of states, some SIPs do not include it. The
State SIP should be checked to determine which requirements are applicable for
a specific source.
Only the compounds listed in Section 1.2.2 and any compounds given the
status of "negligibly photochemicaliy reactive" by the U.S. EPA in a future
Federal Register may be considered as exempt from Federal enforcement of
applicable State SIP VOC regulations. Also, Rule 66 or similar regulations
based on solvent substitution and reactivity should not be referenced for
exempting compounds as per 42 FR 35314, July 8, 1977. (15) For the purpose of
determining compliance, negligibly photochemicaliy reactive solvents should be
treated just like water.
There are two graphic arts categories covered by New Source Performance
Standards (NSPS). These are publication rotogravure and flexible vinyl and
urethane coating and printing. The publication rotogravure regulation applies
to printing presses modified or constructed after October 28, 1980. It limits
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VOC emissions to. 16 percent of the total mass of VOC solvent and water used at
the facility during any one performance averaging period, The water used
includes only that water contained in the water-borne raw inks and related
coatings and the water added for dilution with water-borne ink systems, The
flexible vinyl and urethane coating and printing NSK5 regulation applies to
each rotogravure printing line used to print or coat flexible vinyl or urethane
products which was modified or constructed after January 18, 1983. Hie
standard states that the owner or operator must either use inks with a weighted
average VOC content less than1.0 kilogram VOC per kilogram ink solids or
reduce VOC emissions to the atmosphere by 85 percent from each affected
facility. (16)
In addition to the capture and control system option, emissions from
flexographic and rotogravure presses may be reduced by reformulation. Water-
borne inks contain about 75 percent less VOC than conventional inks. (This
number can vary from 65 to 100>er<^t.) Tnese water-borne inks are
extensively in printing corrugated paperboard for containers or multi-walled
bags and other packaging materials made of paper. Only a limited amount of
water-borne ink can be put on thin stock before the paper wUl be seriously
weakened. Some printing systems may be able to use water-borne inks'fpr
complete coverage but still require some solvent-borne inks for printing '
smaller designs which partially cover the web. In complete coverage, large
areas of a given color are applied; however, in partial coverage a thin strip
of a given color is applied and more precision is required. High solids inks
have met with little success in rotogravure and flexographic printing due to v
the design of the process. However, research is being conducted in the
development of a high solids ink which is compatible with existing equip-
ment. (17)
1.5 CALCOIATIONS
The remaining sections in this document present sample calculations
typical of those used to determine .compliance or to evaluate control strategi-
es. These step-by-step calculations are accompanied by explanations that
are useful to persons familiar with graphic arts operations. Basic
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calculations are included along with a variety of more complex problems to
demonstrate emission calculations for different scenarios.
The basis for most of the sample calculations is the information and
procedures discussed in Procedure for Certifying Quantity of Volatile Organic
Compounds Emitted bv Paint. Ink, and Other Coatings. EPA-450/3-84-019, December
1984, which is reprinted as Appendix A of this report and referred to as the
"VOC Data Sheets". On June 19, 1985, two pages, IIX-4 and III-9, were revised
and issued. The first VOC Data Sheet provides information on the VOCs present
in a coating or ink when it is sold by the manufacturer to the coater or
printer. This is referred to as the VOC content of the coating "as supplied
by the coating manufacturer to the user." The second VOC Data Sheet provides
information on the VOCs present in the coating or ink as it is used by the
coater or printer and includes the effect of dilution solvent added before
application. This is referred to as the VOC content of the coating "as
applied to the substrate by the user." The calculations in this document
assume that the inspector has obtained the ink data from the VOC Data Sheets or
an EPA Reference Method 24 or 24A test as appropriate. It is up to the
inspector to verify data. EPA Reference Method 24A is applicable to publica-
tion rotogravure inks only. Reference Method 24 data is acceptable for all
other inks. However, the appropriate SIP should be checked to verify which
test method is required. Appendix B contains a copy of Reference Methods 24
and 24A.
To comply with the VOC regulations, a printer might elect to reformulate
to a low VOC content ink or to use add-on controls such as incineration or
carbon adsorption. VOC compliance or non-compliance can be established through
calculations based on either the efficiency of the control system or the
composition of the ink. For example, in cases where compliance is achieved by
use of water-borne or high solids ink, compliance can be determined through
calculations based on analysis of the ink and formulation data. When add-on
controls are used, more complex stack and capture tests and calculations can be
performed to determine the effectiveness of the control system.
In both flexographic and rotogravure printing, VOC may be introduced to
the system in the ink (either in the ink as supplied, as a diluent, or to
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make-up for evaporative losses) and as a cleaning agent. (18) VOC introduced as
a cleaning agent is not normally included in the total VCC emissions tally.
However, sometimes cleaning solvent is included when the facility complies with
the regulations through alternate means (e.g., a bubble). To reduce emissions,
a capture system and a control device may be used. The two add-on control
systems used primarily on flexographic and rotogravure printing are carbon
adsorption and incineration. (19) Condensation, a third add-on control, is also
used but this method is not as effective in reducing emissions, with carbon '
adsorption, VOCs which are water miscible must be separated from the water,
usually by distillation. Plants that use incineration as a control method'
attempt to minimize the expense by recovering as much of the heat as practical
for use elsewhere in the plant such as drying ovens.
Two compounds, 1,1,1-trichloroethane and methylene chloride, are used as
solvents in some inks but are considered negligibly reactive by EPA and are
exempt from regulation inmost SIPs. The method for discounting these
materials is described in some of the examples and in Appendix A. Generally,
these materials, when "exempt" from the applicable regulation, are treated in
the same manner as water in emission calculations. (20)
The overall efficiency of the control system is a product of the capture
system efficiency and the control device efficiency, it is more difficult to
capture VOC emissions from a flexographic press than a rotogravure press due to
the construction design of flexographic presses. Flexographic printing units
and dryers are mounted compactly such that effective hooding and ducting are
difficult to construct without resorting to a total enclosure. Rotogravure
printing units and dryers are mounted such that hoods and ducts can be
constructed, VOCs which are captured may be routed to the control device.
VOCs which are not captured can, be emitted as fugitive emissions, retained in
the product, or disposed. If waste VOCs are improperly disposed of, they can
be emitted as fugitive emissions. VOC initially retained in the product
usually is released over time and therefore, is considered an emission in
compliance calculations.
The following sections contain sample calculations. Section 3 contains
three basic calculations. The purpose of these problems is to familiarize the
reader with the regulatory requirements by determining the compliance status of
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the inks. Section 4 includes three control strategy calculations. One
compliance option is to vise add-on control systems. These problems present
various VOC control strategies and demonstrate how to calculate emissions to
determine compliance. Section 5 presents three compliance determination
calculations. Examples 2 and 3 are more difficult than the basic and control
strategy calculations because they incorporate multiple printing lines and a
variety of compliance techniques. Section 6 contains two complex calculations.
Uiese problems incorporate multiple lines, inks, add-on controls, complying
inks, and noncomplying inks. All factors must be considered and a series of
calculations must be completed. The sections progress from siitple to complex
so the reader can master the basics and then progress to more difficult
scenarios.
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1.
2.
3.
4.
5.
REFERENCES
Control of Volatile Organic Emissions from Existing Stationary
Sources - Volume VIII: Graphic Arts - Rotogravure and Flexography.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards. EPA-450/2-78-033. OAQPS No. 1.2-109. December 1978
•p. 1-1.
Ibid pp. 2-4, 2-5.
Ibid pp. 2-1, 2-2. .
Enforceability Aspects of RACT for the Rotogravure and Flexography
Portion of the Graphic Arts Industry. PEDCb Environmental, Inc
prepared for the U.S. Environmental Protection Agency, Division of
Stationary Source Enforcement. Under Contract No. 68-02-4147, Task
No. 123. March 20, 1980, p. 6.
Control of Volatile Organic Emissions from Existing Stationary
Sources - Volume VIII: Graphic Arts - Rotogravure and Flexography.
:5* Jr^S1^^ Protection Agency, Office of Air Quality Planning
and Standards. EPA-450/2-78-033. OAQPS No. 1.2-109. December 1978.
6.
7.
8.
9.
10,
Ibid pp. 2-2, 2-4.
Ibid pp. 2-5, 2-6. •''•:-.
Ibid, p. 2-6.
Enforceability Aspects of RACT for the Rotogravure and Flexography
Portion of the Graphic Arts Industry. PEDCo Environmental, Inc
prepared for the U.S. Environmental Protection Agency, Division of
Stationary Source Enforcement. Under Contract No. 68-02-4147, Task
No. 123. March 20, 1980. p. 7.
Control of Volatile Organic Emissions from Existing Stationary
Sources - Volume VIII: Graphic Arts - Rotogravure and Flexography
^"of^i1^611*31 Protection Agency, Office of Air Quality Planning
and Standards. EPA-450/2-78-033. OAQPS No. 1.2-109 Tbecember^^^
1978. p. 2-5.
11. A Guideline for Surface Coating Calculations. Prepared by PEI
Associates, Inc. for U.S. Environmental Protection Agency/Office of
Air Quality Planning and Standards. May 1986. pp. 3-4.
12. Guidance to State and local Agencies in Preparing Regulations to Control
Volatile Organic Compounds from Ten Stationary Sources. U.S. Environmen-
I?n/??r^0n y^L °ffice Of ^ Qx&Xy Planning and Standards. EPA-
450/2-79-004. September 1979. p. 91. ^«*
13
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13. Ibid.
14. Ibid.
15. A Guideline for Surface Coating Calculations. Prepared by PEI
Associates, Inc. for U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards. May 1986. p. 4.
16. New Source Performance Standards. 40 CFR Part 60. Subpart QQ,
Standards of Performance for the Graphic Arts Industry: Publication
Rotogravure Printing and Subpart FFF, Standards of Performance for
Flexible Vinyl and Urethane Coating and Printing.
17. Control of Volatile Organic Emissions from Existing Stationary
Sources - Volume VIII. Graphic Arts - Rotogravure and Flexography.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards. EPA-450/2-78-033. OAQPS No. 1.2-109. December 1978.
pp. 3-9, 3-10.
18. Guidance to State and local Agencies in Preparing Regulations to Control
Volatile Organic Compounds from Ten Stationary Sources. U.S. Environmen-
tal Protection Agency, Office of Air Quality Planning and Standards. EPA-
450/2-79-004. September 1979. p. 92.
19. Control of Volatile Organic Emissions from Existing Stationary
Sources - Volume VIII: Graphic Arts - Rotogravure and Flexography.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards. EPA-450/2-78-003. OAQPS No. 1.2-109. December 1978.
p. 3-1.
20. Procedures for Certifying Quantity of Volatile Organic Compounds
Emitted by Paint, Ink, and Other Coatings. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards. EPA
450/3-84-019. December 1984. pp. II-3, III-5.
14
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. . • . t SECTION 2
BASIC DATA CONSIDERATIONS
Before doing any calculations, it is appropriate to consider the data
needed to perform these calculations and their availability. The graphic arts
standard in the applicable SIP should be considered first to confirm the
applicability and specific requirements of the standard, Compliance require-
ments vary depending on the control strategy being implemented.
If add-on controls are used, compliance must usually be based on a stack
test and a capture efficiency test on each affected line. She control device
efficiency determined by the stack test multiplied by the capture efficiency
equals the overall efficiency of the control system. In most cases, this
result can be/compared directly to the standard which is.expressed as an
overall efficiency. Once a source demonstrates compliance in this manner,
compliance is checked by monitoring the operating conditions of the control
system to ensure they are consistent with/those recorded during the compliance
test. If there is a significant change in these conditions or the plant's
method of operation, or if the integrity of the control system is in question,
the source should be retested to confirm compliance under the- new operating
conditions. Where the control device is a carbon adsorption system, compliance
may be demonstrated by conducting a liquid material balance (total VOC used
versus total VOC recovered). Compliance can usually be checked by reviewing
plant records over some convenient period of time, preferably coinciding with a
line (or plant if appropriate) shutdown (e.g., on a weekend) or process
turnaround. This avoids problems associated with determining the amount of
material (VOC) in process, since the amount of ink in fountains and reservoirs
on a press is difficult to measure, The carbon adsorber should also be
regenerated to assure that all adsorbed VOC has been desorbed and transferred
to the recovery tank and is not in the carbon bed where it can not be measured.
If add-on controls are not used, the inks used must comply with either the
water-borne or high solids standard. Since the high solids standard is usually
.'.,.'.' is ..... .: : •' '•
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expressed as the volume percent solids in the ink less water, a water-borne ink
which does not comply with the water-borne standard must also be evaluated with
regard to the high solids standard.
Most SIP's high solids and water-borne ink standards are based on the
condition of the ink as it is applied to the substrate. The best way to
determine compliance with such standards is to use the results of a Reference
Method 24 (RM-24) or 24A analysis of the ink taken from the press fountain or g
reservoir and additional ink and dilution solvent formulation information.
Most of the information needed to determine compliance can be found on the "as
applied" VQC data sheet. These data include the volume percent solids, volume
percent water, density of the ink and weight fraction VDC. The volume percent
solids of the as applied ink can be calculated (see equations III-6, III-7,
III-8, and 111-12 in appendix A), but the density and volume percent solids of
the as supplied ink and the density of the dilution solvent must be known to do
these calculations. This information is available on either the "as supplied"
or "as applied" VOC data sheets. If the data sheets are not used, the
inspector may have to perform these calculations. In cases where additional
VOC is added during a press run to make up for evaporative losses which occur
at the press fountain or reservoir, then a different result may be obtained if
the calculations are done using RM-24 (or 24A) analysis of the as supplied ink
and records of all dilution and make-up solvent added during a press run. The
method which should be used will depend on the specific SIP requirement. If
the standard is based on the ink as applied, the as applied analysis is
appropriate. If the standard requires that accumulated additions be con-
sidered, as supplied data and dilution records must be used.
If the applicable SIP standard requires that all solvent additions
(dilution and make-up solvent) be considered, the "as supplied" data sheet and
plant records must be used. The procedure for calculating the volume of solids
applied for an ink "as applied" standard does not apply since that calculation
does not fully account for make-up solvent. If plant records are not adequate
to document all solvent additions, steps must be taken to correct this problem
before a compliance determination can be made.
The volume percent of VOC is also needed but is not stated on the VOC data
sheets, nor is it determined by RM-24 (or 24A) analysis. The weight percent
16
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VOC is stated. To convert the weight percent to volume percent, the density of
the VOC must be determined. If a sample of just the solvent or solvent blend
in the ink as applied can be obtained, then a density can be determined
analytically via ASTM D1475. If this is not possible or practical, an average
density can be estimated from formulation data using equations III-2 and III-3
in Appendix A. Note that these equations, as stated in the appendix, are used
to calculate the density of only the dilution solvent. To perform the
calculation suggested here, the values for each VOC used for dilution (to make-
up for evaporation losses) and in the as supplied ink formulation must ^te
included. If available data is not .sufficient to perform this calculation, it
is suggested that the density of the dilution solvent (VOC portion only) be
used as a representative density. This value is stated on the "as applied" VOC
data sheet.
In most instances, only KM-24 (or 24A) analysis results for an ink sample
taken from the press "as applied" are available. To estimate the ink paramet-
ers needed to determine compliance, the volume of solids is often calculated by
assuming that volumes are additive. This method is often called "back
calculating" volume of solids. It introduces a potential error into the
calculation since volumes are not truly additive. As a result, the volume of
solids may;be understated. This method should only be used if all other
methods are not implementable. To perform the calculation, some VOC formula-
tion data must be provided by the source to determine the density of the VOC.
As noted before, this density is needed to convert the weight percent VOC
result from RM-24 (or 24A) to a volume percent. Once the volume percent of
each component other than solids is known (i.e., VOC, water and exempt
solvent), the volume of solids is calculated by subtracting the sum of all ;
other components (volume percent) from 100 percent. The result is the volume
percent solids based on the assumption that volumes are additive.
Caution must be exercised when results calculated in this manner are used
to determine compliance. To compensate somewhat for the error introduced by
the assumption, it is suggested that the highest density indicated for any VOC
present in the ink be used to calculate the volume of solids. This would
17
-------
result in a minimum calculated value for VOC and a maximum calculated value for
volume of solids. Therefore, the results would tend to give the best possible
situation for the source to demonstrate compliance.
The validity and accuracy of compliance calculations are always enhanced
if good operating data and material-use records are available. Ihis is
especially true for graphic arts sources. The regulatory agency should take
steps to assure that records are generated and maintained by a source and that
these records are adequate to determine compliance with the SIP standard.
Wiere non-compliance is evident by the back calculation method, but existing
records are less than adequate for a more comprehensive evaluation, the source,
at a minimum, should be required to maintain the necessary records for a
specific period of time to confirm its compliance status. ,
One last point must be considered before proceeding with the calculations.
Ihe terms "VOC11 and "solvent" have been used rather indiscriminately in the
past. An effort has been made to correct for this but problems are still
evident. The term VOC as defined by EPA (see page 6) would include most
organic solvents, but is not limited to just organic solvents. In practice,
EM-24 (or 24A) test results may actually define VOC; that is organic compounds
which volatilize under test conditions are VOCs. Virtually all organic
solvents would volatilize under test conditions. However, other organic
compounds, which are not solvents by definition, and products of chemical
reactions taking place at test conditions may also contribute to the amount of
VOC determined by the test.
The terms "dilution solvent" and "make-up solvent" are used in this text
to be consistent with terms used by the industry. For the most part, the VOCs
used for these purposes are being used as solvents. However, when considering
formulation data, be aware that the sum of an the components called "solvents"
may not actually be the total amount of VOC present or that would be determined
by an appropriate test.
18
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BASIC
SECTION 3
CALCOIATIONS
The purpose of this section is to familiarize the reader with the
regulations by presenting three basic examples, ihe examples show how to
determine the volume of, VOC and water in the volatile portion of the ink and
volume of solids in the ink to check for complying ink formulations. Example 1
presents ink data for a packaging rotogravure printer. Ihe problem states the
applicable regulation and asks if the plant is in compliance. Example 2
presents ink data f or a f lexographic printer. The printer's ink, less water,
must contain 60 percent by volume or more of nonvolatile material. The problem
asks if the printer is in compliance with the regulation. Example 3 presents
ink data for a publication rotogravure printer. The problem asks how the.
printer can comply with the regulations.
Example 1 -
A packaging rotogravure printing plant uses one ink whose composition as
applied in volume percent from Method 24 testing, manufacturer's data and
calculations from the VOC Data Sheets (See Appendix A) is 10 percent non-
yolatiles, 20 percent VOC and 70 percent water. The press that uses
ink is uncontrolled. Is it in compliance? ^^.
Ih!lreg!?ation states tfc8* a Packaging rotogravure printing operation
must reduce VOC emissions by 65 percent or use an ink which contains
less water, 60 percent by volume or more of nonvolatile material or
use an ink whose volatile fraction contains 25 percent by volume or
less; of VOC solvent and 75 percent by volume or more of water.
The volume percent of nonvolatile material less water is
10% nonvolatiles '
100% ink - 70% water x 10° = 33*
Since the nonvolatile material does not exceed 60 percent by volume
less water, and the press is uncontrolled, check to see if the plant
complies with the third part of the regulation.
The volume percent of VOC in the volatile fraction of the ink is
19
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20% VOC
X 100 = 22.2%.
20% VOC + 70% water
'Hie volume percent of water in the volatile fraction of the ink can
be calculated by either of the following two ways:
70% water
20% VOC + 70% water
or
x 100 = 77.8%
100% - 22.2% = 77.8%.
•Therefore, the press is in compliance with the third part of the
regulation.
Note: Data provided from the reference test methods include
the following "as applied" data: the ink density
(Di)a, weight fraction of total volatiles (V3v)a, and
weight fraction of water (W^. Manufacturer's
formulation data includes volume percent of each non-
volatile component [(Vn)sJ, and name and either the
mass or volume of each VOC present. Ihe source provides
the density of the dilution solvent. From this data, the
following may be calculated (as per Appendix A) :
Volume percent water
= (Ww)a
-------
Where Rd = the volume of VOC added per unit of ink "as supplied" In
the absence of adequate dilution records, Rd can be calculated from
entries on the VOC data sheets, see Page III-7, Appendix A for
additional information.
Density of VOC "as applied"
100%
m W-4
S _2 ' .•" --'-..-.' .-:. :/-"'
or
Where Dj, Wjf and Vj denote the density, weight percent and volume
percentjof each VOC3 (including dilution VOC) in their* aTapplied
and 'm1 is the number of VOCs present.
Volume percent VOC "as applied"
(W0)a (Dj)a
(V
Example 2 -
Printernuses an ink that has the following composition in
weight percent: nonvolatile material 79.3% and VOC 20.7%. Ihe composi-
tions were obtained during Method 24 testing. The ink density islTo
i0?' "? S6-00 ^enaity is 6-° P°^ds Per gallon (from
data) . Is the ink in compliance with a regulation that
6° P— fc ^ volur^ or more of
Since the information needed to calculate volume of solids using
equation 111-12 on page III-8 of Jfcpendix A is not available, volume
of solids is back calculated in this example from VOC content and VOC
density. : OSiis calculation assumes that the VOC and solids volumes
are additive (see Page 17) .
21
-------
The volume of VOC in one gallon of ink is
11.0 Ib ink 0.207 Ib VOC 1 oal VOC 0.38 oal VOC
1 gal ink x llbink x 6.0 Ib VOC Igalink
The volume percent of nonvolatile material in one gallon of ink is
(1 - 0.38) X 100 = 62%.
Therefore, the ink is in compliance.
Example 3 -
A publication rotogravure printer uses an ink that is 80 _percent VOC
and 20 percent pigments and other nonvolatiles (compositions are in
weight percent). The ink has a density of 7.2 pounds per gallon.
The VOC density is 6.5 pounds per gallon. All data were obtained
through Msthod 24A analyses of the ink as applied except that the VOC
density was computed from formulation data. How can this plant
comply with the regulation for publication rotogravure facilities?
First, check to see if the ink meets the high solids criterium for
complying inks assuming that volumes are additive.
The volume of VOC in one gallon of ink is:
0.886 oal VOC
1 gal ink
7.2 Ib ink 0.8 Ib VOC 1 oal VOC _
1 gal ink x 1 Ib ink 6.5 Ib VOC
The volume of solids in one gallon of ink is
1 - 0.886 oal VOC _ 0.114 oal solids
1 gal ink 1 gal ink
Since the volume of solids of the ink as applied is significantly less
than 60 percent by volume, the plant must install a capture and control
system to reduce overall VOC emissions by at least 75 percent. If the
volume of solids applied calculation had resulted in a value which
approached the 60 percent level, it would have been advisable to seek
additional information about the ink and perform a more exact calculation
using equation 111-12 on page III-8 of Appendix A.
22
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SECTION 4
CONTROL OCMPIIANCE CS^JCOIMTONS
The two problems in this section demonstrate VOC control strategies and
how to calculateemissions^ to determine conpliance. Example 1 presents a
flexographic printer which uses a solvent-based ink. Ink data and the yearly
ink use rate are given.' Ihe plant uses add-on controls to control VOC
emissions. Ihe problem asks what the plant's uncontrolled VOC emissions were
last year and if the plant met RACT, what were its controlled VOC emissions.
Example 2 presents a publication rotogravure plant which uses different inks on
its two printing lines. Data and ink use rate for each ink are provided. lwo
add-on control systems are being evaluated. Efficiencies for the control
devices are given. JThe problem asks the reader to calculate what the efficien-
cies of the capture systems must be to achieve a VOC emission reduction of 75
percent. The problem also asks what the annual uncontrolled emissions and
annual allowable emissions with the add-on control systems are from each press
if the overall reduction is exactly 75 percent. Unless otherwise indicated,
all solvents are considered to be VOCs.
Example 1 - . .. . :
A plant uses a flexographic printing ink that is 80 percent by weight
isopropanol and 20 percent by weight pigments and other nonvolatile as
applied. Ihe ink density is 7.44 pounds per gallon. last year, the plant
used 10,000^ 55-gallon drums of ink. A performance test on the plant's
emission control system showed a 75. percent efficiency for the capture
system for each line and a 90 percent efficiency for the control device.
What were the plant's potential (before control) VOC emissions last year?
If the • requirement is to control at least 60 percent of the VOC emissions
on a line by line basis, is the plant in compliance? What would the VOC
emissions have been last year if the plant just met the RACT standard?
What were the actual VOC emissions last year?
The VOC content of each drum is
55 oal ink 7.44 Ib ink 0.8 Ib VOC
drum x gal ink x Ib ink
327.4 Ib voc
drum
23
-------
Annual potential emissions last year were
327.4 Ib VOC 10,000 drums = 3 274 000 ib VOC = 1637 Tons VOC
cicum y
The overall efficiency for each line = (0.75 x 0.90) x 100 = 67.5% which
is greater than 60%. Therefore, each line is in compliance.
With the existing control system, the annual VOC emissions last year were
(3,274,000) X [1 - (0.75 X 0.90)] = 1,064,050 Ib VOC = 532 Tons VOC.
If the emission control system had just satisfied the RACT requirement (60
percent overall efficiency), the annual VOC emissions last year would have
been
(3,274,000 Ib VOC) X [1 - 0.60] = 1,309,600 Ib VOC = 655 Tons VOC
Example 2 -
A publication rotogravure plant uses different inks on its two printing
presses. Press No. 1's ink is 85 volume percent VOC and 15 volume per-
cent pigments and other nonvolatiles as applied. Press No. 1's VOC
density is 6.8 pounds per gallon. Press No. 2's ink is 80 volume percent
VOC and 20 volume percent pigments and other nonvolatiles as applied.
Press No. 2's VOC density is 7.2 pounds per gallon. For the coining year,
the anticipated ink usage is 400,000 gallons for Press No. 1 and 600,000
gallons for Press No. 2.
The company president is evaluating two add-on control systems for the
presses. For Press No. 1, the control device is guaranteed to be 95
percent efficient. For Press No. 2, the control device is guaranteed to
be 98 percent efficient. If the plant must achieve a VOC emission
reduction of 75 percent for each press, what efficiencies must the capture
systems achieve? What are the annual potential (before control) emissions
and the annual actual emissions with the add-on control systems from each
press if the overall reduction is exactly 75 percent and the anticipated
usage is realized.
The emission reduction achieved is the product of the efficiencies of the
capture system and control device. Since the emission reduction must be
75 percent for each press, the capture system efficiencies can be^
calculated by dividing 75 percent by the control device efficiencies.
For Press No. 1, the capture system efficiency must be at least:
x 100 = 78.95%
24
-------
For Press No. 2, the capture system efficiency must be at least
75%
98%
X 100 = 76.53%
The potential annual VOC emissions from each press are
Press No. 1
0.85 gal VOC 6.8 Ib VOC 400.000 oal ink _ 2.312.000 Ib VQC
1 gal ink.• -.1 gal,VOC x yr ~ - T~ _
_ 1.156 Tons voc
yr ....:.. : ; . . „
Press No. 2 ---'•;•
0.80 oal VQC
x 7.2 Ib VOC 600.000 aal ink 3.456.000 Ib VQC
1 gal ink 1 gal VOC x yr yr
1.728 Tons VOG
The actual annual VOC emissions from each press would be
i' . ' ' .
Press No. 1
2,312,000 Ib VOC x _ . _ 578.000 Ib VQC 289 Ions VOC
yr ' yr yr
Press No. 2
3,456.000 Ib VOC
yr
X (1 - 0 75) = 864-000 Ib VOC = 432 Ions VOC
yr yr
25
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SECTION 5
AND CONTROL OMPLIANCE CAICOIATIONS
This section provides four examples which demonstrate how to determine
whether a printer is in compliance with the regulations. Example 1 presents
ink data for a packaging rotogravure printer. Ink data are given which
describe a higher solids ink that the printer is using. The problem asks if
the printer is in compliance with a regulation that requires the ink as it is
applied to the substrate, less water, to contain 60 percent by volume or more
of nonvolatile material. Example 2 provides ink data and the daily ink use
rate for a graphic arts facility. The problem states that two VOC control
strategies are being evaluated. The reader is asked to calculate the daily
emissions for each control option. Example 3 presents data for a flexographic
printing plant. The facility bubbles emissions from its nine printing lines
based on a SIP revision. The regulations require a 60 percent emission
reduction. The plant uses add-on controls on selected printing lines to
control VOC emissions. The object is to see if the actual emissions are less
than or equal to the allowable emissions. The uncontrolled and actual
emissions are calculated for the plant on a per-line basis and the compliance
status is determined. Example 4 presents data for a packaging rotogravure
plant. Dilution solvent is used at this plant. The facility bubbles its
emissions based on a SIP revision. The plant uses refrigeration condensers to
recover VOCs. The plant must meet RACT requirements which require overall VOC
control of 65 percent. The object is to determine the solvent recovery
necessary by the control system. Note that Method 24 is the regulatory test
for determining the VOC content of inks. Formulation data may not be suffi-
cient to determine compliance because of VOC additions and fugitive losses at
the press. Therefore, the percent fractions of VOC and water in the press-
ready ink could change. Unless otherwise indicated, all solvents are con-
sidered to be VOCs.
26
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Example l -
An inspector visits a packaging rotogravure printer to obtain information
for a file update. 3he printer has recently switched to a high solids
ink. Ihe printer gives the inspector an ink analysis sheet with the
following information that is based on Reference Method 24 and data
supplied by the manufacturer:
BLACK INK IOT 270A
Pigments and other nonvolatiles
supplied = (Vn)s
VOC
Water
Ink density - supplied =
Ink density - applied =
Dilution solvent density (from
formulation data) = Dd (90% VOC,
10% H20 by volume)
60% by volume
30% by weight
10% by weight
9.3 Ib/gallon
8.52 Ib/gallon
6.7 Ib/gallon
Is the printer m compliance with a regulation that requires the ink
as it is applied to the substrate, less water, to contain 60 percent
by volume or more of nonvolatile material?
To calculate the volume of solids as applied, we must calculate the
volume of photochemically reactive organic solvent (VOC) added per
unit volume of "as supplied" ink (Erf. since the dilution solvent
contains water, this is a two step process. First we must calculate
the volume of premixed water and VOC added per unit volume of coatina
"as supplied" "
Da -
= ".9.3 - 8.52
8.52 - 6.7
0.43
Then we can calculate R^ as follows (Note: (Vw)d = Volume percent
water in dilution solvent)
= 0.43 [1 - = 0.39
Now we can calculate the volume of solids as applied (V*) as
n/a
follows
(Vn)<
60%
0.39
= 43.2%
27
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Example 2 —
A flexographic printing facility uses a printing ink that is 80 weight
percent VOC and 20 weight percent solids. The ink density is 7.6 pounds
per gallon. The daily ink use is 900 gallons. The plant operates
two eight-hour shifts with 25 percent press outage due to set-up and
clean-up time.
The company president is evaluating two VOC control strategies. Option
No. 1 involves adding a carbon adsorber to recover solvent. The plant
most reduce VOC emissions by at least 60 percent. Option No. 2 involves
switching to a waterbase ink; the ink supplier indicates that the
composition by volume as applied will be 20 percent VOC, 20 percent
solids, and 60 percent water. The density of the VOC in this ink is 6.6
pounds per gallon. This waterbase ink will meet the standard. The _ ink
use rate and press outage are the same as for the high VOC content ink.
What are the daily emissions for each option?
For Option No. 1, the emission reduction must be at least 60 percent.
Daily uncontrolled emissions for this option are
900 oal ink x 7.6 Ib ink x Q.8 Ib VOC _ 5.472 Ib VOC
day 1 gal ink 1 Uo ink day
The daily emissions with controls are
2.189 Ib VOC
5.472 Ib VOC
day
n /=\ -
" °*6) "
day
For Option No. 2, the daily emissions are
1.188 Ib VOC
900 gal ink 0.2 oal VOC 6.6 Ib VOC _
day xlgalinkxlgalVOC day
Example 3 -
A job-shop flexographic printing plant has nine printing lines. The
regulations allow the facility to bubble the nine printing lines through
an EPA approved SIP revision. To comply with the regulations, a 60
percent emission reduction is required. Emissions from Line Nos. 3, 4, 5,
and 6 are controlled by an incinerator whose VOC destruction efficiency at
the time of its last performance test was 95 percent. A material balance
around the ventilation system for these four lines during the performance
test showed that 75 percent of the solvent emissions were captured by the
ventilation system for each of these lines. The inspector verifies that
28
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the incinerator operating tenperature and face velocities of the capture
hoods are the same as during the performance test so he,assumes that the
capture and control efficiencies are unchanged. Emissions from Line
Nos. 7 and 8 are ducted to a common carbon adsorber whose overall control
efficiency measured at the last performance test was 62 percent for each
line. ^^.
Thinning solvent is used on all lines at a rate of 10 volume percent of
the auk use rate per day. The thinning solvent density is 6.6 Ib per
gallon. The plant's ink formulations, ink application rates, and thinning
solvent use rates for one 24-hour period are shown in the following table.
Printing
line
1
2
3
4
5
6
7
8
9
V10C
density,
lb/gal
6.2
6.2
6.2
6.2
6.2
6.2
6.3
6.3
5.8
As supplied
ink formulations
Volume
percent
solids
20.0
20.0
20.0
20.0
20.0
20.0
9.0
9.0
10.0
Volume
percent
VOC
80.0
80.0
80.0
80.0
80.0
80.0
91.0
91.0
90.0
Undiluted
ink
application
rate, gal/day
75
37.5
90.0
75.0
45.0
125.0
70.0
35.0
80
Thinning
solvent
use rate,
gal/day
7.5
3.75
9.0
7.5
4.5
12.5
7.0
3.5
8.0
The uncontrolled pounds of VOC emitted per day are equal to the ink
application rate (gal ink per day) times the volume fraction of VOC
in the ink (gal VOC per gal ink) times the ink VOC density (Ib VOC
per gal VOC) plus the thinning solvent rate (gal thinning solvent per
day) times the thinning solvent density (Ib solvent per gal solvent).
, For Line No. 1, the uncontrolled VOC emissions are
6.2 Ib VOC -I +
1 gal VOC
. 75 oal ink 0.8 gal VQC
r j~.. x
day
1 gal ink
.7.5 oal thinnincf solvent
I
1 gal thinning solvent
372 Ib VOC 49.5 Ib VOC
day day
421.5 Ib VOC
day
29
-------
For lines with controls, the actual pounds of VOC emitted per day are
equal to the uncontrolled VOC emissions (Ib per day) times one minus the
control system efficiency.
For Line No. 3, the actual pounds of VOC emitted per day are
\7T>r
voc
145.4
145'
VOC
voc
0>75)] =
For line Nos. 1, 2, and 9 the actual VOC emissions equal the
uncontrolled VOC emissions because these lines are not controlled.
The uncontrolled and actual VOC emissions for all nine printing lines
are presented in the following table.
Printing
line
1
2
3
4
5
6
7
8
9
TOTAL
Uncontrolled VOC
emissions, Ib/day
421.5
210.8
505.8
421.5
252.9
702.5
447.5
223.8
470.4
3,656.7
Actual VOC
emissions, Ib/day
421.5
210.8
145.4
121.2
72.7
202.0
170.1
85,0
470 o 4
1,899.1
A 60 percent emission reduction is required. Therefore, allowable
VOC emissions are 40 percent of the uncontrolled VOC emissions.
0.4 x 3656.7 Ib VOC/day = 1462.7 Ib VOC/day.
Since the plant emitted 1899.1 Ib VOC on this day, it is not in
compliance.
Example 4 -
A packaging rotogravure plant uses an ink concentrate (density is 10.8
pounds per gallon) that contains 30.55 percent by weight methanol (density
is 6.6 pounds per gallon) and 69.45 percent by weight pigments. The ink
concentrate is used on six printing lines and is diluted prior to use with
isopropanol or water (isopropanol density is 6.6 pounds per gallon). A
source specific SIP revision allows this facility to bubble all lines that
30
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do not use complying inks. The plant ink and solvent usage on one
particular day is as follows:
Line
1
2
3
4
5
6
Ink cone.,
gallons
30
25
55
20
60
35
Dilution
to concentrate
ratio (by vol.)
1:1
1.5:1
1.5:1
1:1
2:1
0.75:1
Dilution
solvent
VDC
Water
VOC
Water
VDC
VDC
Reduction Lines 1, 3, 5, and 6 are controlled by refrigeration con-
densers. What must the daily solvent recovery be for the plant to meet
RACT requirements (overall reduction in VOCs of 65 percent) if we assume
all solvents are VOCs?
First, calculate the composition of the ink concentrate in volume percent
VOC volume percent is:
.3055 lb methanol 10.8 Ibs ink cone. i gallon methanol '.-
Ib ink concentrate 1 gallon ink cone. x 6.6 Ibs methanol ~
50 oal methanol
100 gal ink cone. or 50 Percent.
•Pigment volume percent is 50% (as supplied from formulation
data).
Since 50 percent is less than 60 percent, the ink concentrate does not
meet the high solids ink criteria (ink as applied to the substrate, less
water, must contain 60 percent by volume or more of nonvolatile material)
The addition of dilution solvent or water can not alter this conclusion.
Therefore, all the as used ink does not comply with the high solids
criteria.
Now, check _ the ink formulations on Lines 2 and 4 to see if either meets
the criteria for water-borne inks as discussed in Examples 1 and 2 of
Section 2.
LINE 2
The dilution to concentrate ratio is 1.5 gallons water to 1 gallon ink
concentrate.
31
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The volume percent VOC is
10.8 Ib ink cane. 0.3055 Ib methanol „ 1 oal methanol
gal ink cone.
0.5 gal methanol
gal ink cone.
1 Ib ink cone.
6.6 Ib methanol
Volatile content = 1.5 gal water + 0.5 gal methanol
= 2.0 gal
One VOC content of the volatile portion is
0.5 oal VOC
-T = 0.25
2.0 gal volatile material
This is a complying water-based ink. The VOC from this ink is therefore
exempt from the 65 percent control requirement.
^ _ .
VOC exempt =
LINE 4
12.5 oal VOC 6.6 Ib VOC
x gal VOC
82.5 Ib VOC
day
The dilution to concentrate ratio is 1 gallon water to 1 gallon ink
concentrate. From Line 2, we know that there is 0.5 gallon methanol per
one gallon of ink concentrate.
Volatile content = 1.0 gal water + 0.5 gal methanol = 1.5 gal
VOC content of volatile portion is
0.5 oal voc
1.5 gal volatile material
= 0.33
The VOC content of the volatile portion of the water-borne ink must not
exceed 25 percent to comply with the regulations. Therefore, Line 4 is
not in compliance with the regulations.
Then, calculate the gallons of VOC used per line that contribute to
the baseline uncontrolled VOC emissions, i.e., Lines 1, 3, 4, 5, and
6:
32
-------
Line
1
3
4
5
6
VOC from ink
cone. , gal
15
27.5
10
30
17.5
Dilution
VOC, gal
30
82.5
0
120
26.25
Total,
gal
45
110
10
150
43.75
358.75
The daily uncontrolled emissions isy weight that are subject to the control
requirement are
358.75 gal VOC
- 2367.75 Ib VOC
Ihe daily solvent reo^ery by refrigeration must be:
2367.75 Ib X 0.65 = 1539 Ib VOC.
33
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SECTION 6
COMPLEX. CALCOIATIONS
Ihis section includes two problems which demonstrate complex situations.
i
TO solve these problems, several factors must be considered and a series of
calculations must be completed. Example 1 presents a packaging rotogravure
printer which uses five inks on four presses. The inks are used in different
proportions on each press. The problem incorporates a variety of compliance
methods. Ihe problem asks if the plant is in compliance with a source specific
SIP revision allowing a daily bubble calculation and a VOC emission reduction
requirement of 65 percent from noncomplying inks. Example 2 presents a
publication rotogravure facility which uses various inks on three presses. Ink
data are provided. Ihe problem asks if the plant is in compliance with the
state SIP that allows a daily bubble calculation and a VOC emission reduction
requirement of 75 percent from noncomplying inks. Unless otherwise indicated,
all solvents are considered to be VOCs.
Example 1 -
A packaging rotogravure printing operation has four presses using the same
five inks, though in different proportions at each press. Ihe density of
water is 8.33 Ib/gal. Ihe ink compositions as applied from Reference
Method 24 testing and supplied manufacturers1 data are as follows:
Ink
A
B
C
D
E
Composition, vol %
Solids
65.0
20.0
10.0
7.5
10.5
VOC
35.0
27.0
22.0
90.0
89.5
Water
0.0
53.0
68.0
2.5
0.0
Ink
density,
Ib/gal
11.85
9.30
8.60
6.91
6.95
VOC*
density,
Ib/gal
6.0
6.5
6.5
6.2
6.0
*From formulation and dilution data for press ready ink.
34
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In a given 24-hour period, ink usage for the four presses is as follows:
Press
1
2
3
4
Ink usage, gallons/day
A
10
—
5
10
B
10
-
15
5
C
10
5
25
10
D
10
30
—
5
E
10
10
5
5
Presses 1 and 2 are controlled by catalytic afterburners that have a
tested combined capture and destruction efficiency of 80.0 percent for
each line. Presses 3 and 4 are uncontrolled. Is the plant in compliance
with a source specific Sip revision allowing a daily bubble calculation to
determine the difference in allowable versus actual emissions for credit
purposes from complying inks and a VOC emission reduction requirement of
65 percent from noncpmplying inks?
Actual VOC emissions must be compared to allowable VOC emissions to
determine compliance. Inks A and C are complying inks; A is a high solids
ink that contains at least 60 percent by volume, less water, nonvolatile
material, and C is a water-borne ink whose volatile fraction is at least
75 percent by volume water and not more than 25 percent by volume VOC. In
calculating the allowable emissions for this source, the VOC emissions
from inks that exactly meet the high solids and water-borne criteria are
included because the facility receives credit for the difference in
allowable versus tptal actual emissions according to the SIP.
ACTUAL VOC EMISSIONS
I. • Press 1 ' •' -/''" . ' • " ', .. -
Ink A " ... ' '"" "' ' " " '••""' ' : " • . v ^ ' .- . • .'
•10 gal ink „ 0.350 gal- voc 6.0 Ib VOC 21.0 Ib VOC
day gal ink gal VOC day ,
Ink B
10 gal ink 0.270 oal voc 6.5 Ib VOC 17.6 Ib
day
Ink C
gal ink
VOC
gal voc
day
10 oal ink 0.220 oal VDC 6.5 Ib VOC 14.3 Ib VOC
day
x
gal ink
x
gal VOC
day
35
-------
Ink D
10 gal ink
0.900 oal VOC 6.2 Ib VOC
x gal ink gal VOC
day
Ink E
10 oal ink „ 0.895 oal VOC
day
gal ink
6.0 Ib VOC
gal VOC
55.8 Ib VOC
day
53.7 Ib VOC
day
Press 1 is controlled by a catalytic afterburner with an overall control •
efficiency of 80 percent. Actual VOC emissions from Press 1 are
[21.0 + 17.6 + 14.3 + 55.8 + 53.7] (1 - 0.80) = 32.5 Ib VOC/day.
II. Press 2
Ink C
5 oal ink 0.220 oal VOC 6.5 Ib VOC _ 7.2 Ib VOC
day x gal ink x gal VOC day
Ink D
30 oal ink 0.900 gal VOC 6.2 Ib VOC _ 167.4 Ib VOC
day x gal ink x gal VOC day
Ink E
10 gal ink „ 0.895 gal VOC
day
gal ink
6.0 Ib VOC
gal VOC
53.7 Ib VOC
day
Press 2 is controlled by a catalytic afterburner with an overall control
efficiency of 80 percent. Actual VOC emissions from Press 2 are
[7.2 H- 167.4 + 53.7] (1 - 0.80) = 45.7 Ib VOC/day.
III. Press 3
Ink A
5 gal ink 0.350 oal VOC 6.0 Ib VOC
day x gal ink x gal VOC
Ink B
15 gal ink
day
0.270
1 VOC 6.5 Ib VOC
gal ink x gal VOC
10.5 Ib VOC
day
26.3 Ib VOC
day
36
-------
Ink C •.-...'-''..''.' ; : _:, . .. .---•' .
25 gal Ink 0.220 oal VQC 6.5 Ib VOC 35.8 Ib VOC
.day gal ink x gal VOC ~ day
0.895 gal VOC 6.0 Ib VOC
gal ink x gal VOC
26.9 Ib VOC
day
Emissions from Press 3 are uncontrolled. Actual VOC emissions are
[10.5 + 26.3 + 35.8 + 26.9] = 99.5 Ib VOC/day.
IV. Press 4
Ink A
10 oal ink 0.350 oal VOC 6.0 Ib VOC 21 0 Ib VOC
day x gal ink x gal VOC ~ day
Ink B
5 gal ink x 0.270 oal VOC v 6.5 Ib VOC 8.8 Ib VOC
. day gal ink gal VOC ~ day
Ink C
10 gal jjik 0.220 oal VOC 6.5 Ib VOC 14.3 Ib VOC
day gal ink x gal VOC ~ day
. ; . Ink-D . .' = . " ^ _ ; "' •" . ''-."" . •
5 gal ink 0.900 oal VOC • 6.2 Ib VOC _ 27.9 Ib VOC
day gal ink x gal VOC ~ day
Ink E
5 gal ink -^0.895 oal VQC 6.0 Ib VOC 26.9 Ib VOC
day gal ink x gal VOC ~ day
Emissions from Press 4 _are?uncontrp;Lled.. Actual VOC emissions are
[21.0 + 8.8 + 14.3 + 27.9 + 26.9] = 98.9 Ib VOC/day.
Actual VOC emissions from all four presses are
[32.5 + 45.7 + 99.5 + 98.9] = 276.6 Ib VOC/day.
37
-------
ALLOWABLE VOC EMISSIONS
For this problem, allowable emissions for complying inks are determined by
calculating the gallons of ink used per day based on solids volume percent
of the ink and the allowed solids volume percent of the complying
fonnulation. By assuming that the VOC densities are the same, the
allowable VOC emissions can be calculated.
I.
Press 1
Ink A:
This ink is a high solids ink (65 volume percent) with 35
volume percent VOC and no water. A complying ink will
apply the same amount of solids but will contain a solids
volume percent of 60. The gallons of solids applied are
10 gal ink ^ 0.65 gal solids _
day
gal ink
6.5 gal solids
day
Hie amount of ink used with an exactly complying formulation applying
the same amount of solids would be
6.5 gal solids
day
x
1 gal ink
0.60 gal solids
10.83 gal ink
day
Assuming the VOC solvent density is the same, the allowable VOC
emissions are
10.83 gal ink 0.40 gal VOC 6.0 Ib VOC _ 26.0 Ib VOC
day x gal ink x gal VOC day
Ink B: This ink is a water-borne ink (53.0 volume percent) with
27.0 volume percent VOC and 20.0 volume percent solids.
Uncontrolled emissions are 17.6 Ib VOC/day.
Allowable VOC emissions are (17.6 Ib VOC/day) (1 - 0.65) = 6.2 Ib
VOC/day.
Ink C: This ink is a water-borne ink (68.0 volume percent) with
22.0 volume percent VOC and 10.0 volume percent solids. A
complying ink will contain the same volumetric amount of
solids; hence, the amount of ink used is the same.
However, the complying ink can have a higher VOC content as
follows:
Volatile portion = 1.0 - 0.1 = 0.90
VOC content = 0.25 x 0.90 = 0.225
38
-------
Assuming the VOC density is the same, the allowable VOC emissions
from the complying ink are
10 qal ink . 0.225 oal VOC 6.5 Ib VOC 14.6 Ib VOC
gal ink gal VOC T day
Ink D: This ink is a solvent-based ink (90.0 volume percent) with
2.5 volume percent water and 7.5 volume percent solids.
Uncontrolled emissions are 55.8 Ib VOC/day.
Allowable emissions are (55.8 Ib VOC/day) (1 - 0.65) = 19.5 Ib
VOC/day.
Ink E: This ink is a solvent-based ink (89.5 volume percent) with
10.5 volume percent solids and no water.
Uncontrolled emissions are 53.7 Ib VOC/day.
Allowable emissions are (53.7 Ib VOC/day) (1 - 0.65) = 18.8 Ib
VOC/day.
Allowable VOC emissions from Press 1 are (26.0 + 6.2 + 14 6 + 19 5
+18.8) = 85.1 Ib VOC/day.
II. Press 2
Ink C: The amount of ink used is the same, but the VOC content is
higher (22.5 volume percent). Assuming the same VOC
density, the VOC emissions from the complying ink are
5 oal ink x 0.225 oal VQC 6.5 Ib VOC 7.3 Ib VOC
day day x gal VOC ~ day
Ink D
Uncontrolled emissions are 167.4 Ib VOC/day.
Allowable emissions are (167.4 Ib VOC/day)(1 - 0.65) = 58.6 Ib
VOC/day.
Ink E " • . ' ; ." - •'•"• : •
Uncontrolled emissions are 53.7 Ib VOC/day.
Allowable emissions are (53.7 Ib VOC/day)(1 - 0.65) = 18.8 Ib
Allowable VOC emissions from Press 2 are (7.3 + 58.6 + 18.8) =
84.7 Ib VOC/day. ... . /
39
-------
III. Press 3
Ink A: A complying ink will apply the same amount of solids but
will contain a solids volume percent of 60. The gallons of
solids applied are
5 gal ink 0.65 gal solids
day x gal ink
3.25 gal solids
day
Hie amount of ink used with a corcplying formulation is
3.25 oal solids l oal ink _ 5.4 oal ink
day 0.60 gal solids day
Assuming the VOC density is the same, the allowable VOC emissions are
5.4 gal ink 0.40 gal VOC 6.0 Ib VOC
day x gal ink x gal VOC
13.0 Ib VOC
day
Ink B
Uncontrolled emissions are 26.3 Ib VOC/day.
Allowable emissions are (26.3 Ib VOC/day)(1 - 0.65) = 9.2 Ib
VOC/day.
Ink C: The amount of ink used is the same, but the VOC content is
higher (22.5 volume percent). Assuming the same VOC
density, the VOC emissions from the complying ink are
25 oal ink 0.225 oal VOC 6.5 Ib VOC
day x gal ink gal VOC
36.6 Ib VOC
day
Ink E
Uncontrolled emissions are 26.9 Ib VOC/day.
Allowable emissions are (26.9 Ib VOC/day) (1 - 0.65) = 9.4 Ib
VOC/day.
Allowable VOC emissions from Press 3 are (13.0 + 9.2 + 36.6 + 9.4) =
68.2 Ib VOC/day.
IV. Press 4
Ink A: A complying ink will apply the same amount of solids but
will contain a solids volume percent of 60. The gallons of
solids applied are
40
-------
10 oal ink 0.65 oal solids _ 6.5 oal solids
day gal ink ~ day
The amount of complying ink used is
ink
= 10.83 oal ink
6.5 oal solids 1 c
day x 0.60 gal solids ~ day
With the same VOC, the allowable VOC emissions are
10.83 oal ink x 0.40 oal VOC 6.0 Ib VOC _ 26.0 Ib VOC
day gal ink x gal VOC ~ day
Ink B " ".'• • : • '." '-. /. ~": '". ' • " ' . " ' - .
Uncontrolled emissions are 8.8 Ib VOC/day.
Allowable emissions are (8.8 Ib VOC/day) (1 - 0.65) =3.1 Ib VOC/day.
Ink C: The amount of ink used is the same, but the VOC content is
higher (22.5 volume percent). Assuming the same VOC
solvent density, the VOC emissions from the complying ink
> ,_ .-are . . . ..-''.'; .
10 aal ink ^ 0.225 oal VQC 6.5 Ib VOC 14.6 Ib VOC
-day gal ink x gal ink ~ day
Ink D
Uncontrolled emissions are 27.9 Ib VOC/day.
Allowable emissions are (27.9 Ib VOC/day)(1 - 0.65) = 9.8 Ib
VOC/day.
Ink E
Uncontrolled emissions are 26.9 Ib VOC/day.
Allowable emissions are (26.9 Ib VOC/day)(1 - 0.65) = 9.4 Ib
VOC/day. • '
Allowable VOC emissions from Press 4 are [26.0 + 3.1 + 14.6 + 98 +
9.4] = 62.9 Ib VOC/day.
Allowable VOC emissions from all four presses are
[85.1 + 84.7 + 68.2 +62.9] = 300.9 Ib VOC/day.
Compare total actual, VOC emissions to total allowable VOC emissions to
determine compliance under the bubble.
41
-------
Press
1
2
3
4
Total
Actual VOC
emissions,
Ib/day
32.5
45.7
99.5
98.9
276.6
Allowable VOC
emissions,
Ib/day
85.1
84.7
68.2
62.9
300.9
Since the total allowable VOC emissions are greater than the total actual
VOC emissions for this day, the plant is in compliance.
Example 2 -
A publication rotogravure facility has three presses. One press uses four
high VOC inks and has a carbon adsorber with a tested combined capture and
recovery efficiency of 78.0 percent. A second press uses two water-borne
inks and a high VOC ink. A third press uses five water-borne inks. The
second and third presses are uncontrolled. The volumes of inks used in a
24-hour period and the ink compositions from Reference Method 24A testing
and manufacturer's data are as follows:
Press
No.
1
2
3
Label
A
B
C
D
E
F
G
H
I
J
K
L
Amount
used,
gal/day
20
20
20
20
40
20
20
15
15
15
15
15
Composition, Vol. %
Solids
5.0
10.0
7.0
8.0
15.0
10.0
10.0
15.0
15.0
10.0
10.0
12.0
VOC
95.0
90.0
93.0
92.0
17.0
27.0
90.0
17.0
21.0
22.5
18.0
15.0
Water
0.0
0.0
0.0
0.0
68.0
63.0
0.0
68.0
64.0
67.5
72.0
73.0
Ink
density,
Ib/gal
7.21
7.98
7.10
7.64
8.94
8.43
7.80
8.94
8.95
8.52
8.58
8.83
Ink VOC
density,
Ib/gal*
6.8
7.2
6.5
7.0
6.0
6.2
7.0
6.0
6.5
6.2
6.0
6.3
*Ercm formulation and dilution data for press ready ink.
42
-------
Is the plant in compliance with the source specif ic SIP revision that
allows a daily bubble calculation to determine any credit due from the
dofference. between allowable and actual emissions for complying inks and a
VOC emission reduction requirement of 75 percent from noncomplying inks?
Actua^VOC emissions must be compared to allowable VOC emissions to
determine compliance. Inks E, H, I, J, K, and L are complying water-
based inks whose volatile fractions are at least 75 percent by volume
water and not more than 25 percent by volume VOC. In calculating the
allowable emissions, the VOC emissions from inks that meet the water-
based criteria exactly are included so that credit may be given for the
difference in allowable versus total actual emissions.
.-..-'• '• •".'•'• * ••• - - ' - • " '
Ihe calculations of actual and allowable VOC emissions are performed for
Inks A, F, and H to illustrate the procedure. P^ormea ror
ACTUAL VOC EMISSIONS
Ink A: Uncontrolled emissions are
20 gal ink 0;95 'gal VQC 6.8 Ib VOC 129.2 Ib VOC
day gal ink x gal VOC ~ day" ~
Ihe emissions are controlled by a carbon adsorber with an overall control
efficiency of 78 percent. Actual emissions are
129.2 Ib VOC
^
X (1 - 0.78)
T/nr-
VOC
Ink F: Uncontrolled emissions are ;
20 oal ink 0.27 oal VQC 6.2 Ib VOC 33 5 Ib VOC
x ~ "
day • gal ink x gal VOC ~ day
Since this press is uncontrolled, actual emissions are 33.5 Ib VOC/day.
Ink H: Uncontrolled emissions are
15 gal ink 0.17 oal VOC 6.0 Ib VOC _ 15.3 Ib VOC
day gal ink x gal VOC ~ day
Since this press is uncontrolled, actual emissions are 15.3 Ib VOC/day.
AIICWABtE VOC EMISSIONS
Ink A: Uncontrolled emissions are 129.2 Ib VOC/day. Required control is
75 percent. Allowable emissions are
129.2 Ib VOC __ 32.3 Ib VOC
day X (1 - 0.75) = - -
43
-------
Ink F: Uncontrolled emissions are 33.5 Ib VOC/day. Required control is
75 percent.
Assuming the VOC solvent density is the same for the two inks, the
allowable VOC emissions from this ink are
33.5 Ib VOC „ ,. n .7^ _ 8.4 Ib VOC
— x (1 - 0.75) - ^
Ink H: A complying water-based ink will contain the same volumetric
amount of solids; hence, the amount of ink used^ remains the
same. However, the complying ink will have a different
allowable VOC content as follows:
Volatile portion = 1 - 0.15 = 0.85.
VOC content = 0.25 x 0.85 = 0.213.
Assuming the VDC density is the same, the allowable VOC emissions from the
complying ink are
15 oal ink 0.213 oal VOC 6.0 Ib VOC _ 19.2 Ib VOC
day x gal ink gal VOC day
Ihe calculations for all inks are summarized in the following table.
44
-------
(
CM CM d CM H co H 'en" d d
nncocoincoScMcM
.>
CO COI H
• • •
o ol o
CM CM CM
1 CO
• - •• •
co TO in , if) o
* CM CM CM CM CM
• « • . .
o o o o o
in
Actual VOC
emissions,
Ib/day
r-H C
I 'OJ £H
S8
*fc -
•
-------
SECTION 7
AIITERNATE EMISSION IJMIT
Ihe U.S. EPA has developed an alternate emission limit applicable to
flexographic printing and packaging rotogravure printing presses which is
available to graphic arts sources through a SIP revision (See Appendix C). It
is particularly useful in emission trading calculations. Ihe alternate
emission limit of 0.5 pound of volatile organic compounds (VOC) per pound of
solids in the ink is essentially equivalent to the RACT limits recommended in
the CK3. Hie 0.5 Ib VOC/lb solids limit includes all VOC added to the ink:
VOC in the purchased ink, VOC added to cut the ink to achieve desired press
viscosity, and VOC added to ink on the press to maintain viscosity during the
press run.
Ihe following three examples show basic procedures for calculating
emissions using this proposed standard.
Example 1 -
A flexographic printer uses one gallon of an ink formulation on a press
with the following characteristics:
total VOC content = 25 weight percent (includes all additions)
solids content = 55 weight percent
water content = 20 weight percent
Does the printer comply with the 0.5 Ib VOC per Ib solids regulation?
Ib VOC _ 0.25 Ib VOC ^ 0.55 Ib solids
Ib ink
Ib solids
0.25 Ib VOC
Ib ink
0.45 Ib VOC
Ib solids
Since 0.45 Ib VOC/lb solids is less than 0.5 Ib VOC/lb solids, the
printer is in compliance.
46
-------
Example 2 - -
A_packaging rotogravure printer vises an ink formulation on two presses
with the foUowijig dharacteristics per gallon of ink:
Press A .'"•"''.!!'.,.'-''•.".' . •.-•' --•'".'-" •--.".'. ";,'.„..•
total VpC content of ink = 0.25 Ib/lb ink (press ready)
solids content of ink =0.50 Ib/lb ink
water content of ink =0.25 Ib/lb ink
dilution solvent added =0.20 Ib/lb ink
Press B
total VOC content of ink =0.15 Ib/lb ink
solids content of ink = 0.55 Ib/lb ink
water content of ink = 0.30 Ib/lb ink
solvent added during
press run = 0.10 Ib/lb ink
Determine the compliance status of each press. This sirrple example
demonstrates the concept. In a real case, several inks with varyina
compositions would be encountered.
Press A
The total amount of VOC used is
0.25 Ib VOC/lb ink + 0.20 lb VOC/lb ink = 0.45 lb VOC/lb ink
lb VOC __ 0.45 lb vor; _
lb solids 0.50 lb solids ~ °'90
Since 0.90 lb VOC/lb solids is greater than 0.50 lb VOC/lb solids
Press A is not in compliance.
Press B
the total amount of VOC used is
0.15 lb VOC/lb ink + 0.10 lb VOC/lb ink = 0.25 lb VOC/lb ink
lb VOC _ 0.25 lb VOC _
lb solids 0.55 lb solids ~ °'45
Iherefore, Press Bis in compliance.
47
-------
Example 3 -
A flexographic printer operates four presses. The printer wishes to
comply with the 0.5 Ib VOC per Ib solids regulation by bubbling the
plant's emissions on a 24-hour basis. The following table summarizes the
printer's formulations and ink and VOC amounts used on the four presses
for the 24-hour compliance period. The dilution solvents are 100 percent
VOC. Does the printer meet the regulatory emission limit based on a
source specific SIP revision allowing the bubble calculation?
Press
A
B
C
D
Total
VOC
content
of ink,
wt. %
10
50
15
-
Solids
content
of ink,
wt. %
70
50
25
80
Water
content
of ink,
wt. %
20
-
60
20
Ink
quantity
used,
gal
15
20
30
15
80
Dilution
solvent A
addition,
gal
-
10
5
-
15
Dilution
solvent B
addition,
gal
-
0
10
5
15
The following densities apply:
Ink - 7.40 Ib/gal
Dilution solvent A - 6.30 Ib/gal
Dilution solvent B - 7.10 Ib/gal
The first step in solving this problem is to calculate the total amounts of VOC
and solids used at the facility as follows:
Press A
m-4. n TW,
Total VOC
;0.10 Ib VOC. .7.40 Ib ink.
~~ l Ib ink ' ( gal ink '
= 11.1 Ib VOC
solids
, . w
gal inlc)
(« gal **,
= 77.7 Ib solids
48
-------
Press B
Total VOG
,0.50 Ib VOC. ,7.40 Ib ink
( Ib ink > ( ; gal ink > (2°
ink)
+ (10 gal dilution solvent) ( ., ' ^"l*3 VOC )
' vgal dilution solvent'
137 Ib VOC
total solids = (
v
solids .7.40 Ib ink
Press C
Ib ink ^ ("Sl ink"^ (20 ^al
74 Ib solids
(30
t (5 gal dilution solvent,
(10 gal dilution solvent) (
7 v
n
gal dilution solvent''
135.8 Ib VDC
Itotal solids - (°*25 **>. solids* ,7.40 Ib ink. .
V Ib mk ; ;< gal ink ' (3°
55.5 Ib VOC
D
-Itotal VOC ., .•. (
dilution solventV
-'•-••- - * — M .-*- - ^-*— - — — f
Ib solids gal dilution solvent
= 35.5 Ib VDC „
Itotal solids = (0-80 Ib^ida. 7.40 Ib ink
v Ib mk ;
40 nk . .
gal ink ' ( gal inlc'
= 88.8 Ib solids
Total VDC emitted from the four presses at the facility during the 24-hour
compliance period is:
11.1 Ib + 137 Ib + 135.8 Ib + 35.5 Ib = 319.4 Ib VOC
49
-------
Total solids applied on the four presses at the facility during the 24-
hour compliance period are:
77.7 Ib + 74 Ib + 55.5 Ib + 88.8 Ib = 296 Ib solids
Finally, the pound of VOC per pound of solids is calculated as follows:
Ib VOC 319.4 Ib VOC = 1.08 Ib VOC
Ib solids 296 Ib solids Ib solids
Therefore, the facility does not meet the emission limit by bubbling its
emissions over a 24-hour compliance period.
50
-------
APPENDIX A
PROCEDURES FOR CERTIFYING QUANTITY
OF VOIATIIE ORGANIC COMPOUNDS
EMITTED BY PAINT,
INK, AND OTHER COATINGS
A-l
-------
-------
United States Office of Air Quality
Protecti°n Planning and Standards
Researcn Triangle Park NC 27711
Agency
EPA-4.50/3-S4-J
December 19841
ures ior
• Quantity...of •"••• •
Volatile Organic
Compounds
JEmitted by Paint,
Inky and Other
Coatings
'Note: ; This copy -Includes the two revised
pages.
' y»VFV*<«fc»a-»jS: vVr*fi>:
-------
-------
EPA-450/3-84-019
Procedure for Certifying Quantity of
Volatile Organic Compounds Emitted
By Paint, Ink, and Other Coatings
Emission Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
; December 1984
-------
This report has been reviewed by the Emission Standards and Engineering 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. N.C. 27711, or
from the National Technical Information Services. 5285 Port Royal Road, Springfield. Virginia 22161.
II
-------
• • . PREFACE / -
_ , This manual was conceived as a way to provide simple step-by-step
]"structions for "certifying the quantity of volatil e organic compounds
(VOC) that will be released by a coating., It has not turned out that
way. The.guidance.is here, but in spite of great diligence, the
instructions remain imposing. /
m The manual-was prepared for several reasons. First, the coatings
industry, as represented by the National Paint and Coatings Association*
had requested a certification procedure which would relieve their custom-
ers the expense of analysis. Second, the complexity of the calculations
necessary to determine compl iance, for example, when dilution solvent is
added to a coating, continue to confound Federal, State and Local enforce-
ment personnel. Finally, results of a recent review of the Agency's
reference method for determining VOC reemphasized the importance of
analytical procedures to verify YOC content.'
In response to the results of the review of the test methods, this
manual reaffirms that Reference Method 24 or its constituent methods
developed by the American Society for Testing and Materials (ASTM)
are the procedures by which the VOC content of a coating will be deter-
mined for compliance with Federal regulations. The earliest guidance
was not so specific. In 1977, the first report1, written to assist
States in developing regulations for sources of VOC emissions, provided
recommendations for, the maximunv al 1 owable VOC content for complying
coatings in a variety of industries. These values were expressed in
mass of, VOC per unit volume of coating. In deriving the recommended
•limitation, the VOC'content of a coating was calculated based on the
solids content provided by the coating manufacturer. The Agency calcu-
lated the mass of YOC in the coating by assuming the VOC had a density
. of 7.36 pounds per gallon.
Solvent and VOC were used somewhat interchangebly even though it
was,recognized that orc.nics such as resin monomer, oligimers, and
reaction by-products co:ld be released by a coating during the cure.
There was no accepted analytical method available for measuring the
total VOC which would be released by a coating. The initial guidance1
provided an analytical method for use only'for air-dry coatings, those
where all VOC emissions would be expected to come as a result of evapor-
:-ation of solvent. On a volume basis, air dry coatings constituted the
largest catagory of coatings then in use. ; '•
*«. " ... " '
The Agency subsequently developed a more general analytical proce-
dure that could be used to determine the total VOC in a coating. On
October 3, 1980, the Agency published "Reference Method 24 (RM-24) -
1Control of Volatile Organic Emissions from Stationary Sources -
Volume II: Surface Caoting of Cans, Coils, Paper, Fabrics, Automobiles
and Light-duty Trucks, Document No. EPA-450/2-77-008.
111
-------
Determination of Volatile Matter Content, Density, Volume Solids and
Weight Solids of Surface Coatings," in the Federal Register (45 FR 65958)
For the first time the Agency formally specified an analytical method
for the VOC content of those coatings that cure by chemical reaction.
Even then, the announcement continued to allow the manufacturer's formu-
lation to be used to calculate the VOC content but specified that the
analytical technique, RM-24, wul d be the reference in any conflict
between the two.
*
During 1981 and 1982, as more State and Federal regulations were
established, the demand for low-solvent coatings began -a continuing
increase in the sales volume of reaction-cure coatings. There was some
concern voiced by the industry in how appropriate the reference method
was for these type coatings. To find out, the Agency began a review of
RM-24 to determine the effect of temperature and exposure time on the
indicated VOC "content". It was concluded that the maximum effect of
those time-temperature combinations that were examined amounted to only
about a 10 percent variation. Somewhat more surprising was that the
solvent sometimes accounted for only 50 to 70 percent of the total
VOC measured by the reference method.
The obvious conclusion was that RM-24 is a better measure of the
total organics freed by a coating than is the solvent. This manual
implements a policy based on that conclusion. Certification of VOC
content on the attached Data Sheets must be based on an analysis using
RM-24. No longer will solvent content be permitted as a surrogate for
VOC unless a showing is first made that its use is a reasonable alter-
native or equivalent method of determining the VOC content of that
particular coating.
* •
One final comment. Since VOC is not always synoncmous with solvent,
it follows that the amount of solids in a coating cannot be obtained by
subtracting the solvent from the total volume of coating. The original
Federal Registt • proposal for RM-24, published on October 3, 1980, recom-
mended the Amer:can Society of Test Materials test Number D2697 as the
appropriate metr.od or determining solids content. Subsequent comments
from the industry maintained that this test is unreliable. As a result,
when promulgated in 1980, RM-24 specified that the solids content of a
coating can be obtained only from the manufacturer's formulation of the
coating.
Dennis Grumpier
December 14, 1984
IV
-------
TABLE OF CONTENTS
CHAPTER
_'
Page
..PREFACE .... ....,,. ... . . .... . . .- . . - . ••"•• fii
GLOSSARY OF TERMS AND SYMBOLS .. . . ... . . ... . vi
1 INTRODUCTION .... . ' . ..;.... ... ../. . i_i
2 -VOC CONTENT OF PAINT, INK, AND OTHER COATINGS "
AS SUPPLIED" BY THE COATING MANUFACTURER ..... u-i
2.1 YOC DATA SHEET TOR "AS ..SUPPLIED" COATINGS .. . .11-2
2.2 IMPLEMENTING INSTRUCTIONS ... ...... . :. ., n-3'
3 VOC CONTENT OF PAINT, INK AND OTHER COATINGS ;
"AS APPLIED" TO THE SUBSTRATE BY THE USER . . . . . ni-i
; 3.1 VOC DATA SHEET. FOR "AS APPLIED" COATINGS ...... III-2
3.2 IMPLD^IENTING INSTRUCTIONS . . . .... .... . . "ni-4 ' '•
-------
GLOSSARY OF TERMS
"As Applied"
"As Supplied"
(Dc)a
w
(Vn)
(VOC)
(VOC)
(W0)
0s
the condition of a coating after dilution by the user
just prior to application to the substrate.
the condition of a coating before dilution, as sold
and delivered by the coating manufacturer to the user.
«
coating density "as applied"
coating density, "as supplied"
density of dilution solvent
density of organic solvent/water mixture.
density of water (8.33 Ib/gal)
dilution solvent ratio, equals the volume of VOC added
per unit volume of coating "as supplied"
equals the volume of premixed water and VuC added per
unit volume of coating "as supplied"
Volume percent solids of coating "as applied"
Volume percent solids of coating "as supplied"
VOC content of "as applied" coating, expressed as mass
of VOC per unit volume of coating less water .or as mass
of VUC per unit volume of solids
'OC content of "as supplied" coating, expressed as mass
of VOC per unit volume of coating less water or as mass
cf VOC per unit volume of solids
the water content, in volume percent, of coating "as applied"
the water content, in volume percent, of the dilution solvent
added to the "as supplied" coating . •
the water content, in volume percent, of tfie coating
"as supplied"
"he organic volatile content, in weight percent, of the
coaling "as applied"
the organic volatile content, in weight percent, of the
coating "as supplied"
VI
-------
(Wv)a
(Wv)s
(Ww>a
(Ww)d
the weight percent of total volatiles in the coatinq
as applied" a
the weight percent of total volatiles in the coatinq
"as supplied" : ; s
the weight percent water in the coating "as applied"
the weight percent water in the dilution solvent
the weight percent water in the coating "as supplied"
v.1 i
-------
-------
: 1. INTRODUCTION .'•••'•
procres 3peced
1-1
-------
-------
2. VOC CONTENT OF PAINT, INK AND OTHER COATINGS
"AS SUPPLIED" BY THE 'COATING 'MANUFACTURER TO THE USER
II-l .
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
VOC DATA SHEET:
PROPERTIES OF THE COATING "AS SUPPLIED" BY THE MANUFACTURER
Coating Manufacturer:
Coating Identification-^
Batch Identification:
Supplied To:
Properties of the coating as supplied! to the customer:
A. Coating Density (Dc)s : _ 1 b/gal _ kg/1
/~7 ASTM DH7b I~T Other2
B. Total Volatiles (Wv)s : _ Weight Percent
/ J ASTM D2369 I 7 Other2
C. Water Content: 1. (Ww)s _ Weight Percent
/ J ASTM D3792 / J ASTM D40L7 / 7 Other2
2. (Vw)s _ Volume Percent
I 7 Calculated I 7 Other?
u. Organic Volatiles (w0)s : _ Weight Percent
£. Nonvolatile* Content (Vn)s :
F. VOC Content (VOC)S: 1.
Volume Percent
1 b/gal coating less water
or
kg/1 coating less water
2.
1 b/gal solids
or
kg/1 solids
Remarks: (use reverse side)
iThe subscript "s" denotes each value is for the coating "as supplied"
by the manufacturer.
2£xplain the other method used under "Remarks".-
Signed:
Date
II-2 '
-------
2.2 IMPLEMENTING INSTRUCTinMS FOR THE~ VQC DATA SHFFT W^ SUPPLIED".
proviJed'tfthe'user I*
VUC DATA SHEET?
•A.
and Related Products."
g: manufacturer and •
be referred to as the "AS SUPPLIED
uy density, (Dc) 2, is determined using
Test Method for Density of Paint, Lacquer,
C. Water Content ~. ;
l°- -•il!«nH^2hl;rS?:J^a?r'u{Ww)s.. ^ determined by "ASTM D3792 - '
Water Content of Water-Reduciole Paints
."J>4 An acceptable alternative to these
of preparing the data sheet "would be to
formulation. "*"' percent watsr from.-the-Manufacturer's coating
fj
iHrM as havin9 negligible photochemical
* ,,1-tncnloroethane and methyl ene chloride etc *n<\
n.2 ass-i t-vi™nbe used in
II-3.
-------
2. The water content, in volume percent, (Yw)s, can be calculated
by the equation:
(YW):
where Dw is the density of water, 8.33 Ibs/gal.
The organic volatiles content, (W0)s, i.e., the VOC content
expressed as a percent by weight, is determined by the following
equation^:
(W0)s = (Wv)s - (Ww)s
If the coating contains no water the weight percent of organic
•volatiles is equal to the weight percent of total voUtiles.
In other words:
(Ww)s = 0 and
(W0)5 = (Wv)
v's
II-l
II-2
The volume percent solids (nonvolatil es), (Vn)s, should be derived
from the coating formulation using the following equation:
11-3
(vn)s = L=i (vn)s.
where (Vn)s.denotes the volume percent of each
nonvolatile component in an "as supplied" coating,
and "p" is the number of nonvolatile components in
that coating. (Also see Footnote 1, Pg. II-3.)
11-4
e precision limit adjustments permitted by Reference Method 24 for
experimentally determined mean Ww and Wv values may be made only by
enforcement agencies tor determination of compliance. Jhe( «^|^ent
•is not to be used for the purposes of completing the AS SUPPLIED
WC~BATA SHEET.
11-4
-------
F.
The VOC content of the "as supplied" coating (YOC)S can now be calculated
and thereby expressed in'terms used by most State or Federal regulations.
1. The mass of VOC per unit volume of coating less water: •.
» ' ' - •'-.••
a. If the coating contains no water, the equation is calculated
as follows:
(vocr
b. If the coating contains water, Equation 11-5 becomes:
II-5
2.
fvnn. = •l"o/s uc s n-6
The VOC content may also be calculated in terms of mass of VOC per
unit volume of solids (nonvolatiles). For both solvent-borne and
waterborne coatings, the equation is:
II-7
.11-5 .
-------
-------
3. VOC CONTENT OF PAINT, INK AND OTHER COATINGS
"AS APPLIED" TO THE SUBSTRATE; BY THE USER-. ' '
III-l
-------
'-«,*o^
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
VOC DATA SHEET:
PROPERTIES OF THE COATING "AS APPLIED" TO THE SUBSTRATE
Coating Manufacturer:
Coating Identification:
Batch Identification:
User:
User's Coating Identification:
Properties of the coating as applied1 by the User:
A. Coating Density (Dc)a: kg/1, or
I~~J ASTM D1475 f~~T Other2
B. Total Volatiles (Wv)a:
I 7 ASTM D2369 /~7 Other2
C. Water Content: 1. (Ww)a
/—7 ASTM D3792 f~7 ASTM D4017 f~~T Other2
2. (Vw)a
I 7 Calculated /7 Other2
Ib/gal
Weiaht Percent
Weight Percent
Volume Percent
3.
D. Weighted Average Density of the dilution solvent (Dd)°:
/7 ASTM D1475 /7 Handbook I 7 Formulation
Ib/gal
(Continued on Reverse Side)
iThe subscript "a" denotes each value is for the coating "as applied" to the
substrate.
2Explain the other method used under "Remarks" on reverse side
3The subscript "d" denotes values are for the dilution solvent
III-2
-------
E.
F.
G.
H.
DiTiitiori Solvent Ratio (Rd):
Organic Volatiles Content5 (W ) :
o a
Non-Volatile^ Content (Vn)a:
VOC Content (VOC)a: 1.
REMARKS:
or
2.
or
gal diluent
(gal coating)
or
liter diluent
(liter coating) 4
Weight Percent
' ••
Volume Percent
Ib/gal of coating less water
kg/1 of coating less water -
Ib/gal solids
kg/1 solids '
Signed:
Date:
S" den0t" valu« ^ f°' the coating "as supplied'^ the
TII-3
-------
PAGE REVISED JUNE 19, 1986
3.2. IMPLEMENTING INSTRUCTIONS FOR THE VOC DATA SHEET FOR "AS APPLIED" COATINGS
This DATA SHEET, henceforth referred to as the "AS APPLIED" VOC DATA
SHEET, is to be completed by the company which applies a coating. It
provides information on the amount of volatile organic compounds (VOC) in
the coating "as applied" to the substrate by accounting for the quantity of
diluent solvent added to the "as supplied" coating prior to application.
If a coating is diluted only with water or a solvent of negligible photo-
chemical reactivity, the user merely doucments the fact (see Step E.I. and
also Footnote 4, Pg. III-5.). Otherwise, several avenues exist for the t
coater to certify the VOC content:
(1) Maintain adequate records of how much organic solvent is added to each
coating and use that information and the "AS SUPPLIED" VOC DATA SHEET? to
calculate the VOC content "as applied." In this case begin with Step D.
(2) If the "AS SUPPLIED" DATA SHEET is available, but dilution records are
not, begin the "As Applied" determination with Step A, skip Steps B and C,
and proceed to Step D.
(The" user may choose to analyze an "As Supplied" coating using Reference
Method 24 and complete the "AS SUPPLIED" VOC DATA SHEET rather than have
the coating manufacturer complete it. The volume percent solids, however,
will necessarily continue to be supplied by the coating manufacturer.)
(3) Analyze each diluted coating with the same method used to generate the
data provided by the coating manufacturer on the "AS SUPPLIED" VOC DATA
SHEET. (See Chapter 2 of this Manual.) In this case begin with Step A.1
A. The "as applied" coating density, (Dc)a2, is determined using "ASTM D1475-
Standard Test Method for Density of Paint, Lacquer, and Related Products.
B. The weight percent of total volatiles in the coating, (Wv)a is determined
by "ASTM D2369-81 Standard Method for Volatile Content of Coatings."
The drying conditions to be used are 11U°C for 1 hour3.
iEPA's Reference Method 24 (40 C.F.R. Part 60, App. A), contains the
ASTM methods'referenced in these instructions.
2The subscript "a" denotes those parameters of a coating in the
"as applied" condition, i.e., after dilution by the user. The subscript
"s" denotes the parameters of a coating in the "as supplied" condition,
before dilution by the user.
3If the manufacturer believes the specified method gives results that
are not representative of the VOC released during the normal cure, he
may petition the enforcement authority for approval of an alternative
analytical method. Any alternate method or alteration to the methods
and procedures in these instructions or in any applicable regulation
would be subject to review and approval by the appropriate State and/or
Federal enforcement agency.
III-4
-------
c.
The water content is necessary only if the coating-has' been '.diluted '
with a mixture of organic solvent and water.*, 5 if the dilution
solvent is lUO^percent organic, or If the weight and volume percent
water in the mixture is known, proceed directly to Step D.
The weight percent water, (Ww)a, is detennined by "AVTM u3792 -
Standard Test Method for Water Content of Water-Reducible
Paints by Direct Injection Into a Gas Chroma tograph," or "ASTM D4017
>h« v nd?rd T6;^ Method for Water in Paints and Paint Materials by
the Karl Fischer Method." (Also see Footnote 3, Pg. III-4. )
the
Volume Percent>
can be calculated by
(Vw),
w
where Uw is the density of water, 8.33 Ib/gal.
^Volatile compounds-classified by EPA as having negl igible photochemical
reactivity such as 1,1 ,1-trichloroethane and methyl enl chloride, ale and
ilSt^af /Xe'"^ ln the 3ppl1cable Federal dnd State Vuc regulation, should
be treated in the same manner as water. The weight percent of negliqiblv
reactive compounds in the dilution solvent must be known either from the
coaters mixing records or the dilution solvent supplier's formulation
The volume percent can then be calculated using Equations lll-t or III-5
.when the weight percent and density of the negligibly reactive organics
are suostituted for those of water. The- weight and volume percent Sf
the negligibly reactive compounds can be substituted in all equations
where the weight and volume percent water, (Ww) and .(Vw), respectively,
clPS US60* - B
The precision limit adjustments permitted by Reference Method 24 for
experimentally determined mean wei ght percent water and tptal vol ati 1 es ,
ww and ,JV respectively, may be made only by enforcement agencies for
determination of compliance. The adjustment is not to be used for the
purposes of completing the "AS APPLIED" VUC UATA~SHtET.
III-5
-------
D. If the dilution solvent consists of a single compound the density
may be obtained from the literature.
If the dilution solvent is a mixture of organic compounds, the
density, D^, can be determined analytically via ASTM U1475, or
an average density can be estimated from the solvent formulation
as shown below. This estimation assumes that volumes are additive.
100%
m
111-2
or
= 1 E VJUJ HI-3
luu* j=i
where: Dj, W ,•, and V-j denote the density, weight percent,
and volume percent or each solvent in the dilution solvent
mixture and "m" is the number of organic solvents in the
dilution solvent mixture.
If the dilution solvent is a mixture of photocnemically reactive
organics and water, the coater must know the weight percent, (Ww)d,
or volume percent, (Vw)d, of water from his mixing records or the
supplier's formulation, or he must analytically determine the weight
fraction of water in the dilution solvent using ASTM D3792 or ASTM
D4017. The density, L)d, of the dilution solvent may then be deter-
mined by analytically measuring the density of the organic solvent/
water mixture, Ddt, using ASTM U1475 and adjusting it for the water
content using the following equation. (See also Footnote 4, Pg. II1-5.
= °d
t [100% - (Ww)dl
III-4
- (Vw)dj
Note: If either the weight or volume percent water in the
dilution solvent is known, the other can be calculated by the
equation:
ni-5
'w
where "Dw" is the density of water.
6The subscript "d" denotes a parameter that pertains to that solvent
used by the coater to dilute the "as supplied" coating.
III-6
-------
E.
-R
1.
Vo1ume Photochemical^ reactive dilution solvent.
Volume or "as supplied" coating
2.
,
In the absence of adequate dilution records, Rd can be
s °" the voc UATA d"
,b.
a. When the dilution solvent consists only of VQC,
• d. 77!t 7—r 1 ' • ' . -
II1-6
.the dilution solvent is a mixture of water and
'orsanic so1
111-7
fo see
RHf "fl - (Vw)
-------
F. The organic volatile content (W0)a, I.e. the VOC content expressed
as a percent by weight of the diluted coating, can now be calculated
by either of two ways:
1. From analyses of the coating using the following equation:
(W0)a " a * (Ww}a
(See Footnotes 4 and 5, Pg. III-5.)
If the coating does not contain water, the weight percent of
organic volatiles is equal to the weight percent of total
volatiles, or
(W0)a = (Wv)
I1I-9
v'a
III-1G
2. By using the data from the "AS SUPPLIED" VOC DATA SHEET, the
dilution solvent ratio, and the density of the dilution solvent
with the following equation:
(W0)a -
_ C(DC)S (M0)s/100%] + (RdOd)
III-L1
G. The volume percent solids, or nonvolatiles, (Vn)a, must be calculated
from the following equation where (Vn)s is obtained from the "AS
SUPPLIED" VOC DATA SHEET.
111-12
TTT
H. The VOC content of the "as applied" coating (VOC)a, can now be
calculated and thereby expressed in terms used in most State or Federal
regulations.
1. The mass of VOC per unit volume of coating, less water, is
calculated in either of two ways.
a. Using the results obtained by analyzing-the coating with EPA
Reference Method 24 or its constituent ASTM Methods:
(1). If the coating contains no water the equation is:
(VOC,a -
a
111-13
iuo
III-8
-------
PAGE REVISED JUNE 19, 1986
(2"). If the'coating contains water the following equation
• must be used: _-, ,
rvnr?d
111-14
^1ng the VOC content of the "as supplied" coating, (VOCC )
the dilution solvent ratio, and the density of the solvent
the equation is: '
(RdDd)
ni_15
•• r Where ,(VOC)S in this case must be in units of
Ibs VOC/gal .coating less water.
2. The VOC content may also be calculated in terms of mass of VOC '
per unit volume of solids (nonvolatiles).
-.a. Using the results obtained by-analyzing the coating with EPA
.., Reference Method 24 or its constituent ASTM methods,
. .the equation for both solvent-borne and waterborne coatings,
1 5 • • * • • .-.-.-,.'-.- " -'-,--".---='
• (V }
, - -V-.n'-
111-16
•b.
'Using dilution information and calculation procedures only
the- equation is: . " . J>
; {voc) ;.-
•
C(voc)
(Vn)s/l.UU%
Where (VOC.) 5 in this case must be in units of
Ibs VOC/ gal coating less water.
II1-9
-------
TECHNICAL REPORT DATA 1
(Please read Insmtcrions on (he reverse before completing) |
1. REPORT NO.
EPA 450/3-84-019
2.
4. TITLE AND SUBTITLE
Procedures for Certifying Quantity of Volatile Organic
Compounds Emitted by Paint, Ink, and Other Coatings
7. AUTHOR(S)
9. PERFORMING ORGANIZATION NAME AND AOORESS
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency (MD-13)
Research Triangle Park, NC 27711
12. SPONSORING AGENCY NAME AND ADDRESS
3. RECIPIENT'S ACCESSION NO. I
5. REPORT DATE
December 1984
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT N
10. PROGRAM ELEMENT NO.
t
11. CONTRACT/GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERS
14. SPONSORING AGENCY CODE
EPA/ 200/04
15. SUPPLEMENTARY NOTES
16, ABSTRACT
This manual provides procedures by which firms may voluntarily
certify the. quantity of volatile organic compounds which will be emitted
by a paint, ink, or other coating. Two data sheets are provided. One
is to be used by the manufacturer of the coating, the other by the user.
Analytical test methods and procedures for preparing the data sheets are
included, as are the equations and instructions necessary to convert the
analytical results into a format suitable for determining compliance with
State or Federal regulations.
17. KEY WOROS AND DOCUMENT ANALYSIS ~~
a. DESCRIPTORS
Air Pollution
Coatings
Compliance Calculations
Pollution Control
Reference Method 24
Test Methods
Volatile Organic Compounds
18. DISTRIBUTION STATEMENT
b.lOENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
19. SECURITY CLASS (This Report )
Unclassified
2O. SECURITY CLASS (This page)
Unclassified
c. COSATI Field/Grou
13-B
21. NO. OF PAGES
15
22. PRICE
IPA Fo»m 2220—1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
-------
APPENDIX B
EPA REFERENCE TEST METHOD 24
EPA REFERENCE TEST METHOD 24A
B-l
-------
M-Aod 14—DataoBlaatioai of Volatile Matter
Content Water Content. Dan»ity, Volume ,17
ioUd*. and Weight Solids of Surface Coating.
I. Applicability and Principle
11 Applicability. This method applies to
the determination of volatile matter content.
water content density, volume solids, and
weight solids of paint varnish, lacquer, or
related surface coatings.
1,2 Principle. Standard methods are used
to determine the volatile matter content
water content density, volume solids, and
weight solid* of the paint varnish, lacquer, or
related surface coatings.
Z Applicable Standard Methods
Us« the apparatus, reagents, and
procedures specified in the standard methods
tl" ASTMD1475-60(Reapproved 1980).
Standard Test Method for Density of Paint
Varnish. Lacquer, and Related Products
(incorporated by reference—see i 60.17).'"
ZZ ASTM D2369-8I. Standard Test
Method for Volatile Content of Coatings
(incorporated by reference—see S 60.17J.I"
2.3 ASTM D3792-79. Standard Test
Method for Water Content of Water-
Reducible Paints by Direct Injection into a
Cat Chromatograph (incorporated by
reference—see i 60.17).177
2.4 ASTM D4017-81. Standard Test
Method for Water in Paints and Paint
Materials by the Karl Fischer Titration
Method (incorporated by reference—see
I6017J.177
3. Procedure.
31 Volatile Matter Content. Use the
procedure in ASTM D2369-61 (incorporated
by reference—see 5 60.17) to determine the
volatile matter content (may include water)
of the coating. Record the following
information;!77
W,-Weigh I of dish and sample before
heating, g. ..
W,-Weight of dish and sample after healing.
W.-Sample weight, g.
Run analyses in pairs (duplicate sets) for
each coating until the criterion in section 4.3
i. met. Calculate the weight fraction of the
volatile matter (W.) for each analysis as
follows:
using the procedure in ASTM D1475-60
(Reapproved 1960) (incorporated by
reference—e-e i 60.17).
Run duplicate set* of determinations for
each coating until the criterion in section 4.3
is met. Record the arithmetic average PJ. 1/7
3.4 Solids Content Determine Ae volume
fraction (VJ solids of the coating by
calculation using the manufacturer s
formulation.
4. Data Validation Procedure
4.1 Summary. The variety of coatings that
may be subject to analysis makes it
necessary to verify the ability of the analyst
end the analytical procedures to obtain
reproducible results for the coatings tested.
This is done by running duplicate analyse* on
each sample tested and comparing result.
with the within-laboratory precision
•tatements for each parameter. Because of
the inherent increased imprecision in the
determination of the VOC content of
waterbome coatings as the weight percent
water increases. nwMured parameters for
waterbome coatings are modified by the
appropriate confidence Hmits based on
between-laboratory precision statements.
4.2 Aiwrytioal Precision Statements. The
wtthi»4eboretory and between-laboratory
precision statements are given below:
*h» to it. volatile *«*™.*
duplicate setTof determination, until *e
criterion in .action « is met. Record the
arithmetic average IW.J- 1"
JUi Coating Density. Determine the
Oenfity (0 Jk*»ter) of the surface coaling
adjustment for the parameter.
S. Calculations
5.1 Nonaqueous Volatile Matter.
5.1.1 Solvent-bom* Coatings.
W.-W. Eq. 24-4
Where:
W.=Weight fraction nonaqoeous volatile
matter, g/g.
5.1.2 Waterbome Coatings.
W.=W,-W, Eq.24-3
5.2 Weight fraction solids.
W.=1-W, Eq.Z4-«
Where: W.=Weight eolids, g/g.
_
-- w,
Eq24-1177
lUcord th« arithmetic average (W.).
Mi Water Content. For waterbome (water
reducible) coatings only, determine the
weight fraction of water (w) using «>*« .
••Stindard Content Method Test for Water of
W^fMudU. PainU by Dire* flection
Mo . Cas Chromatograph" "'fStandard
Test Method foe Water in P tint and Paint
Materials by Karl Fischer Method. (These
& mefeod. «e incorporated by »««**-
•ee 1 60.17.) A waterbome coating is any
which contains more than 5 percent
™.**
Wtttwv
Wxxmlwy
(•boraury
votau. »»«•'«—«. W- « ** *•
4 3 Sample Analysis Criteria. For W, and
W^ ron duplicate analyses until the
difference between the two values in a set H
less than or equal to the within-laboratory
precision statement for that parameter. For D,
run duplicate analyses until each value in a
set deviates from the mean of the set by no
more than the within-laboratory precision
statement If after several attempt, it is
concluded that the ASTM procedures cannot
be used for the specific coating with the
established within-laboratory precision, the
Administrator will assame respoiuribility for
providing the necessary procedures for
revising the method or precision statements
upon written request to: Director. Emission
Standard* and Engineering DivwJoo. (MD-13)
Office of Air Qmality Planning and Standards,
U.S. Environmental Protection Agency.
Re*Mrct> Triangle Park. North CWO&M
27711.
4.4
WateroM oa.
laboratary fMcMoa »UUi»i»i*s. csJcatate the
confidence limit, for waterbome coatings a*
°To calculate the lower confidence limit
subtract the appropriate between-Jaboratory
precision value from the measured mean
Value for that parameter. To c"^"^**,
Bpoer confidence limit add the appropirat*
b5ween4abor«tory precision value to the
oMMured im«n value for that parameter. For
W, «nd D. oa. th. low« <>onftd«« Itait..
. WM *• *W« conBaence
v7tooalaU.tad.thar. to «o
B-2
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Matbod 24A—D«torraination of Volatile
Matter Content and Density of Printing Inks
«od Related Coatings'69
1. Applicability and Principle.
• 1.1 Applicability. This method applies to
the determination of the volatile organic
compound (VOC) content and density of
solvent-borne (solvent reducible) printing
inks or related coatings.
1.2 Principle. Separate procedures are
used to determine the VOC weight fraction
and density of the coating and the density of
the solvent in the coating. The VOC weight
fraction is determined by measuring the
weight loss of a known sample quantity
which has been heated for a specified length
of time at a specified temperature. The
density of both the coating and solvent are
measured by a standard procedure. From this
information, the VOC volume fraction is
calculated.
2. Procedure.
2.1 Weight Fraction VOC.
2.1.1 Apparatus. .
2.1.1.1 Weighing Dishes. Aluminum foil,
58 mm in diameter by 18 mm high, with a flat
bottom. There must be at least three weighing
dishes per sample.
2.1.1.2 Disposable syringe, 5 ml.
2.1.1.3 Analytical Balance. To measure to
within 0.1 mg.
2.1.1.4 Oven. Vacuum oven capable of
maintaining a temperature of 120±2"C and
an absolute pressure of 510 ±51 mm Hg for 4
hours. Alternatively, a forced draft oven
capable of maintaining a temperature of 120
±2'C for 24 hours.
2.1.1.5 Analysis. Shake or mix the sample
thoroughly to assure that all the solids are
completely suspended. Label and weigh to
the nearest 0.1 mg a weighing dish and record
thi* weight (Mu).
Using • 5-ml syringe without a needla
remove • sample of the coating. Weigh the
syringe and sample to the nearest 0.1 mg and
record thi* weight (MeYI). Transfer 1 to 3 g of
the sample to the tared weighing dish.
Reweigh the syringe arid sample to the
nearest 0.1 mg and record this weight (Mcyz).
Heat the weighing dish and sample in a
vacuum oven at an absolute pressure of 510
±51 mm Hg and a temperature of 120 ±2'C
for 4 hours. Alternatively, heat the weighing
dish and sample in a forced draft oven at a
temperature of 120 ±2*C for 24 hours. After
the weighing dish has cooled, reweigh it to
the' nearest 0.1 mg and record the weight
(Mrf). Repeat this procedure for a total of
three determinations for each sample.
2.2 Coating Density. Determine the
density of the ink or related coating
according to the procedure outlined in ASTM
D1475-60 (Reapproved .1980), which is
incorporated by reference. It is available
from the American Society of Testing and
Materials, 1916 Race Street, Philadelphia.
Pennsylvania 19103. It is also available for
Inspection at the Office of the Federal
Register, Room 8401.1100 L Street. NW.,
Washington, D.C. This incorporation by
reference was approved by the Director of
the Federal Register on November 8V 1982.
This material is incorporated as it exists on
the date of approval and a notice of any
change in these materials will be published in
the Federal Register.
2.3 Solvent Density. Determine the
density of the solvent according to the
procedure outlined in ASTM D 1475-60
(reapproved 1980). Make a total of three
determinations for each coating. Report the
density D. as the arithmetic average of the
three determinations. '76
3. Calculations.
3.1 Weight Fraction VOC. Calculate the
weight fraction volatile organic content W.
using the following equation:
W.=
,i + McVi -
Equation 24A-1
176
Report the weight fraction VOC w",, as the
arithmetic average of the three
determinations.
3.2 Volume Fraction VOC. Calculate the
volume fraction volatile organic content V0
using the following equation:
Equation 24A-2
176
4. Bibliography.
4.1 Standard Test Method for Density of
Paint, Varnish. Lacquer, and Related
Products. ASTM Designation D 1475-60
(Reapproved 1980).
4.2 Teleconversation. Wright, Chuck,
Inmont Corporation with Reich, R. A., Radian
Corporation. September 25,1979. Gravure Ink
Analysis. .
4.3 Teleconversation. Oppenheimer,
Robert Gravure Research Institute with Hurt.
Rick, Radian Corporation, November 5.1979.
Gravure Ink Analysis.
B-3
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APPENDIX C
AlfTERNftTIVECCMPI^IANCE FOR GRAPHIC ARTS RACT
C-l
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
SEP 9 1987
MEMORANDUM
SUBJECT. Alternative
FROM:
TO:
Compliance for ffraonic ArtsXKACT
Darryl D. Tyler, Director
Control Programs DevelopmeW^ bTvj^dn (MD-15)
.Director, Air Division, Regions I-X
• As an outgrowth of comments on simplifying recordkeeping and determining
compliance in the flexographic and packaging rotogravure printing industries,
the Agency has decided to accept an emission limit of 0.5 Ib of volatile
organic compound (VOC) per pound of solids in the ink as alternative
emission limit which is essentially equivalent to the reasonably available
control technology (RACT) level recommended in the graphic arts control
technique guideline (CTG), "Control of Volatile Organic Emissions From
Existing Sources Volume VIII: Graphic Arts, Rotogravure, and Flexography,"
EPA-450/2-78-033, December 1978. A source-specific State implementation
plan (SIP) revision for a graphic arts facility which is based on this
equivalent alternative RACT emission limit will be considered valid and
will be expeditiously reviewed.
Rather than applying this limit on a source-specific basis', a State
may wish to revise its SIP to apply this alternative limit to all
affected sources so that there will be no need for a source-specific SIP
revision for each particular industrial facility. Such an approach will
be acceptable to EPA.
• However, States are not required to revise SIP's and adopt the 0.5 Ib
VOC/lb solids RACT equivalent. The EPA still considers the RACT limitations
recommended in the CTG and already incorporated into most SIP's to be
valid and does not propose to prohibit their use. If a State chooses to
revise its SIP to apply the 0.5 Ib VOC/lb solids RACT equivalent to all
sources, this should be as an alternative in addition to, rather than as a
replacement for, the RACT limitations recommended in the CTG and already
incorporated into most SIP's.
The 0.5 Ib VOC/lb solids limit includes all solvent added to the ink:
solvent in purchased ink, solvent added to cut the ink to achieve desired
press viscosity, and solvent added to ink on the press to maintain viscosity
during the press run. Method 24 test procedures and procedures to account
for thinning solvent as specified in "Procedures for Certifying Quantity
of Volatile Organic Compounds by Paint, Ink, and Other Coatings", EPA
450/3-84-019, must govern in determining VOC compliance of an ink in an
enforcement situation.
-------
" . &=.. . .'...:. . ' ','.-_'. . ' - '" - '*--': , " .
This limit applies to flexographic printing and packaging rotogravure
printing presses. Publication rotogravure presses are not covered by
tnis guidance. . J , . .
cc:
Regional Administrator, Regions I-X
Chief, Air Branch, Regions I-X
Ron Campbell
Gerald Eraison
B. J. Steigerwald .
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1.
-88-004
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLtAND SUBTITLE .
A Guideline for Graphic Arts Calculations
5. REPORT DATE
June 1988
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
3830-108
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
PEI Associates, Inc.
1006 N. Bowen Road
Arlington, Texas 76012
11. CONTRACT/GRANT NO.
68-02-3963
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Stationary Source Compliance Division
Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Contact: Vishnu
Washington, DC 20460
Katari/Linda Lay, TSB, SSCD
Telephone: 202/382-2848
16. ABSTRACT
The calculation of volatile organic compound emissions from graphic
arts operations to determine compliance is often a complicated task, some-
times creating confusion with compliance authorities and sources alike.
In an attempt to minimize this confusion, EPA (OAQPS) has periodically issued
guidance in this area, generally in the form of memoranda to the EPA Regional
Offices. EPA guidance for submitting data on ink formulations and performing
basic calculations is contained in the document entitled "Procedures for
Certifying Quantity of Volatile Organic Compounds Emitted by Paint, Ink and
Other Coatings," EPA 450/3-84-019, published in December 1984. On June 19,
1985, two pages, III-4 and III-9, were revised and issued.
"A Guideline for Graphic Arts Calculations" takes the above guidance
process one step further. Example calculations are included for basic
emission problems, compliance determinations, control strategy problems,
and complex emission problems.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air Pollution
Inks
Compliance Calculations
Pollution Control
Rotogravure Printing
Flexographic Printing
Graphic Arts Calculation
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report)
Uncl assified
21. NO. OF PAGES
44
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Fwm 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
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