oEPA
             United States
             Environmental Protection
             Agency
             Air Pollution Training Institute
             MD20
             Environmental Research Center
             Research Triangle Park NC 27711
             Air
APTI
Course 482
Sources  and Control
of Volatile Organic
Air  Pollutants
EPA 450/2-81-011
March 1981

             Student Workbook

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United States
Environmental Protection
Agency
Air Pollution Training institute
MD20
Environmental Research Center
Research Triangle Park NC 27711
EPA 450/2-81-011
March 1981
Air
APTI
Course  482
Sources  and  Control
of  Volatile  Organic
Air Pollutants

Student  Workbook
Technical Content By:

J.A. Jahnke, PhD.
D.S. Beachler
J.T. Joseph
J.E. Maroney
Northrop Services, Inc.
P.O. Box 12313
Research Triangle Park. !\!C 27709
Under EPA Contract No.
68-02-2374
EPA Project Officer
R.E. Townsend

United States Environmental Protect'on Agency
Manpower and Technical Infoimation Branch
Office of Air Quality Planning and Standards
Research Triangle ParK, NC 27711

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                                    Notice
This is not an official policy and standards document. The opinions and selections are
those of the authors and not necessarily those of the Environmental Protection
Agency. Every attempt has been made to represent the present state of the art as well
as subject areas still under evaluation. Any mention of products or organizations does
not constitute endorsement by the United States Environmental Protection  Agency.
                                 Availability
 This document is issued by the Manpower and Technical Information Branch, Con-
 trol Programs Development Division, Office of Air Quality Planning and Standards,
 USEPA. It was developed for use in training courses presented by the EPA Air Pollu-
 tion Training Institute and oth  r  Deceiving contractual or grant support from  the
 Institute. Other organizations are welcome to use the document.
 This publication is available, free of charge, to schools or governmental ail pollution
 control agencies intending to conduct a training course on the subject covered. Submit
 a written request to the Air Pollution Training  Institute. USEPA, MD-?0, Research
 Triangle Park, NC 27711.
 Others may obtain copies, for a fee, from the National Technical Information Service
 (NTIS), 5825 Port Royal Road,  Springfield, VA 22161.
 Sets of slides and films designed for use in the training course of which this publication
 is a part may be borrowed from the Air Pollution Training Institute upon written
 request. The slides may be freely copied. Some films may be copied; others must be
 purchased from the commercial distributor.
                                          it

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                          Course Description

This course is designed for engineers and other technical personnel who are respon-
sible for the development and implementation of programs dealing with the control
of organic air pollutants.  The course  emphasis is focused on the source categories
contributing major amounts of volatile organic pollutants into the atmosphere.
Details of process operation and methods of controlling these emissions through
process, or design changes such as alternate uses of materials, will be discussed.
The specific application of techniques such as scrubbing, condensation and
incineration, used  to control organic emissions, will also be reviewed. The relation-
ship between organic materials and the problem of photochemical oxidants will be
discussed with regard to regulatory programs. The development of emission inven-
tories for sources of organic air pollutants and examples of control plans developed
for inclusion in State Implementation Plans will be examined within the context of
the other subject matter of the course.
  EPA technical guidance documents for the control of VOC emissions from
specific  source categories will be discussed.  Approximately one-third of the course
will deal with the regulatory problems of emission inventories, measurement, and
surveillance.  One-third of the  course will concern the description of VOC problems
associated with source  categories addressed in the EPA technical guidance
documents for VOC control. The remaining third of the course will address control
methods for VOCs through the application of design or process changes or the use
of control equipment.

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                   How  to Use  This  Workbook

This workbook is to be used during the course offering. It contains a chapter cor
responding to each of the eighteen lessons and a chapter containing two problem
sets.
  Each chapier contains  a listing of the lesson goal, the lesson objectives, and any
special references that might be helpful to you.  Each chapter also contains several
pages of black-and-white line-art reproductions  of selected lecture slides. These
reproductions are intended to generally follow the slide presentations ^iven in the
lecture. However, the instructor may on occasion change the order or present new
material not included in the workbook. It is therefore recommended that the stu
dent take notes throughout the course and not rely on the  graphic reproductions as
representing the total course cc.ui.~-nt.
  Space is provided for note-taking in each chapter of the workbook.

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                         Table of Contents


                                                                       Page
Chapter 1
  Introduction
  Course Objectives and Overview	1-1
Chapter 2
  Regulatory Review	2-1
Chapter 3
  Organic Chemistry Review	3-1
Chapter 4
  VOC Emission Measuring Techniques	4-1
Chapter 5
  VOC Emissions from Industrial Surface Coating Operations	5-1
Chapter 6
  VOC Emissions from Coil Coating Operations	6-1
Chapter 7
  VOCs and Photochemical Oxidants	7-1
Chapter 8
  VOC Emissions from Degreasing Operations	8-1
Chapter 9
  VOC Emissions from Petroleum Refineries	9-1
Chapter  10
  Operation-Maintenance-Inspection—Petroleum  Refinery Leaks	10-1
Chapter  11
  VOC Emissions from Storage of Petroleum Products 	11-1
Chapter  12
  VOC Emissions from Gasoline Marketing Operations	12-1
Chapter  13
  The Regulatory Approach to VOC Control — I	13-1
Chapter  14
  Liquid Asphalt	14-1
Chapter  15
  The Regulatory Approach to VOC Control —II 	15-1
Chapter  16
  Methods of VOC Emission Control— Incineration	16-1
Chapter  17
  Methods of VOC Emission Control — Adsorption	17-1
Chapter  18
  The State VOC Control Program —an Example	18-1
Chapter  19
  Homework Problems	19-1

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                       Chapter   1
                         Introduction
The goal of this course is to provide you with the necessary background needed to
develop, implement and enforce the federal, state, and local volatile organic emis-
sion control programs. You will learn about organic emissions problems of the
major sources of such air pollutants and the common methods used to control these
emissions from each source category. Associated topics such as emission inventories,
emission estimation and measurement methods, and inspection programs are also
included to provide a thorough ground in the topic of organic emissions control.
                     Course Objectives
Upon completion of this course, you should be able to:
• Identify by name the symbols and acronyms commonly used when describing
  VOC emissions and the control of such emissions from stationary sources.
• Describe the relationships between volatile organic air pollutants and the
  photochemical air pollution problem.
• Identify the various regulatory requirements dealing with sources of organic air
  pollutants; describe the methods of preparing emission inventories and the types
  of volatile organic emission control regulations developed for inclusion in the
  SIPs.
• List and describe the common methods used to estimate and measure volatile
  organic emissions, including methods of material balance, loss estimation, sam-
  ple collection, and analysis by chromatography and spectroscopy.
• Sketch flow diagrams which illustrate the working principles of typical control
  systems used for reducing the emission of volatile organic air pollutants. You
  should be able to give examples of the application of such devices as  adsorbers,
  incinerators, and condensers.
• Describe the common methods of material and process modification used  to
  reduce organic emissions for each of the major source categories discussed in the
  course.
                                    1-1

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Identify the types of organic emissions and emission points for each of the source
categories listed below.
— petroleum refining
— petroleum storage, transportation, and marketing
— degreasing operations
— cutback asphalt processes
— industrial surface coating operations
Describe the inspection procedures which can be used for checking a VOC
emission source.
Describe key aspects of equipment appearance and process operations which
should be observed in order to determine that organic emissions are being
properly controlled, including evaluation of data from processes and emission
monitoring instrumentation.
Explain the use of EPA's control technique guidelines in the development and
implementation of a State V oo control strategy.
                                    1-2

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                      Chapter   2
                   Regulatory Review
Lesson Goal:           To provide a technical and regulatory vocabulary which
                      will enable you to understand the detailed course material
                      to be presented in subsequent lectures.

Lesson Objectives:       Upon completion of this lesson, you should be able to:
                      •  Identify all of the following acronyms: AQCR, SIP,
                        CTG, VOC, RFP, RACT, BACT, LAER, I/M, PSD,
                        NSPS, OAQPS, ESED, O/M,  NSR, RM, TGNMO.
                      •  Explain how states are required to include VOC control
                        plans in their  SIPs for nonattainment AQCRs.
                      •  Describe the role of CTGs in the development of SIPs.
                      •  Define RACT
                      •  Explain how EPA concepts such as BACT, RACT,
                        PSD, etc., apply  to new and existing sources in attain-
                        ment and nonattainment areas.
                      •  Locate information on VOC control.
                      •  Explain how State air pollution agencies can use EPA
                        Control Technique Guideline  Documents in the
                        development of State VOC programs.

References:             Environmental Protection Agency (EPA). 1980. Office of
                      Air Quality Planning and Standards (OAQPS).  Guidance
                      for the Control of Volatile Organic  Compounds Emitted
                      by 10 Selected Source Categories.
                      Environmental Protection Agency (EPA). 1978. Summary
                      of Group 1 Control Technique Guideline Documents for
                      Control of Volatile  Organic Emissions from Existing Sta-
                      tionary Sources.  EPA-450/3-78-120.
                      Environmental Protection Agency (EPA). 1978.
                      Regulatory Guidance for Control of VOC Emissions from
                      15 categories of Stationary Sources.  EPA-905/2-78-001.
                      Environmental Protection Agency (EPA). 1979. Summary
                      of Group II Control Technique  Guideline Documents for
                      Control of Volatile  Organic Emissions from Existing Sta-
                      tionary Sources. EPA-450/2-80-001.
                                  2-1

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Environmental Protection Agency (EPA). 1979. 44 Fed.
Reg. 53761 (September 17,  1979). State Implementation
Plans:  General Preamble for Proposed Rulemaking on
Approval of Plan Revisions for Nonattainment
Areas—Supplement on Control Technique  Guidelines.
Environmental Protection Agency (EPA). 1979. Guidance
for Lowest Achievable Emission Rate from  18 Major
Stationary Sources of Particulate, Nitrogen Oxides, Sulfur
Dioxide,  or Volatile Organic Compounds.
EPA-450/3-79-024.
The Clean Air Act (as Amended  August 1977). Serial No.
95-11.  November 1977.
Proceedings: Mid-Atlantic States  Section APCA Semi-
Ann 
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          6O%
        All Other
         Sources
    VOC Problem - 3O million tons
                    AIR QUALITY
                  CONTROL REGIONS
      nONATTAINMENT OF PHOTOCHEMICAL
             OXIDAPITS. AUGUST 1977
     Primary NAAQS
     not attained
       i part of county
              Qroup I
        CTG Source Categories
      •  gasoline loading terminals
      •  gasoline bulk plants
      •  service stations • Stage I
      •  fixed roof petroleum tanks
      •  miscellaneous refinery sources
      •  cutback asphalt
      •  solvent metal cleaning
              Group 1
       CTG Source Categories
             (continued)
•urface coating oft
    • can*          • aatOBMbilea and
    • metal coll*       llobt track.
fabric*
paper
prodMcU
                      «eUU f«™l*»re
                      larac appUajKca
                                                  2-3

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             Group II
     CTG Source Categories

   • leaks from petroleum refineries
   • miscellaneous metal parts
     surface coating
   • surface coating of flat wood
     paneling
   • syntactic pharmaceutical
     manufacture
             Group II
      CTG Source Categories
            (continued)
     • rubber tire manufacture
     • external floating roof petroleum
       tanks
     • graphic arts
     • perchloroethylene dry cleaning
     • gasoline truck leaks and vapor
       collection
 GROUP 111= CONTROL TECHNIQUES
           GUIDELINES SOURCE
           CATEGORIES"
• Storage, Transportation and Marketing
  of VCX
  • Oil ond 6as Production one) Practising
    • Fuglovt VOC Ott at* Go» frodunlan
    • Fuptiv* VOC Ntnunn On and GaMfcw harming flgmi
  • Bulk Ttminols - Volotll. Oigonlc UquW
    Uxxftng Into Hollcors
  • WkPtanti-Volottl* Organic Liquid
    Storoot
  GROUP III1 CONTROL TECHNIQUES
            GUIDELINES SOURCE
            CATEGORIES0
            (continued)
    • Industrial Processes
       •  Organic Chwnkal Manufacture
         • FugHlv* VOC. SOCMJ
         • All OOOoUon. SOCMI
       •  SOR Monufaauf*
       •  Pofymn and Resins Manufacturing
  GROUP III' CONTROL TECHNIQUES
            GUIDELINES SOURCE
            CATEGORIES0
            (continued)
     •  Industrial Surface Coating
       •  rOOnC PnfrtiOQ
     •  Honlndostriol Jurfoc* Coating
       •  Architectural Coatings
                                                 2-4

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  GROUP III' CONTROL TECHNIQUES
         GUIDELINES SOURCE
         CATEGORIES"
          (continued)

  • Oth*f Solvent Us*
   • Drydeaning • Petroleum Solvent System
   • Graphic Arts • Letterpress Printing 6 Offset
     Lithography
  • Other Mrsc«tlo«*ous Sources
   • Wast* Solvent Recovery Processes'1
REGULATIONS AFFECTING
    EXISTING SOURCES

   Examples:

    •  SIP - RACT

    •  Federal, state and
      Local Permit Systems
            RACT
    Reasonably Available
      Control Technology

    •  reasonably available
      technology
    •  considers cost
         REGULATIONS
  AFFECTING HEW SOURCE
       CONSTRUCTION

New Source Review (HSR)
  • process for reviewing new sources
           NSPS
         New Source
  Performance Standards

• promulgated for various source
  categories
• specify emission limitations
• can be found in CFR
                                     2-5

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         BACT
     Best  Available
   Control Technology

• best technology available

• considers cost and energy
  requirements
         LAER
   Lowest Achievable
     Emission Rate

 control devices to achieve
 lowest possible emission r.*t<

 required for sources in
 nonattainment areas
          PSD
      Prevention of
Significant Deterioration

   • EPA policy applied to
     new sources in an
     attainment area
                 RFP
              Reasonable
                Further
               Progress
           I/M
   Inspection / Maintenance
                                   2-6

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  Controlled Trading

    • Off set Policy
    • Bubble Policy
    • Banking Emissions
     Offset Policy

• required for new sources
  in nonattainment areas

• "trade-off" of emissions
 42O Ihs/hr

   3OO Ibs/hr
      VOC
1OO Ibs/hr
  VOC
        Offset
 Existing Source
               new Source
                 Bubble
                  Policy
               Banking
              Emissions
                                 2-7

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     DIRECT IMPACT OF FEDERAL
 POLICIES OPI STATIONARY SOURCES
      Existing Source Policies —
	Unmodified	
    Don-      ^^*=^~~~-.
  attainment
                   /
               RFP
                 	 IBUBBLB
                         / Attainment
               OFFSET '-/    Area
     DIRECT IMPACT OF FEDERAL
 POLICIES OH STATIONARY SOURCES

             Source Policies	
                 IXSR
                             DSPS
                             •ACT
                             PM>


                        Attainment Area
     DIRECT IMPACT OF FEDERAL
 POLICIES OPI STATIONARY SOURC
     Existing Source Policies -
   attainment,
     Area "V      "»T
                             BACT
           \ OFFSET   '/     PSD

Attainment Area
                                               2-8

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                      Chapter  3
            Organic  Chemistry Review
Lesson Goal:
Lesson Objectives:
References:
          l/Vt
To review the basic concepts and terminology of organic
chemistry so that you will have a referent for the more
detailed course material.

Upon completion of this lesson, you should be able to:
• Identify organic compounds in terms of their chemical
  classification, for compounds in the following classes:
      — Hydrocarbons — (alkanes-alkenes-alkynes)
      —Hydrocarbons
      — Oxygenated Compounds—(ethanols-ethers
                              ketones- aldehydes
                              esters-acid)
      — Amines
• Discuss reactivity in terms of Rule 66 and EPA's cur-
  rent policy of positive emission reduction.

Brewster and McEwen. 1962. Organic  Chemistry.
Prentice-Hall, Inc. New Jersey.
National Academy of Science. 1976. Vapor-Phase
Organic Pollutants— Volatile Hydrocarbons and Oxida-
tion Products. Washington, DC.
Environmental Protection Agency (EPA). 1977. Recom-
mended Policy on Control of Volatile Organic Com-
pounds. 44 Fed. Reg. 35314 (July 8, 1977).
Environmental Protection Agency (EPA). 1978. Memo:
Clarification of EPA Policy on Emissions of Methyl
Chloroform, from Walt Barber to Regional
Administrators. August  24, 1978.
Environmental Protection Agency (EPA). 1978. Memo:
Definition of Volatile Organic Compound from Vera
Gallagher to James C. Berry. October  26, 1978.
                                  3-1

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             voc

 "A volatile organic compound (VOC) to
  any organic compound that, when
  released to the atmosphere, can remain
  long enough to participate in
  photochemical reactions .... almost all
  organics which can be considered VOC/   ^t-^JU-t^-r
  have vapor pressures greater than s                *
 s^^^^n^^r     ^
 HC      Hydrocarbon

THC     Total
           Hydrocarbon
           NonMcthanc
           Hydrocarbon
      HYDROCARBONS
               i	
          I              I
       Aliphatic        Aromatic
  AlkwMs Alkene* Alkynes    f\

  CHjCHs CH'CH2 HC1CH  benaene
  ethane ethylenc ethyne  '   x^/CH3
             (acetylene)   C^J
    •	1»V   toluene
      NOMENCLATURE
       1 carbon    CH4  nMthan*
  •th-  2carfaoa*   CjH6  ethaoe
  prop- 3carbon*   CjHg  propane
  but-  4carbon*   C^y, butane
  pent- 5carbon*   CjHu pratane
  ha-  6carbon*   C(HM hoxane
  hcpt- 7carbon*   C?H16 heptane
  oct-  8carbon*   CgHu octane
                                      3-2

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  Alcohols  Aldehydes


             9
                   Ketones
   H-OH    R-C-H   R,- C-R2
   Esters    Acids     Ethers

   9        9
 R-C-O-R   R-C-OH    R-O-R
 HALOCARBONS
a       a
  X
a       a
               H      a
              H-,c-cra
               H      a
perchloroethylene   trkhoroethane
              (methyl chloroform)
 NITROGEN COMPOUNDS
Nitroparafflns
9
CHj-CH2-O-N=O
A*k>il •.!*••.*.»
•tnin atiMw
o
nltroethane
AmlMM >x- t^^1-"
r
R-NH2
CCH
NH2
2-propylamine
          NASTIES
          Cl
                Cl
                     C=C-C-H
  beiuopyran   pdychlortnated
            blphmyl
  a   o  "a   CH3-c-o-o-N02

    dioxln (TCDD)      pmnucctyl nHraM
                                     3-3

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oi
            RULE 66



        high reactive HC's


           replaced with


         low reactive HC's




        EPA REVIEW OF RULE 66

        • little reduction of oxidant levels

        • few low reactivity organic*

        • manyVOC: suspected mutagens,
         carcinogens, or teratogens

        • ozone layer problems

        • low reactivity compounds
         have limited applications
                                        3-4

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                      Chapter  4
  YOG Emission  Measuring Techniques
Lesson Goal:
Lesson Objectives:
References:
To familiarize you with methods used to measure organic
emissions quantitatively.

Upon completion of this course, you should be able to:
• Describe the operating principles of instruments used to
  measure VOC emissions:
     -Non Dispersive Infrared Spectrometer (NDIR)
     — Gas Chromatograph (GC)
     — Flame lonization Detector (FID)
• Describe the difference between gas-liquid and gas-solid
  chromatography
• Recognize the components of a typical gas
  chromatographic system
• Describe the following VOC measurement/sampling
  schemes:
     —material balance
     — activated carbon adsorption
     — universal collector (carbon and Tenax GC)
     — cold trap/evacuated cylinder
     — syringe or purged flask
     — collapsible Tedlar bags
     — direct sampling with an FID (Total Hydrocarbon
       Analyzer)
     -GC and NDIR
• Recognize Reference Method 25 —TGNMO sampling
• Describe the sampling equipment set-up for RM 25
• Name the components analyzed in RM 25

Environmental Protection Agency (EPA). 1978. Measure-
ment of Volatile Organic Compounds. OAQPS No.
1.2-115. RTF, NC. EPA-450/2-78-041.
McNair, H. M., Bonelli, E. J. 1968. Basic Gas
Chromatography. 5th edition. Walnut Creek, CA: Varian
Aerograph.
Environmental Protection Agency (EPA). 1979. Method
25—Determination of Total Gaseous Nonmethane
Organic Emissions as Carbon: Manual Sampling and
Analysis Procedure. 44 Fed. Reg. 57808-57822 (October
5, 1979).
            4-1

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     MATERIAL BALANCE
AMOUNT
                SAMPLING
               APPARATUS
 I
   ACTIVATED CARBON ADSORPTION
   Filter
       Activated Carbon Section


                    Pump
        UNIVERSAL COLLECTOR
   SAMPLE M
    OUTLET
                         CLOSED
          SAMPLE COLLECTION
     UNIVERSAL COLLECTOR
           ACT. CHARCOAL

          SAMPLE RECOVERY
                                       4-2

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              AND

        SYRINGE SAMPLE
                    BAG SAMPLE
                             FLOW METER
 I
     COLD TRAP-
EVACUATED CYLINDER
VACUUM
 GAUGE
           LABORATORY
             ANALYSIS
           NDIR ANALYZER

INFRARED    BEAM    SAMPLE  SAMPLE
         CHOPPER,   IN   EXHAUST  lOETECTOR
                               SENSOR
                                         4-3

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     GAS-SOLID
             OOQ
             ooo
     GAS-LIQUID
             OOO
GAS CHROAAATOGRAPHIC SYSTEM
Injection
 Port
mm
ilisH-Sij
Detector
         Column
   Carrier
   Gas
   Bottle
  Chromatogrom

     >uAUU
                Recorder
  Injection
   Port
              Carrier
                Gas
               Bottle
               Column
                         4-4

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     GAS-LIQUID

               COO
               coo
              Detector
THERMAL CONDUCTIVITY CELL

Electric Leads.
FLAME IONIZATION DETECTOR
            Exhaust
            I	
                  J_
      Sample H2   Air
 Chromatogram
              Recorder
                               4-5

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        Thermostats
             -"T
 GAS CHROAAATOGRAPHIC SYSTEM
                        Recorder
        BYRON ORGANIC ANALYZER
Somp).
        AUTOAAATIC
   PROGRAMMED ANALYSIS
                                  4-6

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                 FID
              Used as a Total
            Hydrocarbon Analyzer
 METHOD 25 SAMPLING TRAINS
METHOD 25 ANALYSIS

     • Condensate
     • Tank
         METHOD 25 LAB ANALYSIS
         1 Step 1: Condensate Trap
         METHOD 25 LAB ANALYSIS
         Step 2: Sample and Intermediate
         Tanks
                                   4-7

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        METHOD 25

COMPONENTS ANALYZED


  • NonmethaneOrganics

  •CO,CO2,andCH4
        EMISSION VALUES

          (ppm equivalents)


                   Carbon
                   • FID calibrated using
                   methane
                   Propane
                   • FID calibrated using
                   propane
       VOC CONCENTRATION

          CALCULATION


    ppm              ppm
    propane   ^  3 =  carbon

    equivalent           equivalent
    value              value

    Example:

     100 ppm  x  3 —  300 ppm
     prooanp            carbon
     equivalent           equivalent
     value              value
                                   4-8

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                      Chapter   5
       VOC  Emissions from  Industrial
           Surface  Coating Operations
Lesson Goal:
Lesson Objectives:
To familiarize you with the impact of surface coating
operations as a source of VOCs. To provide for you a
basis for understanding the types of coating processes,
problems, and control operations that are available.

Upon completion of this lesson, you should be able to:
• Recognize the relationship between VOC emission and
  the quantity and types of organic solvents within the
  coating material.
• Define in general terms:
     — paint
     — transfer efficiency
     -flash off
     — powder coating
     — electrodeposition
• Describe three processes that may be used for drying
  common coating materials, giving an example of each:
     — evaporation—lacquer
     — oxidation — enamel
     — polymerization — epoxide
• List and describe the  five applications commonly used to
  apply surface coatings.
     — spray
     — dip
     — flow
     — roller
     —knife
• Describe the relative transfer efficiencies for the five
  application methods listed above.
• Identify the industrial uses of each of the five applica-
  tion methods listed above.
• For each application method, describe the relative emis-
  sion quantities for each step of the process:
     — application
     — pre-drying
     — curing

             5-1

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                       • List and describe five methods for controlling VOC
                         emission from surface coating operations which can be
                         considered RACT.
                             — formula change
                             — radiation method
                             — powder application
                             — process changes
                             — add-on control
                       • Describe the advantages and disadvantages of each of
                         the above five RACT methods.
                       • Describe the terms in which the recommended VOC
                         standards for surface coating are given.
                       • Calculate the VOC emissions for a coating containing
                         both organic solvents and water, given the percentages
                         of each in the coating.
                       • Using the graph found in EPA-450/2-77-008, page 1-4,
                         calculate the emissions reduction obtained by using a
                         coating with a higher solids content.

References             Environmental Protection Agency (EPA). Control
                       Technology Guideline Documents.
                         November 1976. Control of Volatile Organic Emissions
                         from  Existing Stationary  Sources— Volume I: Control
                         Methods for Surface-Coating Operations. OAQPS No.
                         1.2-067. EPA-450/2-76-028.
                         May  1977.  Control of Volatile Organic Emissions from
                         Existing Stationary Sources— Volume II: Surface
                         Coating of Cans,  Coils, Paper, Fabrics, Automobiles
                         and Light-Duty Trucks. OAQPS No. 1.2-073.
                         EPA-450/2-77-008.
                         December 1977. Control  of Volatile Organic Emissions
                         from  Existing Stationary  Sources— Volume HI: Surface
                         Coating of Metal Furniture. OAQPS No. 1.2-086.
                         EPA-450/2-77-032.
                         December 1977. Control  of Volatile Organic Emissions
                         from  Existing Stationary  Sources— Volume IV: Surface
                         Coating for Insulation of Magnetic Wire. OAQPS No.
                         1.2-087. EPA-450/2-77-033.
                         December 1977. Control  of Volatile Organic Emissions
                         from  Existing Stationary Sources— Volume V: Surface
                         Coating of Large  Appliances. OAQPS No. 1.2-088.
                         EPA-450/2-77-034.
                                    5-2

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  June 1978. Control of Volatile Organic Emissions from
  Existing Stationary Sources— Volume VI: Surface
  Coating of Miscellaneous Metal Parts and Products.
  OAQPS No. 1.2-101. EPA-450/2-78-015.
  June 1978. Control of Volatile Organic Emissions from
  Existing Stationary Sources— Volume VII: Factory Sur-
  face Coating of Flat  Wood Paneling. OAQPS No.
  1.2-112. EPA-450/2-78-032.
  December 1978. Control of Volatile Organic Emissions
  from Existing Stationary Sources— Volume VII:
  Rotogravure and Flexography. OAQPS No. 1.2-109.
  EPA-450/2-78-033.
Environmental Protection Agency (EPA). 1977. Con-
trolling Pollution from the Manufacturing and Coating
of Metal Products. Environmental Research Center,
Cincinnati, OH. EPA-625/S-77-009.
               5-3

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                    many different types
                    of materials used for
                    decoration and
                    protective coating
                    of various surfaces
1,020,000 Metric Tons
  Industrial Surface Coating
                             14,660,000
                               METRIC
                              TONS/YR
      FACTORS AFFECTING EMISSIONS
  NON - PROCESS FACTORS   PROCESS FACTORS
    TYPICAL OIL BASE WHITE HOUSEPAINT
                % BY WEIGHT



HEAT BODIED LINSEED OIL'"''""''
THINNER »«miHHi..u,.mi.i..H.H,u,HM.Mm.i.,,..m,



«», i2\
mm I",
mm 1 91
                                                  5.4

-------
RULE 66 FORMULATIONS

                     3.5% ALCOHOLS

                     6.7% AROMATICS

                     47 % SATURATED
                         ALIPHATICS
                     42.8% NON-
                          VOLATILE
                          PORTION
                 FORMAT FOR EMISSION
                      LIMITATIONS
                    tbs. organic volatile*
                   gallon coating (-water)
  RACT RECOMMENDED EMISSION

2.55 Ibs solvent
gallon (-water)
               Coil Coating
1.89 Ibs solvent  . .  0 .
gallon (-water)  Auto Pnmer Coating
2.96 Ibs solvent
 gallon (-water)  Metal Furniture Coating
             Paints
EVAPORATION
Lacquers
Shellac
Varnishes




OXIDATION
Enamels
Acrylics

POLYMERIZATION
Epoxies
Latex
Urethanes
                                           5-5

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CO
•o
1
         ALTERNATIVE TOPCOATS
           Lacquer
             Dispersion Lacquer
               -Current Enamel
                        -Nonaqueous Enamel
                             Urethane
                                   Cathodic E-Coat
                                       odic E-Coat-
                          Powder Coating
   2030405060708090100
Percent Solids by Volume, excluding water
 (0
                     40    Transfer Efficiency
                       50
     20      30     40     50     60      70     80
     Percent Solids by Volume, excluding water
     I	_L	1	1	1	1	,
           60S     518    432     395    259
           Solvent Content, grams per liter
                                 5-6

-------
           PROCESSING FACTORS
 APPLICATION
              PRE-DRYING
                             CURING
         AMOUNT APPLIED
 TRANSFER EFFICIENCY
                      >   .}  THICKNESS
                          AREA TO COAT
               PAINT
    % SOLVENT
     THINNER
                               1GAL.
SURFACE COATING = SOLIDS + SOLVENT
  20% SOLIDS •
80% SOLVENT


t
                             .2 mil
                                                 5-7

-------
  Estimation of Solvent Emissions
           .
         ef=
               VSQ
              1 -ws

    In units of Ib VOC/lgal - H20)
  PROCESSING
   FACTORS
  COATING
  PROCESSES
    FLOW

             SPRAY
              ROLL
                          DIP
                        KNIFE
  SPRAY
TECHNIQUES
           SPRAYING
     SPRAY
     BOOTH
                     Transfer
                     Efficiency

                    30%-60%
                                     5-8

-------
      DIP
   COATING  /
           Transfer Efficiency 75% - 95%
             FLOW COATING
    ROLLER COATING
    TOP COi
                             TO OVEN
                        BOTTOM COAT
                         TRANSFER
                       EFFICIENCY 95%
                Sheet-ted offset press.
COATING
                 KNIFE COATING
                   TRANSFER
                   EFFICIENCY 95%
                                           5-9

-------
             FLASH OFF

         • quantity of solvent
           evaporated from the
           coated surface during
           a specific time
DRYING: Removal of Volatiles
BAKING: Curing of the Coating
              OVEN DESIGN
          Sufficient Pre-dry Time
          Initial Low Temperature Zone
          Sufficient Curing Time & Temperature
          Cool Down
          Emission Removal

          Adequate Air
            HEAT SOURCES
     DIRECT FIREO
      GAS HEAT
INDIRECT FIREO
  GAS HEAT
ELECTRICAL
  HEAT
           > OF TOTAL EMISSIONS

SPRAY
FLOW
DIP
ROLLER
APPLICATION
30-50
30-50
5-10
0-5
PREDRY
10-30
20-40
10-30
10-20
CURING
20-40
10-30
50-70
60-80
   Source: Foster D. Snell Inc.
                                       5-10

-------
       METHODS OF CONTROL
        • Formula Changes
        * Radiation Methods
        • Powder Coats
        • Process Changes
        • Add-on Control Equipment
         WATER BORNE PAINTS
   ADVANTAGES
                          DISADVANTAGES
• Reduced Flammability
• Wide Range
        of Formulations
* Higher Solid Content'
             Viscosity
• Reduced Emissions
• Lower Materials Cost
* Ease of Cleanup
                         • Untried Technology
                         • Higher Energy
                                  Requirements
                         • Corrosion
                         • Increased Treatment
                         • Humidity Problems
         HIGH SOLIDS COATING
    ADVANTAGES
                          DISADVANTAGES
• Reduced Inventory Space
• Reduced Drum Handling
• Reduced Solvent
         Removal Energy
• Increased Compliance
             Potential
• Reduced Freight Colt
                       • Higher Coaling Viscotrty
                       • Reduced Storage Stability
                       • Fewer Formulations
 RADIATION  CURING SYSTEMS
                          uv
                          or Electron Beam

          RADIATION CURING
   ADVANTAGES
                        DISADVANTAGES
• Emissions Reduction
• Highspeed
• low Operating Coil
• Reduced Floor Span
                      • High Formula Coil
                      • Limit Formula Selection
                      • Need for Radiation Protection
                      • Equipment Coats
                                                       5-11

-------
        POWDER COATS
          POWDER COATS
ADVANTAGES
                     DISADVANTAGES
  > Very Low
    Emissions
  > Reduced Energy
    Needs
 Higher Cost
 Limited Selection
• Variable Adhesion
 Incompatible with
    Existing Equipment
 Uniformity Problems
 Color Changes
        PROCESS CHANGES
   •  Improved Application Efficiency
   •  Use of Prefinished Roll Stock
   •  Use of Metalized Coating
   •  Increase Vapor Concentration
                                                5-12

-------
                     Chapter   6
                VOC  Emissions from
              Coil Coating Operations
Lesson Goal:
Lesson Objectives:
References:
The purpose of this lecture is to give you an example of
the type of information that is needed when developing
RACT guidelines for State Implementation Plans for a
typical coatings industry.

Upon completion of this lesson, you should be able to:
• Diagram the coil coating process.
• Point out the VOC emission points of a coil coating
  operation.
• List at least two RACT methods appropriate for coil
  coating operations.
• Recognize the fuel saving aspect of incineration when
  applied to coil coating.
• Develop an analysis of the type of control options
  available to another industry emitting volatile organic
  compounds.

Environmental Protection Agency (EPA). 1977. Control
of Volatile Organic Emissions from Existing Stationary
Sources— Volume II: Surface Coating of Cans, Coils,
Paper, Fabrics, Automobiles, and Light Duty Trucks.
OAQPS  No. 1.2-073. EPA-450/2-77-008 (May 1977).
U.S. Department of Energy. 1978. Oven Curing:  Energy
Conservation and Emission Control in Coil
Coating—Technical Briefing Report—Technology
Transfer TID-28705.
                                  6-1

-------
     TYPICAL COATING MATERIALS
       Coating
       Acrylics
       Epoxies
       Phenolics
       Polyesters
       Silicones
    Volatile
(weight percent)
     40 - 45
     45  70
     45 - 5O
     45 • 5O
     35 - 5O
        HYDROCARBON
            SOLVENTS
          • Xylene
          • Toluene
          • NEK
          • Other Alcohols
             and Ketones
                      A,"
      DIAGRAM OF COIL
      COATiriO LINE WITH  »£• **•  ,!•»
      EMISSION POINTS
TYPICAL REVERSE ROLL COATER
                       	into oven
 applicator roll
        N-
flow of metal
 into coaler
                                       6-2

-------
             APPLICABLE
   SYSTEMS OF EMISSION REDUCTION
  Electro-Deposition — primer use
  Radiation Cure   — lack of monomers
  Powder Coating   — uniformity problems
  Water • borne     — limited range of paints
                — flexibility problems
  High Solids      — viscosity too high
  Adsorption      — limited because of
                  effluent temperatures
  Incineration     — energy problem?


      INCINERATION

         ECONOMICS


Retrofit — justifiable with

            8O% energy savings


     Solvent VOC's - BTU's
              RACT

            2.6lb. solvent
             gallon — H2O

       Based upon incineration of
     organic solvent-borne coating
    containing 25% solids by volume.
                                          6-3

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                      Chapter  7
    VOCs and Photochemical Oxidants
Lesson Goal:
Lesson Objectives:
References:
To give you an understanding of the role of volatile
organic compounds in the development of photochemical
smog.

Upon completion of this lesson, you should be able to:
• Diagram the photostationary state for Os production.
• Describe how peroxy radicals affect the photostationary
  state to produce a net increase in ozone.
• Explain why ambient NOT levels are a significant factor
  in the development of photochemical smog.
• Tell what effect high, low, and intermediate values of
  the VOC/NO, ratio have on the photochemical oxidant
  cycle.
• Use the EKMA graphs to determine ozone levels given
  different oxidant precursor conditions.
• Discuss the effect of natural sources of volatile organic
  compounds in the photochemical cycle.

Williamson, S. J.  1973. Fundamentals of Air Pollution.
Addison-Wesley Publishing Co. Mass. Chp. 10, pp.
296-305.
Environmental Protection Agency (EPA).  1977. Effec-
tiveness of Organic Emission Control Programs as a Func-
tion of Geographic Location. January 1977. CPDD,
OAQPS, EPA. EPA paper in support of ANPR for 41 FR
55558 December 21, 1976.
Environmental Protection Agency (EPA).  1978. Questions
and Answers Concerning the Basis for the Agency's Posi-
tion on Controlling Hydrocarbons to Reduce Oxidant.
Memo from David G. Hawkins (EPA-OANR) to
Regional Administrators. July 28, 1978.
Anderson, L. G. "Effects of Nighttime Chemistry upon
the Transport of Ozone and Ozone Precursors."/. Air
Pollut. Control Assoc. Vol 29: 970-973. September 1979.
Dimitriades, B. Issues Regarding the Role of Natural
 Organics in Photochemical Air Pollution.  Paper 80-69.1
presented at 73rd Annual Meeting of Air Pollut. Control
Assoc., June 22-27, 1980 Montreal, Quebec.
             7-1

-------
Environmental Protection Agency (EPA).  1977. Uses,
Limitations and  Technical Basis of Procedures for Quan-
tifying Relationships Between Photochemical Oxidants
and Precursors. EPA-450/2-77-021a, November 1977.
Environmental Protection Agency (EPA).  Procedures for
Quantifying Relationships Between Photochemical
Oxidants and Precursors: Supporting Documentation.
EPA-450/2-77-021b.
Environmental Protection Agency (EPA).  Relation of
Oxidant Levels to Precursor Emissions and Meteorological
Features.
  Vol. I: Analysis and Findings, EPA-450/3-77-022a.
  Vol. II: Review of Available Research Results and
                          FPA-450/3-77-022b.
  Vol. Ill Monitoring Data; tr^ o.,
Seinfeld, J. H. 1975. Air Pollution— Physical and
Chemical Fundamentals. New York: McGraw Hill.
Stevens, P. K. 1980. "Characterization of the Aerosol in
the Great Smoky Mountains", ,  . .  _ „
Assoc.  14:1491-1498.        J An Pollut'  Contr°l
              7-2

-------
fln   oc PHOTOCHEMICAL
                VOCs AND
                HEMICAL
               OXIDANTS
NO CONVERTS TO  N<>2
2NO + O2
  NO + O3
              2NO2
              NO2 + O2
     ~  compounds

      new organic
      compounds
            increases,
        O3 increases.
    Where:
      k = reaction rate constant
                                 7-S

-------
 ROv  or   R-O-O-
Rtl -t- HO»=t R'O2- + R"CHO
                                 7-4

-------
0.50
0.40
f  C.30

 3O: I
                                           7-5

-------
              THE EMPIRICAL KINETIC MODELING APPROACH:  EKMA
0.28
                                                                                 0.12
                                                                                 0.08
          0.2
                  0.4
                         0.6
0.8     1.0     1.2
   NHMC, ppm C
                                                        1.4
                                                                       1.8
 NATURAL VOCs

 • Areas with high values of
   natural VOCs generally have
   low NOji values; therefore.
      levels of oxidant

    'A position: natural sources
   jof VOCs do not contribute to
   smog formation
                                      7-6

-------
                      Chapter  8
                     VOC Emissions
          from  Degreasing Operations
Lesson Goal:
Lesson Objectives:
References:
To familiarize the students with the operation of vapor
and liquid degreasing processes, the VOC emissions
generated by them and the types of emission controls
available for degreasing operations.

The student should be able to:
• Identify the typical solvents used in degreasing
  operations.
• Describe three types of degreasers and the typical emis-
  sion points for each.
• Recognize the control methods for each type of
  degreaser.
• Recognize inspection procedures and EPA RACT
  guidelines for degreasers.

Environmental Protection Agency (EPA). 1977. Control
of Volatile Organic Emissions from Solvent Metal
Cleaning. OAQPS No. 1.2-079. RTP,  NC.
EPA-450/2-77-002.
Environmental Protection Agency (EPA). 1977. Con-
trolling Pollution from the Manufacturing and Coating of
Metal Products, Solvent Metal Cleaning Air Pollution
Control—II. Technology Transfer Seminar Publication.
EPA-625/3-77-009.
Environmental Protection Agency (EPA). 1979. Solvent
Metal Cleaning, Inspection—Source Test Manual.
Washington, B.C. EPA 340/1-79-008.
Environmental Protection Agency (EPA). 1980. "Organic
Solvent Cleaners; Standards of Performance for New
Stationary Sources; Proposed Rule and Notice of Public
Hearing". 45 Fed. Reg. No. 114, 39766-39784 (June 11,
 1980).
                                  8-1

-------
          voc
     EMISSIONS
         FROM
    DECREASING
    OPERATIONS
Used to clean
       SOLVENTS

  • Aliphatics
    • kerosene
    • heptane

  • Aromatics
    • toluene
    • turpentine

  • Keytones, Alcohols, Ethers

  • Halogenated Organics
    HALOGENATED
       ORGANICS

   • trichloroethylene
   • 1,1,1 trichloroethane
   • perchJoroethylene
   • methylene chloride
   • trichlorotrifluoroethane
                             8-2

-------
    TYPES OF
  DEGREASERS

   • Cold Cleaner
   • Open Top
   • Conveyorized
COLD CLEANER
 DEGREASER
  ,  ,  X^XX COLD CLEANER
«poJ^ X^-X*.'*.''' DEGREASER
    6.V.'!. * .,«•  EMISSION
                 POINTS
                 'carry-out
            OPEN TOP
 condensing coils   DEGREASER
           heating elements
   „„,,.    \   REFRIGERATED
         X     FREEBOARD
                CHILLER
                              8-S

-------
                     OPEN TOP
                    DEGREASER
               exhaust   WITH LIP
                     EXHAUST
         TWO
   COMPARTMENT
      OPEN TOP
     DEGREASER
      offset solvent
    boiling chamber
                     warm solvent
                   immersion chamber
   roofvent^ diffusion and
             convection  OPEN TOP
              \  -L   DEGREASER
  _.  ~ —     'J** ^  EMISSION
 adsor&er'  n   ^.i-i.iii*:.?.. POINTS
    waste
       MONORAIL
    CONVEYORIZED,
      DEGREASER
      boiling chamber
         CROSS-ROD
CONVEYORIZED DEGREASER
                                      8-4

-------
          MESH BELT
       CONVEYORIZED
         DEGREASER
CONVEYORIZED DEGREASER
   EMISSION POINTS
  carry-out
                        bcr
    FIELD INSPECTION
                  carbon
                adsorption
                  svstem
        SOURCE MEASUREMENT
             METHOD 23
       Ted la r or
      aluminiyed
       Mylar bag
    rigid leak-proof
       container
                METHOD 23
              LAB ANALYSIS
                                   8-5

-------
GUIDELINES FOR RACT

• Control System A
  •  operating and working practices
  •  inexpensive control

• Control System B
  •  all of Control System A plus
    more control
         EPAs POLICY
        ON EXEMPTIONS

 • Cold Cleaners in rural
   nonattainment areas with
   emissions < 100 tons per year

 • Open Top Degreascrs with open
   area < 1.0 m2

 • Conveyorized units with air/vapor
   interface < 2.0 m2
                                       8-6

-------
  EPA's Policy on RACT  Regulations for Degreasers

EPA's guidelines for RACT as applied to degreasers are divided into separate
guidelines for cold cleaners, open top vapor degreasers, and conveyorized
degreasers. Each guideline is divided into two levels of control. Control System A
consists of operating practices and simple, inexpensive control equipment. Control
System B consists of System A plus additional requirements to improve the effec-
tiveness of control.

Application of Control Systems A and B

An approvable State Implementation Plan (SIP) must require the application of
Control System B throughout urban nonattainment areas (> 200,000 population)
seeking an extension and to all facilities emitting VOCs in excess of 100 tons per
year in other nonattainment areas. Facilities emitting 100 tons per year or less of
VOCs in  other nonattainment areas must  apply Control System A as a minimum.
However, EPA encourages States to control all degreasers in  nonattainment areas
to the Control System B level.


              Control Systems for  Cold Cleaning

Control System A—(work practices)

                             Control Equipment
  1. Cover
  2. Facility for draining cleaned parts
  3. Permanent, conspicuous label, summarizing the operating requirements.

                          Operating Requirements
  1. Do not dispose of waste solvent or transfer it to another  party, such that
    greater than 20 percent of the waste (by weight) can evaporate into the
    atmosphere.* Store waste solvent only in covered containers.
  2. Close degreaser cover whenever not handling parts in the cleaner.
  3. Drain cleaned  parts for at least 15 seconds or  until dripping ceases.
   *Water and solid waste regulations must also be complied with.


                                     8-7

-------
Control System B—(includes all of Control System A)

                             Control Equipment

 1. Cover:  Same as in System A, except if (a) solvent volatility is greater than
    2 kPa (15 mm Hg or 0.3 psi) measured at 38°C (100°F),*  (b) solvent is
    agitated, or (c) solvent is heated, then the cover must be designed so that it
    can be easily operated with one  hand. (Covers for larger degreasers may
    require mechanical assistance, by spring loading, counterweighing or powered
    systems.)
 2. Drainage facility: Same as in System A,  except that if solvent volatility is
    greater than about 4.3 kPa (32 mm Hg or 0.6 psi) measured at 38°C (100°F),
    then the drainage facility must be internal, so that parts are enclosed under
    the cover while draining. The drainage facility may be external for applica-
    tions where an internal type cannot fit into the cleaning system.
 3. Label:  Same as in System A.
 4. If used, the solvent spray must be a solid, fluid stream (not a fine, atomized or
    shower type spray) and at a pressure which does not cause excessive splashing.
 5. Major control device  for highly volatile solvents: If the solvent volatility is
    >4.3 kPa (33 mm Hg or 0.6 psi) measured at 38°C (100°F), or if solvent is
    heated  above 50°C (120°F), then one of the following control devices must be
    used:
    a. Freeboard that gives a freeboard ratio**  >0.7
    b. Water cover (solvent must be insoluble in and heavier than  water)
    c. Other systems of equivalent control, such as a refrigerated chiller or carbon
       adsorption.

                          Operating Requirements

Same as in  System A


                    Complete Control Systems
               for  Open Top Vapor Degreasers

Control System A

                             Control Equipment
 1. Cover that can be opened and closed easily without disturbing  the vapor zone.

                          Operating Requirements
 1. Keep cover closed at  all times except when processing work loads through the
    degreaser.

  'Generally  solvents consisting primarily of mineral spirits (Stoddard) have volatilities <2 kPa.
 **Freeboard ratio is defined as the freeboard height divided by the width of the degreaser.


                                     f8-~8

-------
2. Minimize solvent carry-out by the following measures:
   a. Rack parts to allow full drainage.
   b. Move parts in and out of the degreaser at less than 3.3 m/sec (11 ft/min).
   c. Degrease the work load in the vapor zone at least 30 sec or until condensa-
      tion ceases.
   d. Tip out any pools of solvent on the cleaned parts before removal.
   e. Allow parts to dry within the degreaser for at least  15 sec or until visually
      dry.
3. Do not degrease porous or absorbent materials, such as cloth, leather,  wood or
   rope.
4. Work loads should not occupy more than half of the degreaser's open top area.
5. Never spray above  the vapor level.
6. Repair solvent leaks immediately, or shut down  the degreaser.
7. Do not dispose of waste solvent or transfer it to another party such that greater
   than 20 percent of the waste (by weight) will evaporate into the atmosphere.
   Store waste solvent only in closed containers.
 8. Exhaust ventilation should not exceed 20 mVmin per  m2 (65 cfm  per ft2) of
   degreaser open area, unless necessary to meet OSHA requirements. Ventilation
   fans should not be used near the degreaser opening.
 9. Water should not be visually detectable in solvent exiting the water separator.


Control  System B

                              Control Equipment

 1.  Cover (same as in System A).
 2.  Safety switches
    a. Condenser flow switch and thermostat — (shuts off sump heat if condenser
       coolant is either not circulating or too warm).
    b. Spray safety switch — (shuts off spray pump if the vapor level drops
       excessively, about 10 cm (4 in.).
 3.  Major Control Device:
    Either:
    a. Freeboard ratio greater than or equal to 0.75, and if the degreaser opening
       is  >1 m2 (10 ft2), the cover  must be powered,
    b. Refrigerated chiller,
    c. Enclosed design (cover on door opens only when the dry part is actually
       entering or exiting the degreaser),
    d. Carbon adsorption system, with ventilation >15 mVmin per m*
       (50 cfm/ft*) of air/vapor area (when cover is open),  and exhausting
        <25 ppm solvent averaged over one complete adsorption cycle, or
    e. Control system, demonstrated to have control efficiency, equivalent to or
       better than any of the above.
 4. Permanent, conspicuous label,  summarizing operating procedures #1  to #6.

                            Operating Requirements
Same as in System A.
                                      8-9

-------
       Control  Systems for Conveyorized Degreasers

Control System A

                          Control Equipment: None
                           Operating Requirements

 1. Exhaust ventilation should not exceed 20 mVmin per m2 (65 cfm per ft2) of
    degreaser opening, unless necessary to meet OSHA requirements. Work place
    fans should not be used near the degreaser opening.
 2. Minimize carry-out emissions by:
    a.  Racking parts for best drainage.
    b.  Maintaining vertical conveyor speed at <3.3 m/min (11 ft/min).
 3. Do not dispo:•»  " waste solvent or transfer it to another party such that greater
    than 20 percent of the waste (by weight)  can evaporate into the atmosphere.
    Store waste solvent only in covered containers.
 4. Repair solvent leaks immediately, or shutdown the degreaser.
 5. Water should not be visibly detectable in the solvent exiting the waste
    separator.

Control System B

                             Control Equipment
 1. Major control devices; the degreaser must be controlled by either:
    a.  Refrigerated chiller.
    b.  Carbon adsorption system, with ventilation > 15 mVmin per m2
       (50 cfm/ft2) of air/vapor area (when down-time covers are open), and
       exhausting < 25 ppm of solvent by volume averaged over a complete
       adsorption cycle, or
    c.  System  demonstrated to have control efficiency equivalent to or better than
       either of the above.
 2. Either a drying tunnel,  or another means such as rotating (tumbling) basket,
    sufficient to prevent cleaned parts from carrying out solvent liquid or vapor.
 3. Safety switches:
    a.  Condenser flow switch and thermostat —(shuts off sump heat if coolant is
       either not circulating or too warm).
    b.  Spray safety switch — (shuts off spray pump or conveyor  if the vapor level
       drops excessively, e.g.  > 10 cm (4 in.).
    c.  Vapor level control thermostat —(shuts off sump heat when vapor level rises
       too high).
 4. Minimized openings: Entrances and exits should silhouette  work loads so that
    the average clearance (between parts and the edge of the degreaser  opening) is
    either < 10 cm (4 in.) or  < 10 percent of the width of the opening.
 5. Down-time covers: Covers should be provided for closing off the entrance and
    exit during shutdown hours.
                                    8-10

-------
                         Operating Requirements
1.  to 5. Same as for System A.
6.  Down-time cover must be placed over entrances and exits of conveyorized
   degreasers immediately after the conveyor and exhaust are shutdown and
   removed just before they are started up.
                                    8-11

-------
                     Chapter  9
       VOC  Emissions from  Petroleum
                         Refineries
Lesson Goal:
Lesson Objectives:
References:
To describe the operation of a typical refinery and iden-
tify the potential sources of VOC emissions from these
operations.

Upon completion of this lesson, you should be able to:
• Recall the magnitude of VOC emissions from a refinery
  compared to the total from stationary sources in the
  USA.
• List and describe the three major steps in refining:
    — separation
    — conversion
    — treatment
• List at least three sources of emissions from a refinery
  and recall methods for their control.
    — vacuum producing systems
    — wastewater treatment
    — process turn arounds

Environmental Protection Agency (EPA). 1973. Air Pollu-
tion Engineering Manual, Second Edition. AP-40.
Environmental Protection Agency (EPA). 1977. Control
of Refinery  Vacuum Producing Systems, Wastewater
Separators, and Process Unit Turnarounds, Guideline
Series. EPA-450/2-77-025.
American Petroleum Institute (API). 1973. Hydrocarbon
Emissions from Refineries. Bulletin 928.
Film: "Refining". Peckham Productions. New York. Film
#4879.
                                  9-1

-------
     STATIONARY SOURCES
     OFVOC
                         lOfog*. tronipoMQtion
                          ond morH«img of
                         petroleum product!
     PETROLEUM REFINERY
separot
processes
 crude
                                    •urn
                                products
                   treatment processes
   VACUUM
     UNIT
light gases



light gas oils

gas oils

lube oils
                           residuums
                       light product!
                    »
-------
              accumulator
                      CC*»f
                      gosolln*
                  COKING
                    UNIT
TREATMENT PROCESSES
      • Hydrotreoting
      • Sweetening
      • Acid Treating
      • Solvent Treating
      • Blending
      • Asphalt Blowing
                     toracovwy
                ASPHALT AIR
                  BLOWING
    - inlduum fMd
  VACUUM
 PRODUCING
   SYSTEM
                                 9-3

-------
       TYPES OF VACUUM

   PRODUCING SYSTEMS (VPS)

    • Steam Ejector with Contact
       Condenser

    • Steam Ejector with Surface
       Condenser

    • Mechanical Pump
  Incoming  _
non-eondensables
                        - jet st*am
                       • exhaust
                       •mission!
    hot well
                 TWO STAGE
             CONTACT CONDENSER
 water
vapor

 I   SHELL-AND-TUDE   t
      CONDENSER
                     non-condensate
                      coodensote
      CONTROL METHODS
 FOR VACUUM PRODUCING SYSTEM
Source
Nan-
CoodensoWes

Hot W«ll


Control
incinerate,
compress, or
send to fuel
gas/firebox
cover and
Incinerate
vapors
Emission Factor
(uncontrolled)
145 kg/100 m'
or
51 lb/10'bbl

_


      voc
                   WASTE-
                   WATER
                 TREATMENT
                                 9-4

-------
        TYPES OF
WASTEWATER SEPARATORS
     • API Separator
     • Corrugated Plate
        Interceptors (CPI)
     • Flocculation
     • Air Flotation
     API SEPARATOR
      skimmer
         T
      underflow baffle
DISSOLVED-AIR FLOTATION
                      aerated
                      water
                      oil and
                      water
 COVERED API  SEPARATOR
    floating cover
       underflow t sffle
                 vent emissions
              PROCESS
           TURNAROUNDS
                                  9-5

-------
         PROCESS
     TURNAROUND
   EMISSION FACTOR

uncontrolled 860 kg/103 m3
       refinery feed
      HYDROCARBON EMISSION
   SOURCES IN PETROLEUM REFINERIES
              Uncontrolled Controlled
                 
-------
                    Chapter  10
    Operation-Maintenance-Inspection
          —Petroleum Refinery Leaks
Lesson Goal:
Lesson Objectives:
References:
To describe the need for an operation-maintenance-and
inspection program for organic emission control equip-
ment and describe the benefits gained by initiating such a
program.

Upon completion of this lesson, you should be able to:
• Define what an operation—maintenance —inspection
  program is and list three major reasons why such a pro-
  gram should be implemented.
• Recognize the U.S. EPA, CARB, and Illinois
  Environmental Protection Agency documents dealing
  with O-M-I programs.
• Recognize a typical O-M-I program for oil refineries
  and identify the important features of the program.
• Identify two data reporting needs of an O-M-I program
  and give examples of each.

Environmental Protection Agency (EPA). 1978. Control
of Volatile Organic Compound Leaks from Petroleum
Refinery Equipment. Emissions Standards and Engineer-
ing Division.  OAQPS No. 1.2-111.  EPA 450/2-78-036.
State of California Air Resources Board. 1975. Emissions
from Leaking Valves, Flanges, Pump and Compressor
Seals, and Other Equipment at Oil Refineries. The Legal
Affairs and Enforcement and the Stationary Source Con-
trol Divisions, Report No. LE—78-011, Sacramento, CA,
April 1978.
Cross, Frank L., Jr.; Hesketh, Howard E., editors. 1975.
Handbook for the Operation and Maintenance of Air
Pollution Control Equipment. Westport, CT: Technomic
 Publishing Co. Inc.  1975.
 Wallace, Michael J. 1979. Controlling Fugitive Emissions.
 Chemical Engineering. August 27,  1979.  78-92.
 Morgester, J. J. et al. 1979. Control of Emissions from
 Refinery. . .Valves and Flanges.  Chemical Engineering
 Progress. August 1979. 40-45.

            10-1

-------
Hughes, T. W., Tierney, D. R., and Kahn, Z. S. 1979.
Measuring Fugitive Emissions from Petrochemical Plants.
Chemical Engineering Progress. August 1979. 35-39.
              10-2

-------
               OPERATION MAINTENANCE
               STAGE - Continued Surveillance
        CONTROL STAGE- Installation Of
                       Equipment
MONITORING STAGE- Detection Of Pollutants
                  And Sources
AN  O/M/I  PROGRAM IS
         » Training
         * Administration
         • Inspection
         * Preventive Maintenance
         • Corrective Action Procedures
         * Spare Parts
                            WHY O/M/I ?
                     1. Legal Requirementi
                     2  IniureNAAQSandSIP
                        In-plant Benefits
IN-PLANT BENEFITS OF O/M/I
      1. Reduced Operating Cost
      2. Compliance
      3. Extended Equipment Life
      4. Equipment Failure Detection/Prediction
      5. Equipment Damage Prevention
      6. Sustained Emissions Compliance
      7. Product Recovery
      8. Safety
                                                  10-3

-------
           INSPECTIONS
  ANNUALLY    QUARTERLY
WEEKLY
INSPECT
VOC Detector
• Pump seals
•Pipeline valves
- liquid
•Process drains
INSPECT
VOC Detector
•Compressor seals
•Pipeline valves -
gas
•Pressure relief
valves - gas
INSPECT
Visually
• Pump seals


        LEAKING COMPONENT
        7
                     10,000 ppm

                     1,000 ppm @ 5 cm
   GLOBE
   VALVE
 Possible
 Leak
 Areas
         VISUAL INSPECTION
"SNOOP BUBBLES
                                          10-4

-------
 BAG TECHNIQUES •     *"•*"'
 HIGH LEAK RATE
  BAG TECHNIQUES
  LOW LEAK RATE
                Aitalynr
        SIMPLE MECHANICAL SEAL
                         Product
                         Being Pumped
Possible
Leak
Areas
        TYPICAL AVERAGE LEAKS
Valves
Compressor
Seals
Pump Seals
0.2 kg/day
0.7 kg/day
1.1 kg/day
      ESTIMATING COSTS-ANNUAL
 TOTAL .
$115,000
                            4.9 Capital
                           25.2 Inspection
                           31.7 Administrative
                               and Support

                           53.2 Repair and
                               Maintenance
                                                  10-5

-------
BLACK GOLD REFINERY


Estimated
Emissions
1000 METRIC
TON/YEAR

Emissions
Reduced
with O/M/I
500 METRIC
TON PER YEAR

Savings
Per Ton
Reduced
J 150 PER
METRIC TON
iiHiHHimMiiiiiiiniiiniinNi

Annual
Savings
$75.000

TOTAL
ANNUALIZED
COST
O/M/I
$115,000


—



ANNUAL
SAVINGS
$75,000



_


NET
REFINERY
COST FOR
O/M/I
$40,000
                                  10-6

-------
                    Chapter   11
         VOC  Emissions  from Storage
               of Petroleum  Products
Lesson Goal:
Lesson Objectives:
References:
To examine the types of vessels used to store petroleum
liquids, their potential emissions, and their control as
outlined in the CTG Documents.

Upon completion of this lesson, you should be able to:
• List the factors affecting emissions from fixed-roof
  tanks.
• Describe the RACT requirements for fixed-roof tanks
  and their control efficiency.
• Describe three types of floating roofs.
• Describe the RACT requirement for external floating
  roofs.
• Describe the difference between RACT requirements
  for welded tanks and riveted tanks.

Environmental Protection Agency (EPA). 1978. Control
of VOC from Petroleum Storage in External Floating
Roof Tanks. Guideline Series. EPA-450/2-78-047.
Environmental Protection Agency (EPA). 1977. Control
of VOC from Petroleum Storage in Fixed Roof Tank.
Guideline Series. EPA-450/2-77-036.
American Petroleum Institute. 1980. Evaporation Loss
from External Floating Roof Tanks. Washington, DC.
API Publication 2517.
                                 11-1

-------
             RACT
All Tanks > 40,000 gal @ v.p.> 1.5 psla
      STORAGE TANKS
Fixed Roof  Floating Roof   Pressure
        PETROLEUM STORAGE
Product
Crude.
Lub Oils
Kerosene.
Gasoline,
Fuel Oils
Butane,
Propane
Volatility
Low

Intermediate


High

v.p. Range
< 1.5 psio

1.5 - 11.2
psio

> 11. 2 psio

Tank Type
Fixed

Float


Pressure

                    Inspection hatch
           rrwnhol*
 Breathing Losses  Working Losses
                                    11-2

-------
FACTORS AFFECTING VOC LOSSES
• true vapor pressure
• temperature changes
• tank diameter
• turnaround
• condition of P/V valves
• color and condition tank
• height of vapor space

     FIXED ROOF TANK WITH
    INTERNAL FLOATING COVER
  wlp*r-s*ol
  loom-filled coated fabric wol
         buoyant pantl
 ,- jtn
  foom-flll*d coot*d fabric s*ol
           **l pan
  INTERNAL
 FLOATING
   ROOFS
   EXTERNAL FLOATING ROOF TANK
                      (drain
              Pan
            Pontoon
          Double-Deck
TYPES OF
EXTERNAL
FLOATING
  ROOFS
                                     11-3

-------
               MECHANICAL
                SHOE  SEAL
 RESILIENT FOAM AND LIQUID SEALS
  Liquid-Mounted    Vapor-Mounted
          RACT
 (for External Floating Roofs)

  •  secondary rim-mounted
    seal covering the primary
    seal
      SECONDARY  SEALS
     secondary seat
                     secondary seal
SECONDARY SEAL REQUIRED
  Riveted
   Tank
           When.
            •«>»v.p.>1Jpila
                               11-4

-------
 SECONDARY SEAL REQUIRED
   Welded
    Tank
  When took equipped with,


     • vapor mourned i«al

      ana t»u« v.p _; l.Spjia

         or


     • shew s«al

     • licm'd mounted t*al
  1    and iiu* v.p _^ 4 0 piia
           -gap area

               - i*cor>dofy rim seal
                   seal fabric
                gpp area
area
                   secondary rim seal
                 HSPS
         Gap Measurements
     Shoe
   or Liquid
   Mounted
            Primary Seals
10.0 in.' per foot
of tank dtomttK

no gop • 1 '/i In.
           Secondary Seals
•  1.0 in.1 p»f foot
  ot tank dlanrt*t»(

•  no oop > V7 in.
     Vopor
    Mounted
             1 0 In.' p*r foot
             of tank dtom»t«<
                         • no gopi
   VARIABLE SPACE TANKS
       Liftei
     Roof Tank
             Flexible
          Diaphragm Tank
                                                 11-5

-------
    VAPOR
RECOVERY SYSTEM
                     11-6

-------
                    Chapter   12
        VOC  Emissions  from Gasoline
               Marketing Operations
Lesson Goal:
Lesson Objectives:
 References:
To introduce you to hydrocarbon control strategies for
gasoline marketing operations, as outlined in the EPA
guideline series.

Upon completion of this lesson, you should be able to:
• Distinguish between and describe the causes of VOC
  emissions from
    — bulk plants
    — bulk terminals
• Describe the RACT requirements for bulk plants and
  bulk terminals.
• Describe three types of vapor recovery  systems
  applicable to bulk terminals
    — carbon adsorption
    — refrigeration
    — incineration
• Distinguish between and discuss  Stage  I and Stage II
  controls for service stations.
• Describe three types of Stage II control systems
    — balance
    — vacuum
    — hybrid

 Environmental Protection Agency (EPA). 1977.  Control
 of Hydrocarbons from Tank Truck Gasoline Loading
 Terminals. Guideline Series. EPA-450/2-77-OS6.
 Environmental Protection Agency  (EPA). 1977.  Control
 of VOC from Bulk Gasoline Plants. Guideline Series.
 EPA-450/2-77-035.
 Environmental Protection Agency  (EPA). 1978.
 Hydrocarbon Control Strategies for Gasoline Marketing
 Operation. EPA-450/3-78-017.
                                 12-1

-------
    imported B***1*
             GASOUNE MARKETING
   Bulk Terminal
      • daily throughput > 20,000 gal
   Bulk Plant
      • daily throughput < 20,000 gal
   Service Station
EMISSIONS FROM GASOUNE MARKETING
Terminals
Plants
Service
Stations
Number
1,925
23367
184,000
Typical
Capacity
250,000 gal/day
5,000 gjl/day
1300 gal/day
10,000 gal /tank
HC Emissions
(total)
690,000 ton, year
200,000 ton year
530,000 ton/year
 TYPES OF LOADING
   • Splash Loading
   • Submerged Loading
   • Bottom Loading
    SPLASH LOADING
                Vapor Emissions
                12.0 lb/103 gal
                     or
                  1.4 kg/1031
                                  12-2

-------
    SUBMERGED FILL PIPE

V . '.'.

• •' ' •
'•.'/.'
'/.-;/;
L-
~~ , •
',' t /.'••''••*•

>•«*.•;:•:.•:•;
i. •.'. ' •• .-•> '
: \' • • \ - .•

                  Vapor Emissions
                   ao lb/103 gal
                     balanced
                        or
                   5.0 lb/103 gal
                      normal
     BOTTOM LOADING

                   Vapor Emissions
                     8.0 lb/103 gal
                      balanced
                         or
                  |  5.0 lb/103 gal
               1	-j     normal
         RACT
    (for Bulk Terminals)
Vapor Recovery/Control System
• emission limit of 0.67 fc/10' gal
• no leaks in vapor collection system
   during operation
                                     12-3

-------
 TYPES OF VAPOR CONTROL SYSTEMS

  • Carbon Adsorption

  • Compression - Refrigeration - Absorption

  • Refrigeration

  • Compression - Refrigeration - Condensation

  • Thermal Oxidizer
               £$•:,..      Splash
   1331 fb/gal 10s ..>£.*•;... 1X0 lb/103 gal
                •'*••'•
ALTERNATIVE I   .^jV^vV-
Submerged Fill ':--.'£&?'
                             f.-W:
      WV*:

        ^	j>   >x
         Total Reduction  =   27%
 ALTERNATIVE II ..>;..;.-.
 Submerged   •W-y'/'.'i':':.
 ft* i     .    •»•.*.;•.•
 nil plus partial  ••-••;'-'•-'••
 Vapor Balance    ''^l
      Total Reduction  = 64%
  ALTERNATIVE III
  Submeiged fill plus Complete Vapor Balance
     /^V^
     SB—u^  ,.>j
       Total Reduction  =  92%
                                              12-4

-------
  STAGE
COAXIAL
CONNECTOR
    VAPOR
    BALANCE
    SYSTEM
   STAGE II
                                      12-5

-------
   VAPOR RECOVERY NOZZLE
 VACUUM
 ASSIST SYSTEM
 STAGE II
ASPIRATOR   ' '
ASSIST
SYSTEM
                (to underground tank
                                   12-6

-------
                    Chapter  13
           The  Regulatory  Approach
                  to VOC  Control—I
Lesson Goal:
Lesson Objectives:
References:
 Emission Inventory

To acquaint you with emission inventory preparation, its
importance in preparing VOC control plans, and the general
methods of preparing VOC emission inventories.

Upon completion of this lesson, you should be able to:
• State the purpose of preparing VOC emission
  inventories.
• Identify sources for required or acceptable emission
  inventory formats.
• Describe the relationship of the emission inventory to
  VOC strategy preparation and Reasonable Further Pro-
  gress (RFP) planning and tracking.

Environmental Protection Agency (EPA). 1980. Pro-
cedures for the Preparation of Emission Inventories for
 Volatile Organic  Compounds. Vol.  I,  2nd ed. Research
Triangle Park, NC: U.S. EPA (OAQJPS, MDAD).
EPA-450/2-77-028.
Environmental Protection Agency (EPA). 1979. Pro-
cedures for the Preparation of Emission Inventories for
 Volatile Organic  Compounds. Vol.  II. Research Triangle
Park,  NC: U.S. EPA (OAQPS, MDAD).
EPA-450/4-79-018.
Environmental Protection Agency (EPA). 1978. Develop-
ment of an Emission Inventory Quality Assurance Pro-
gram. Research Triangle Park, NC: U.S. EPA (OAQPS).
 EPA-450/4-79-006.
 Environmental Protection Agency (EPA). 1980. Final
Emission Inventory Requirements for  1982 Ozone State
 Implementation  Plans. Research Triangle Park, NC: U.S.
 EPA (OAQPS, MDAD). EPA-450/4-80-016.
                                 13-1

-------
           EMISSION
         INVENTORIES
 What are the Clean
Air Act requirements
     for emission
     inventories?
   REQUIREMENTS

 • Clean Air Act §172(b)(4)

 • comprehensive, accurate,
  current inventory
    What are the
   purposes of an
      emission
     inventory ?
      PURPOSES

   • plan development
   • reasonable further
     progress evaluation
                           13-2

-------
   What areas
   need to be
   inventoried?
     AREAS

• nonattaintnent
  areas
• significant
  sources
  All sources must have
  emissions quantified.
        1] ^^-T^-*:	^_/






       ^ngClP
     Nonattainment
 Significant sources must
have emissions quantified.
      Attainment
  What sources
  of emissions
    should be
  inventoried?
                          13-3

-------
         SOURCES
   •  sources with potential
     for emitting more than
     1OO tons/year
   •  aggregate of sources with
     significant total emissions
    (accurate accounting is
     important)
 What information
      needs to be
       included?
   INFORMATION REQUIRED
 • enough to be useful in
   development of plan

 • usually:
     • emission points
     • type of process
     • type and quantity of
      emissions
     • stack parameters
      What year
      should the
      inventory
        be for?
YEAR OF INVENTORY

  • consistent with AQ
    data used for
    development of plan

  •  usually will be 1977
                              13-4

-------
  What format
    should the
inventory be in?
is-re;:-
:&.',"•"
-~^, — •
Diy^ IMXI

--
— —
^
El
f|
-• ^
--^
_-=-T-
- . 	 ^
._ ^JL^IH
±ttJ



FORMAT
• designed for
nonreactive
pollutants
• important
differences
for VOCs
      ACTUAL EMISSIONS
            Those emissions
        (determined by source
         test, emission factor.
             etc.) which are
         physically emitted to
            the atmosphere
              Allowable
              emissions
              are the most
              stringent of
              these three.
      VOC SUMMARIES
SOURCE
•tnneRlE&
TMAntrOHIATlOn
II IHMIM.T1TWJ
or rrTHOLEu*
inutSlKIAL
race uses
, " x
~^~~~^
TOTAL VOC tmsAI
»TATIOn*«V *OU«


oos r*on
cts
TOTAL voc emissions tpiow
rtOBILt MJUBCtS
emissions
BAM VC4II
[missions


^-— ;


rROJtCTEO
ALLOWABLE
rnrssions








~ <




..



                               13-5

-------
    EXEMPTED VOCs

      42 Federal Register
       35314-35316
        (July 8,1977)
     EXEMPTED VOCs
  Negligible Photochemical
  Reactivity:
   • methane
   • ethane
   • 1,1,1- trichloroethane
   • trichlorotrifluoroethane
  Separate inventory for
  each nonattainment
  pollutant

  Regulatory Requirements
  • 4OCFR§§51.321-324
  • ACROS Users Manual on NEDS
        SUMMARY

 • CAA §  172 (b)(4) requires
   inventories
       • comprehensive
       • accurate
       • current
• Inventory purpose must
  be clearly stated

     •  plan development
     •  RFP tracking
                                13-6

-------
  Inventory area must
  be clearly defined

  •  nonattainment areas
    for Part D purposes
  All sources having
  significant impact
  must be taken into
  account
 • Year of inventory
  must be clearly
  associated with data
 • Formats
     • required by law
      and regulation
     • should be useful
Expect to read and
ask questions before
applying any
technique on your own
                              13-7

-------
                 Federal Register  /  Vol.  45, No.  142 / Tuesday, July 22,  1980 / Notices
                                                                 48941
 ENVIRONMENTAL PROTECTION
 AGENCY

 [FRL 1545-7]

 Air Quality; Clarification of Agency
 Policy Concerning Ozone SIP
 Revisions and Solvent Reactivities
 AGENCV: Environmental Protection
.Agency [EPA).
 ACTION: Notice.

 BACKGROUND: This notice is published
 under the authority of section 10l(b) and
 section 103 of the Clean Air Act. The
 notice provides further clarification of a
 policy announced in EPA's
 "Recommended Policy on the Control of
 Volatile Organic Compounds," 42 FR
 35314 (July 8,1977) and "Clarification of
 Agency Policy Concerning Ozone SiP
 Revisions and Solvent Reactivities," 44
 FR 32042 (June 4,1979) and 45 FR 32424
 (May 18.1980).
 DISCUSSION: The previous policy
 statements on the control of volatile
 organic compounds (VOCs) noted that
 despite concerns about their potential
 toxicity 1,1,1-trichloroethane (methyl
 chloroform) and methylene chloride are
 negligibly photochemically reactive and
 do not appreciably contribute to the
 formation of ozone. Today's statement
 expands the list (45 FR 32424) of organic
 compounds (VOCs) of negligible
 photochemical reactivity to include the
 following chlorofluorocarbons (CFC) or
 fluorocarbons (FC):
 trichlorofluoromethane (CFC-H):
 dichlorodifluoromethane (CFC-12);
 chlorodifluoromethane (CFC-22);
 trifluoromethane (FC-23):
 trichlorotrifluoroethane (CFC-113):
 dichlorotetrafluoroethane (CFC-114);
 and chloropentafluoroethane (CFC-115).
   EPA has determined that these
 halogenated compounds are no more
 photochemically reactive than methyl
 chloroform and methylene chloride and
 do not appreciably contribute to the
 formation of  ambient ozone.
 Consequently, controls on emissions of
 these compounds would not contribute
 to the  attainment and maintenance of
 the national ambient air quality
 standards for ozone. EPA cannot
 approve or enforce controls on thtse
compounds as part of a Federally
enforceable ozone Stale Implementation
Plan (SIP). EPA will take no action on
any measures specifically controlling
emissions of these compounds which
are submitted by the States as ozone SIP
measures for EPA approval. (See 45 FR
32424.)
  However, EPA would like to reiterate
its continuing concern over the possible
environmental effects from emissions of
these compounds. As such, EPA is not
precluding the possible future regulation
of these compounds.
  It should be recognized that the two
halogenated compounds, methyl
chloroform and CFC-113. stated to be of
negligible photochemical reactivity in
the July 8,1977 Federal Register,  have
been implicated in the depletion of the
stratospheric ozone layer. This layer is a
region of the upper atmosphere which
shields the earth from harmful
wavelengths of ultraviolet radiation that
increase the risk of skin cancer in
humans.            /
  In response to  this concern, the
Agency promulgated oji March 17,1978
(43 FR 11318), rules under the Toxic
Substances Control Act (TSCA) to
prohibit the nonessential use of fully
halogenated chlorofluoroalkanes as
aerosol propellants. Restrictions  were
applied to all members of this class,
including CFC-113, since they are
potential substitutes for CFC-11, CFC-
12, CFC-114, and CFC-115. which are
currently used as aerosol propellants.
The Agency is investigating control
options and substitutes for
nonpropellant uses.
  EPA has proposed new source
performance standards under Section
111 for organic solvent cleaners (45 FR
39766, June 11,1980). These proposed
standards would limit emissions of the
reactive volatile  organic compounds
trichloroethylene and perchloroethylene
as well as methyl chloroform, methylene
chloride, and trichlorotrifluoroethane
(CFC-113) from new, modified, or
reconstructed organic solvent
degreasers. If these standards are
promulgated, EPA will develop a
guideline document for States to ust hi
developing regulations required under
Section lll(d) for existing organic
solvent cleaners that use any of the
designated compounds.
  Whether, and to what extent, methyl
chloroform and melhylene chloride are
human carcinogens or have other toxic
effects, and to what extent methyl
chloroform. CFC-113, and other CFCs
deplete the ozone layer, are issues of
considerable debate. Detailed health
assessments of methyl chloroform,
methylene chloride, and CFC-113 are
being prepared by EPA's Office of
                                                                              48942
Research and Development. These
assessments will be submitted for
external review, including a review by
the Science Advisory Board, prior to
promulgation of the regulations and the
proposal of EPA guidance to States for
developing existing source control
measures. The extent to which the
preliminary findings are affirmed by the
review process may affect the final
rulemaking for new as well as existing
sources.
  Until these issue»of environmental
impact are fully resolved, EPA remains
concerned that if these chemicals are
exempted from regulation, the
substitution of exempt for nonexempt
solvents cculd result in large increases
of emissions of pollutants that may have
adverse health impacts.
  The emissions of CFC-22 and FC-23,
also of relatively low photochemical
reactivity, are of continuing concern
with regard to possible environmental
effects. Consequently, EPA is not
precluding the possible future regulation
of these compounds as well.
  Finally, EPA wishes to point out  that
this notice addresses only the Agency's
lack of authority to include in Federally
approved SIPs controls on substances
whose emissions do not contribute,
either directly or indirectly, to
concentrations of pollutants for which
NAAQS have been established under
Section 109 of the Act. This policy notice
does not address the question of SIP
measures which, control substances
contributing to concentrations.of
pollutants for which NAAQS have been
established, but which are contended to
be more strict than absolutely necessary
to attain and maintain the NAAQS. EPA
has no authority to exclude such
measures from SiPs.
FOR FURTHER INFORMATION CONTACT:
C. T. Helms, Chief, Control Programs
Operations Branch (MD-15). Research
Triangle Park, North Carolina 27711,
(919) 541-5226, FTS 629-5228.
  Dated: July 16.1980.
David G. Hawkins.
Assistant Administrator for Air. Noise, and
Radiation.
(FR Doe. 60-219*1 Filed 7-Z1-ME £43 am)
BILUNO CODE &MO-01-M
                                                      13-8

-------
                          SUMMARY FORMAT FOR VOC
tOURCE
PETROLEUM REFINERIES


STORAGE TRANWyRTATIpN
• MARKEtlNC OF PETROLEUM
PRODUCTS







INDUSTRIAL PROCESSES




INDUSTRIAL SURFACE
iOATING
NON-INDUSTRIAL SURFACE
COATINGS
OTHER SOLVENT USE
OTHER MISCELLANEOUS
REFINERY FUGITIVES Illlkll
MISCELLANEOUS SOURCES
•I Proctu Drami «nd Witu
b] Vacuum Producing Sv»t«ms
cl Proc*H Unit Slowdown
OTHER
OIL t GAS PRODUCTION FIELDS
NATURAL GAS AND NATURAL
GASOLINE PROCESSING
PLANTS
GASOLINE & CRUDE OIL STORAGE*
SHIP AND BARGE TRANSFER OF
GASOLINE & CRUDE OIL
BULK GASOLINE TERMINALS J
GASOLINE BULK PLANTS3
SERVICE STATION LOADING llUOI II
SERVICE STATION UNLOADING (ttag* II)
OTHER
ORGANIC CHEMICAL MANUFACTURE
PAINT MANUFACTURE
VEGETABLE OIL PROCESSING
PHARMACEUTICAL MANUFACTURE
PLASTIC PRODUCTS MANUFACTURE
RUBBER PRODUCTS MANUFACTURE
TEXTILE POLYMERS MANUFACTURE
OTHERS
LARGE APPLIANCES
MAGNET WIRE
AUTOMOBILES
CANS
METAL COILS
PAPER
FABRIC
METAL FURNITURE
WOOD FURNITURE
FLAT WOOD PRODUCTS
OTHER METAL PRODUCTS
OTHERS
ARCHITECTURAL COATINGS
AUTO REFINISHING
OTHERS
DECREASING
ORY CLEANING
GRAPHIC ARTS
AOHESIVES
CUTBACK ASPHALT
OTHER SOLVENT USE
FUEL COMBUSTION
SOLID WASTE DISPOSAL
FOREST. AGRICULTURAL, AND OTHER
OPEN BURNING
TOTAL VOC EMISSIONS FROM STATIONARY SOURCES

HIGHWAY VEHICLES
•) Li0tt Duty Automobiles
bl Lilht Duty Truck!
«> Huvy Duty Onolliw Truck!
<) Hwry Duty DMMl Truck!
•) MotorcyclM
OFF-HIGHWAY VEHICLES
RAIL
AIRCRAFT
VESSELS
TOTAL VOC EMISSIONS FROM MOBILE SOURCES
TOTAL VOIATM.E ORGANIC (MISSIONS

BASE VEAR
EMISSIONS
•77




















































IM2 IIM7I PROJECTED ALLOWABLE EMISSIONS
EMISSIONS FROM
SOURCES EXISTING
INIS77




















































GROWTH SINCE
1*77




















































OTAL





















J






























i ««clMtto! ««pt tarn M HNIM ttrtgm and bulk plum.
                                   13-9

-------
                    Chapter  14
                     Liquid  Asphalt
Lesson Goal:
Lesson Objectives:
References:
To illustrate the reductions in VOC emissions that result
from changing from cutback asphalt to water-emulsified
asphalt.

Upon completion of this lesson, you should be able to:
• Define cutback asphalt.
• List three types of cutback asphalt.
• Describe how  an emulsified asphalt is produced.
• Recall the VOC emissions from solvent-based cutback
  asphalt.
• Recall the VOC emissions from emulsified asphalt.
• Recall the relative costs of producing cutback and
  emulsified asphalt.

Environmental Protection Agency (EPA).  1977. Control
of Volatile Organic  Compounds from the  Use of Cutback
Asphalt. EPA-450/2-77-037.
The Asphalt Institute. 1979. A Basic Asphalt Emulsion
Manual. College Park, MD: Manual Series No. 19
(MS-19).
                                 14-1

-------
    LIQUID ASPHALT
                   Binder
  CUTBACK ASPHALT
   Asphalt
RAPID CURE  MEDIUM CURE SLOW CURE
                            14-2

-------
        LIQUID ASPHALT USES

            Prime Coat
            Tack Coat
            Pavement Sealers
            Surface Treatment
            Road Mixing in Place
            Blade Mixing
            Cold Mix - Patch
            Mulch Treatment
Pavement Sealers
       SURFACE TREATMENT
   Aggregate  ^
    Spreader/
      ROAD MIXING IN PLACE
                       Travel Plant
                                       14-3

-------
   BLADE MIXING
 COLD MIX - PATCH
  MULCH TREATMENT
 EMISSION FACTOR -
SOLVENT EVAPORATED
               Average
 Rapid Cure        80%
 Medium Cure      70%
 Slow Cure
25%
     EXCEPTIONS
 • cold weather < 50' f
 • stockpile storage longer than
  one month
 • prime coat
 • demonstration of no VOCs
  from cutback
                             14-4

-------
                    Chapter   15
           The  Regulatory Approach
                 to VOC Control—II
     Regulatory Strategies for NAAQS Attainment
Lesson Goal:


Lesson Objectives:
 References:
To describe the function of VOC regulations in plans for
meeting the oxidant standard in nonattainment areas.

Upon completion of this lesson, you should be able to:
• Describe in general terms the process for developing
  emission control regulations for a nonattainment area
  from ambient air quality data and emission
  information.
• Identify the role of the New Source Review (NSR) pro-
  cess in attaining and maintaining the ozone standard.
• Explain the relation of Reasonable Further Progress
  (RFP) tracking to the other elements of the nonattain-
  ment area SIP.
• State the authoritative sources of guidance concerning
  Reasonably Available Control Technology (RACT).

Environmental Protection Agency (EPA). 1979. Guideline
for Interpretation of Ozone Air Quality Standards.
EPA-450/4-79-OOS.
Environmental Protection Agency (EPA). 1979. Example
 Control Strategy for Ozone, Volume 1: General Guidance
for Nonattainment Areas.  EPA-450/2-79-001a.
 Environmental Protection Agency (EPA). 1979. Example
 Control Strategy for Ozone, Volume 2: Case Study of the
 San Francisco Bay Region. 1976-1978.
 EPA-450/2-79-001b.
 Environmental Protection  Agency (EPA). 1977. Uses,
 Limitations,  and Technical Bases for Procedures for
 Quantifying  Relationships Between Photochemical
 Oxidants and Precursors. EPA-450/2-77-021a.
                                 15-1

-------
 200,000
  90,000
     1979
REGULATORY
 STRATEGIES
 FOR NAAQS
ATTAINMENT
     1987
      DETERMINING REQUIRED
      EMISSION REDUCTIONS
      1. Establish baseline air quality
      X Establish baseline emission
        inventory
      3. Apply models
      4. Calculate required reductions
    1.  Establish baseline air quality
  Averaging Tune:
        • inherent in all measurement
          methods and models
        • must be compatible
  1.  Establish baseline air quality
      Design value:
      •  concentration that should be
        reduced to standard
     • ozone — expected exceedances
       equal to 1
     • from current, consistent, reliable
       AQdata
2. Estabish baselne emission inventory
     1977 or
     most recent
     inventory
                     HC
                           H.I.K .—1 i*. ,«.(..
  alt elements
  in consistent
  measurements
                                                15-2

-------
  •  do not "grow"
    inventory
credit reductions
in El
Emission Inventory
200,000
 90,000
   Air Quality
      28ppm
                               .12ppm
     1979                     1987
       • target will be % reduction
     3. Apply models
        Bask Principles
        •  select best model for specific
           pollutant
        • select best model consistent with
           available resources
        •  apply model accurately
        •  model cannot be more accurate
           than available data

         SELECTING BEST MODEL
            m
                               Photochemical
                                Dispersion
                                 EKMA
                                 Rollback
     • data      • money/   •  levels of
                   personnel     analysis
    SaECTlNC CONSISTENT MODEL
          Sophisticated Models
  •  extensive   •  money/     • detailed
     computer      personnel     input data
     time
                                                 15-3

-------
       Agency Resource Limitations
   little access   •  limited     • uncertain or
   to advanced    personnel,    aggregated
   computer      money, time  data
    APPLYING MODEL ACCURATELY
 • Overestimation
Underestimation
        MODELING POINTS

    • critical computational step


    • potentially expensive


    • results are no better than quality

      and control of data
   4.  Calculate required reductions
                     AQ.,,i, - •
                      24 - 5 (.04)

                      .12
                     —  =»•
Emission Inventory
 90,0001
     Air QuaEty
       28ppm
                             12ppm
     W79                    1987
       •  target will be % reduction
                                             15-4

-------
  Control              H»°-12 PPm ^3
  1. Determine design AQ value
  2. Adjust for background and transport
  3. Enter AQ data into rollback equation
  4. Calculate overall required reductions
   1.  Determine design AQ value
2. Adjust for background and transport
     •  Additiviry (A) 20% - 70%
     •  Natural Background .02 - .06 ppm
     •  Manmade Background
     •  Reducible Transport (TR)
     •  Adjusted Air Quality (AQjdj)
 • Calculating reducible transport
       TR  =  TO •" TF
 • Calculating adjusted air quality
 AQadj  = AQdes  - A' TR
                                                15-5

-------
   AQdes-A-TR  =AQadj

     28  -5 (.12-.04) = 24
  3. Enter AQ data into rollback equation
                   - A-T
               34 - .12
               24 - 3 (04)

               '•=  = 55% reduction
 4. Calculate overall required reductions
                      baseline
 200,000
          R 
-------
I. REQUIREMENTS
  A. SECTION 172 (b) (2) OF THE CLEAN AIR ACT

11. APPLICABILITY OF DISCUSSION
  A. RACT
  B. STRINGENT BUT REASONABLE MEASURES
              RACT

    "THE LOWEST EMISSION LIMIT THAT A
    PARTICULAR SOURCE IS CAPABLE OF
     MEETING BY THE APPLICATION OF
     CONTROL TECHNOLOGY THAT IS
   REASONABLY AVAILABLE CONSIDERING
 TECHNOLOGICAL AND ECONOMIC FEASIBILITY-
MI.  DEFINITION OF RACT

    A. TECHNICALLY FEASIBLE
    B. ECONOMICALLY FEASIBLE
    C. APPENDIX B, 40 CFR PART 51
      DOES NOT REPRESENT RACT
 IV. TECHNOLOGICAL FEASIBILITY

     A.STRINGENT.EVEN
       "TECHNOLOGY FORCING"

     B.SIMILARITY OF SOURCES
 V.  ECONOMIC FEASIBILITY

    A. SOURCE SPECIFIC
    B. ECONOMIC WEIGHING OF BENEFITS

    C. PRESENT VALUE ANALYSIS
                                    15-7

-------
               REVIEW
  NSR
    * COMPLEMENTARY DRIVING FORCE
          ADDITIONAL CLEAN UP
          NEW TECHNOLOGY DEVELOPMENT

    * CONSISTENT WITH RFP

    * INSTANTANEOUS "WATCHDOG"
          RFP AND ATTAINMENT
      PART D NSR REQUIREMENTS

      1979 PLAN MUST:
           1. ATTAIN ON TIME - AVOIDS SANCTIONS
           2. IDENTIFY ALLOWABLE GROWTH
           3. CONTAIN NSR REGULATIONS
             *LAER (as defined)
             ^STATEWIDE COMPLIANCE
             *2 OPTIONS ~ un-by-cnt offsets
                     accomodative SIP
             *SIP CARRIED OUT

      POST '82 ATTAINMENT
           4. CONTAIN NSR EVALUATION PROGRAM
     REGULATORY NSR REQUIREMENTS
LOWEST ALLOWABLE EMISSION RATE  (LAER)

           #171 Dfffinition
           * tat SIP
           * In Practice
           * NSPS Minimum
     STATEWIDE COMPLIANCE


          -A1 COMPLIANCE BY APPROVAL

          * APPLICABILITY

            Existing SIP Limits

          * MAJOR EXISTING SOURCES
                                         15-8

-------
      NEW SOURCE REVIEW OPTION
    (ose-by-cos*
        offsets
                  J
occoModative
     SIP
              REASONABLE
                 FURTHER
                   PROGRESS
                      RFP
              Part D Requirements
171(1)     Definition
        • Annual Incremental Reductions
        • Substantial Early Reductions — Regular thereafter
        • Provides for Attainment
172(b)(3)  Plan Requirements

         • Require RFP including RACT
              MSI '12 SIP'S / ItCKUTE IFF
          !•?» M SI  I!
                        • I ••  «7 M
                RFP TRACKING
             3 MECHANISMS
              • annual emission trends
              •Ad trends  qualitative
              • NSR Instantaneous
                                                 15-9

-------
          AFP SCHEDULES
 I   "
              'Linear Prismption
               1979 Submittals  optimal
               Later revision as necissarj
               1912 tttiiMMts
                     {all
              I|PI ll IIF IcIlUll
      SUMMARY
•  need for attainment
   plans for nonattainmenl
   areas
• Determining required emission
  reductions
  • baseline air quality
  • baseline emission inventory
  • air quality modeling
  • calculation of reductions
    Obtaining emission
    reductions
    • RACT — existing sources
    • NSR — new or modified sources
    • LAER
                                        15-10

-------
• Reasonable further
  progress requirements
  • annual incremental reductions
  • annual tracking reports
    Bask goal
    • attaining and maintaining
     the ozone NAAQS
                                   15-11

-------
                     Chapter   16
            Methods of  VOC  Emission
               Control—Incineration
Lesson Goal:
Lesson Objectives:
 References:
To provide you with an understanding of the basic con-
cepts of incineration and heat recovery as they apply to
VOC control.

Upon completion of this lesson, you should be able to:
• List three methods used to incinerate VOCs
• Identify the conditions necessary for efficient combus-
  tion of organic materials in a direct flame
  incinerator—including the effect of gas conditioning,
  temperature, and residence time.
• Explain the operation of at least two types of direct
  flame incinerators—including the purpose of baffles,
  multijets, and distributed burners.
• Identify the conditions necessary for the efficient com-
  bustion of organic materials in catalytic incinerators—
  including the effect of catalysts, temperature, residence
  time, etc.
• Discuss the advantages and disadvantages associated
  with catalytic incineration.
• Discuss the problems inherent hi using process boilers
  for incineration.
• Diagram at least two types of methods used for heat
  recovery.
 • Discuss the advantages, problems, and  limitations
  associated with primary and secondary heat  recovery.
 • Discuss the factors (including relative cost) to consider
  when determining what type of heat recovery system to
  use.
 •  List several sources of VOC emissions that would most
   likely use incineration as a method of VOC control.

 National Technical  Information Services (NTIS). 1972.
 Afterburner Systems Study. PB-212 560.
 Environmental Protection Agency (EPA). 1977.  Con-
 trolling Pollution from the Manufacturing and Coating of
 Metal Products. Metal Coating Air Pollution Control.
 Technology Transfer Publication. EPA-625/S-77-009.
             16-1

-------
     DIRECT FLAME INCINERATION
       Fum*
  Fuel
                            Exhouit
  "
o
i
                    EFFECTS OF
                 TEMPERATURE AND
                  TIME ON RATE OF
               POLLUTANT OXIDATION
   400 tOO 1000  1200 1400 1600 1400 2000
         Increasing T»mp»ratur«
       TYPICAL AFTERBURNER
     OPERATING TEMPERATURES

                  1200°-1500°F
                  'H000-1500°F
                  1300°-2000°F
              	1300°-1500°F
Wire Enameling     1300°- 1400°F
 Coil
 Paint Dake Ovens
 Petroleum Refining
       DESIGN RANGES
 Temperature  1300 ° - 1500° F
 Detention     0.3 - 0.5 seconds
 Time
 THERMAL DESIGN FACTORS
 Efficiency increases withi
     • operating temperature
     • detention time
     • Initial hydrocarbon concentration
     • flame/solvent contact
     • good mixing
     • CO removal
        (at temperatures >1000°F)
                                      16-2

-------
     CATALYTIC INCINERATION
 Diffusion
         (bi
   Adsorption
              PRINCIPLES OF
               OPERATION

         Reaction
           Desorption
Diffusion and
    Mixing
    ADVANTAGES OF
CATALYTIC INCINERATION

 • lower operotingjemperotures
 • lower ouxilory fuel needs
 • lower construction materials cost
   DISADVANTAGES OF
CATALYTIC INCINERATION
    • partlculate fouling
    • thermal aging
    • catalyst poisoning
    • suppressants
        PLATINUM
    CATALYST POISONS
Fast
P
Dl
As
Sb
Hg
Slow
Zn
Pb
Sn
High Temp.
( >1100°F)
Fe
Cu
                              16-3

-------
            PLATINUM
   CATALYST SUPPRESSANTS
           •Sulfur
           • Halogens

       action is reversible
           PROCESS
           BOILERS
CONDITIONS FOR INCINERATION USE

  • sufficient residence time

  • no dependency
  • low fuel/oxygen rat*
  • unaltered flame and radiation patterns

  • non-fouling or add fumes
                   Catalyst. If any
Contaminated Vaste Gat
                           To
                           ^Atmosphere
                       Afterburner
I Process
 AFTERBURNER CONFIGURATION
    WITHOUT HEAT RECOVERY
       AFTERDURNER CONFIGURATION
      WITH PRIMARY HEAT RECOVERY
                                     16-4

-------
                             Afterburner

                Recycle Heoi Recovery



                        To Atmosphere

         AFTERBURNER CONFIGURATION WITH
            PRIMARY HEAT RECOVERY
        AND DIRECT RECYCLE HEAT RECOVERY
    Primary Heat
    Recovery
   ^^^^^     I          Afterburner

   •Processi    I AFTERBURNER CONFIGURATION
   VHBf    I WITH PRIMARY AND SECONDAP
    ^^^     Y       HEAT RECOVERY
  Sccondar
  H«ot Recovery
                             To Atmosphere
  RECUPERATIVE
      HEAT
   RECOVERY
     DEVICE
REGENERATIVE
    HEAT
 RECOVERY
   DEVICE
   (Reeco)
        Hmtocavwy
                               Fum*s From
   TUDULAR HEAT EXCHANGER SYSTEMS

 ' Effectiveness ratio, E
     1. Stage SOX mox.
     2. Stag* 62 X max.
     3. Stage 83X mox
  Limitation
     Easily fouled
     Structural failures
     Cherrtcol Interactions with fume components
     Corrosion
                                                   16-5

-------
  AFTERBURNER PROCESS HEAT RECOVERY
                              -1JOO°f	
  I..
                      MOTE, Final T»mp»ratur»
                        of Hu» 001 = 350° F
                        Fum* strcom used for
                        oxygen supply

                        12,000
           4.000   EOOO   12,000  16.000
            Aft»rborn«r Capacity,tcfm
       CAPITAL COST OF INCINERATION
        • Thermal • Catalytic
          -Vlthoul (xchangif
                 10    13   20
               Flow, 5cfm x 10a
                                      30
ANNUAL VARIABLE COST OF INCINERATION
     243 I	
             Thermal   • Catalytic
             •  Without Mttlionon

        .——  Vlth (xlmoiy <
        ._._._  vith pamaiy and.
                 10    19    20
                 Flow.srfm x 10 a
                                                   16-6

-------
                    Chapter   17
            Methods of  VOC Emission
                Control—Adsorption
Lesson Goal:
Lesson Objectives:
References:
To provide an understanding of the basic concepts of car-
bon adsorption as applied to VOC control.

Upon completion of this lesson, you should be able to:
• Define the following terms as they apply to the adsorp-
  tion process: adsorption, adsorbent, adsorbate, activa-
  tion, build-up, retentivity, regeneration and
  breakthrough.
• Explain, with the aide of suitable diagrams, the
  dynamics of the adsorption process.
• Explain the relative effects of temperature, gas velocity,
  preferential adsorption, concentration, bed depth,
  pressure, and paniculate matter on the adsorption
  process.
• Diagram a regenerative adsorption system and list three
  problems associated with the recovery process.
• Summarize the exhaust gas stream conditions under
  which effective adsorption occurs.

Bethea, R. Air Pollution Control Technology. 1978.
Chapter 13. New York. Van  Nostrand Reinhold Co.
Environmental Protection Agency (EPA). 1973. Packing
Sorption Device System Study. Washington, DC. EPA-
RZ-73-202.
 Parmele, C.  S., O'Connell, W. L. and Basdekis, H. S. 1979.
 Vapor Phase Adsorption Cuts Pollution Recovers Solvent,
 Chemical Engineering.  82:58-71.
                                 17-1

-------
                  ADSORPTION
                       ~rasatw-~~
                    TYPES OF

                  ADSORBENTS

                   • activated carbon
                   • molecular sieves
                   • silica gels
&/)
VAN DER
WAAL
FORCE
               molecule
               adsorbate V
molecules in
 adsorbent
  wall
                            wall of
                            absorbent
                   ;-V-7Y  CU	
                  v/ ^ / r
                                        17-2

-------
  RETENTIVITY
        Temperature
 TYPICAL ADSORPTION
M      ISOTHERM
i100
1
  20
                  77 op
      0.001  0.01  0.1   1.0

       Partial Pressure, psla
 »>
 I
 I
        Surface Area
   Molecular Weight of Solvent
                              17-3

-------
  Adtorbtion Zone  Saturated Bed
        BED
   GEOMETRY
  EFFECT OF GAS VELOCITY
EFFECT OF BED DEPTH
 0    10   20   30  40   50

       Bed Depth, inches
    MULTIPLE SOLVENTS
Decreasing  ^^^^^^^ ~       , A
    Muy  ^^^^^^H Compound A
         •^^H^^B^^^B^^^^ml
                  Compound B

                  Compound C
I
                             17-4

-------
 HUMIDITY


    /OC
45% - maximum relative humidity
                          '
-------
    REGENERATIVE CYCLE
                      Condenser
                      Solvent
   ADSORPTION CYCLE
                      Condenser
              V - SHAPED
                 BED


             —— Housing
              — Carbon
                                      
-------
         ROTARY BED
           Steam And Vapor Out
                 REGENERABLE
                 Fluidized Bed
     APPLICATIONS

    • Coating Operations
    • Degreasing Operations
    • Gasoline Marketing
    • Odor Control
      ADSORPTION
• 90%+ efficiency
• Handles high VOC concentrations
• Humidity > 45% decreases efficiency
' Design problems with VOC mixtures
• Higher MW compounds adsorbed
 more readily
                                    17-7

-------
   Chapter 18

The State VOC Control
Program—an Example
         18-1

-------
18-2

-------
18-3

-------
  Chapter 19
Homework Problems
       19-1

-------
U1
                              Problem Set 1—Coating Calculations

                  A captive can coater roller-coats sheet stock to prepare cans for a food processing
                  plant. As a result of recent changes in the State Implementation Plan (SIP), he is
                  now required to meet RACT emission limits of 2:/79Jbs VOCs/gallon of coating
                  (minus water) for the interior base coat.

                  Part A

                  If the coater presently uses a rosin ester containing 35% by volume of solids
                  (remaining content organic volatiles) for the interior base coat, compute the
                  following:                ^fYo
                    1. the present-emissions (Ibs VOCs/gallon coating (less water)).
                    2. the emissions (Ibs VOCs/gallon coating (less water)) if the coating formulation
                      for the interior base coat was changed to a water borne coating containing
                      50%  solids with an 80:20 (80% water, 20% organics) water borne solvent.
                    3. the percent VOC reduction realized.
                    Assume  a VOC solvent density of 7.36 Ibs/gallon.
                    Hint: Use Figure 1  and Figure 2 for this part of the problem.
                                                         Answer #1 =   ^    '  /   1h«/ga11on

                                                         Answer #2 =     	Ibs/gallon

                                                         Answer #3 =.
                                                      19-2

-------
            -77%
PartB

If a can coater presently uses a tt% so]ids hy vnlnmp polyester resin for an exterior
base coat with a 60^40 water borne solvent (60% water, 40% organics),  compute
the following:
  1. the present emissions (Ibs VOCs/gallon coating (less water)), (assume solvent
     density to be 7.36 Ibs/gallon).
  2. the emissions (Ibs VOCs/gallon coating (less water)) if the coating formulation
     for the exterior base coat was changed to 80% solids in a 70:30 water borne
     solvent (70% water, 30% organics).  In this case,  the density of the organic
     solvent was not 7.36 Ibs/gallon,  but  had a value of Tjt&Jbs/gallon.
  3. the percent VOC reduction realized.
  Hint: Use the calculation methods given in the "Coating Calculations" discussion
which follows.
                                        ,   /
                                       w" •
                            Answer #1  /«£/

                            Answer #2.

                            Answer #3
   VOC/gal coating (less HZO)
Ihs VOC/gal coating (less H2O)

-------
                                    20        40       60        80
                                    Volume % solids in coating

       Figure 1. Weight of organic solvent per gallon for 3 coatings as a function of solids content.
                                                          Solvent content of
                                                          oriemai coating
                                   1234567
*7 Aw ^e>Vi€*vC'     Pounds of solvent per gallon of replacement coating (less water)

              Figure 2. Percent VOC emission reduction using replacement coatings.
                                  (Solvent density a 7.36 Ib/gal)
                                                19-4

-------
Coating Calculations

This discussion provides assistance in working Problem Set 1 .  It reviews methods of
                   farforg for coatings in terms of the RACT units: Ibs
VOC/(gallon coating applied— H20). The purpose of excluding water is to avoid
the problem of achieving compliance merely by diluting the paint. Another method
of describing VOC emissions from a coating formulation is on the basis of Ibs
VOC/gallon solids.  If the surfajcp ?rea of the material being coated is koQwji and if
the dry coating thickness can be determined, the amount of VOCs emitted can
easily be determined by finding fhe flum,ber pf gallons of solids that would give the
      a^y fflYfjagf— The analytical methods of measuring the  volume ot cured
coating can be complex. As an alternative, the RACT limits were developed in
terms of Ihs J/OCjej gallpn of uncured solvents and organic solvent less water.
  Two methods for calculating emissions in terms of RACT units (Ibs
VOCs/ (gallon coating— HZ0)) are presented in Problem Set 1. The first method
uses Figure 1 .  Figure 2 enables you to calculate percent reductions realized by
changing coatings. Figure 1 assumes that the organic solvent of the coating has a
density of 7.36 Ib/gal (note: this is the density only of the organic solvent, not the
total solvent or the total paint composition). The figure gives only information for
paints of three solvent compositions— an organic borne coating, an 80:20 water
borne coating (80% HZ0) and a 70:30 waterborne coating.
  To use the graph, locate the volume % of solids on the x-axis. Draw a vertical
line to the curve which describes the solvent composition  (you would have to inter-
polate or develop other curves for compositions differing  from the three given).
Draw a horizontal line to the y-axis and read the solvent  emissions in terms of Ibs
solvent/(gal— HZ0). Do this for both the presently used coating and the replace-
ment coating.
  Figure 2 is used to determine the percent reduction in  emissions which will be
realized by going to the replacement coating. To use Figure 2, find the curve cor-
responding to  the solvent content of the original coating (you may have to inter-
polate between curves). Next, locate the solvent content in lbs/(gal — H20) of the
replacement coating on the x-axis. Draw a vertical line up to the curve corres-
ponding to the original coating. Locate the point of intersection and then draw a
horizontal line from that point to the y-axis. Read the percent reduction from the
y-axis.
  This graphical procedure is given in the CTG: "Control of Volatile Organic
Emissions from Existing Stationary Sources— Volume II," EPA-450/2-77-008, May
1977. The graphs can give you a quick way of determining emission levels and
emission reductions. The graphs were developed from simple mathematical calcula-
tions and  are not empirical in nature. In cases where the organic solvent density is
not 7.36 Ibs/ gal,  or where it is desired not to interpolate, the mathematical pro-
cedures which follow can be used.
                                     19-5

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                                                                  -v     ,   .-  |;   A
                                                                  t   *f,c<$      f  ^ ^


                  Part B of Problem I  can be solved by using the following expressions:

                  • Emission factor in  RACT units Ibs VOC/(gal-H20).
                                                    ef=
                                                       1— ws


                  Where:   ef = emission factor Ibs VOC/(gal-H20)

                             _ % organic volatiles in solvent
                            v                —-



                                % H20 in solvent
                                       100

                               % solvent  in the paint
                           s=	*•	
                                        100


                           QV = density organic volatiles (  — j.
                                                       \ga1-/

                  • Emission factor on a solids' basis (Ibs VOC/gal solids)


                                                    r»    Vs6v
                                                   et  = ——
                                                         l-s


                  Where:  ef' = emission factor Ibs VOC/gal solids


                  • Percent emission reduction



                                          % reduction = ef°'"'~ ef~" iQO



                Where:   ef^, = emission factor on a solids' basis for original coating

                         efr'.p = emission factor on a solids' basis for replacement coating


                  The following examples  illustrate the use of these equations:

                  Example 1: Determine the emission factors, ef and ef', for an organic solvent-

                borne coating which contains 40% organic solvent  having a density of 7.36 Ibs/gal.

                                             IX.40x7.36
                                    ibs/(gal_H,0)
         -ws         -                 V6       '

 c,   vsgv    IX. 40x7. 36
ef ' = — m. = - =
      l-s        1-.40
                                                                    n»,     ,.,
                                                                 4.90 Ibs/Wl solids
DT?o.(flU'.c.  -Sois^va  r  *1
   u
                                                      19-6

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  Example 2^_Determine the emission factors ef and ef ' , for a waterborne coating
containing fiFffi solvent with 80% of the solvent being water. The density of the
organic portion of the solvent is 7.36 Ibs/gal.

           ef=J.gJL=(.20)(.65)(7.36)=_:957_ ^ lbs/(gal_Hj0)
               1-ws    1-(.80)(.65)    1-.52

              .,   vsov    (.20)(.65)7.36    .957   _ __ „   .  ,   r ,
             ef ' = — ^L = .i - ii - L - =  - =2.73 Ibs/gal solids
                  1-s       1-.65        .35

  Note here that vs= .20X .65= .13 is the volume fraction of organic solvent in the
gallon of paint and .80 X .65 = .52 is  the volume fraction of water in the gallon of
paint.
          ^B: Calculate the percent reduction in volatile organic emissions
achieved by switching from the coating given in Example 1 to that given in
Example 2.
                         % reduction =
                                     , 4.90- 2.73
                                           4.90

                                     = 44.3%

  Note: This calculation is performed using the emission factor computed on a
solids ' basis. This is done so that we are comparing the same things. A gallon of
paint with 60% solids will cover more surface area (1 mil thick) than will a 35%
solids paint. [If the calculation was performed using  the other emission factors
(Ibs/gal— H20), we would just be comparing the reduction of volatiles between
buckets of paint (with water removed). That is, to cover a given surface area  1 mil
thick, we  might need 1 bucket of one coating, but using another, 1 Vi buckets. This
factor does not appear in doing the %  reduction using ef values.]
                                     19-7

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(D
   Qtr
           '1J-
   6
                                      (.A 2,0
                                                            0
                              o. ^ s
                                                   <2JUL

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Problem Set l__rvi   ,
    v        '-Calculation Sheet
       J9-9

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           Problem Set 1—Coating Calculations
                                     Name.
                                     Date _
Hand in Answer Sheet (to be handed in Wednesday morning)
Part A
  Answer #1 =.
  Answer #2 =.
  Answer #3 =.
Jbs/gallon coating (less H2O)
Jbs/gallon coating (less H2O)
Part B
  Answer #1 =.
  Answer #2 =.
  Answer #3 =.
Jbs/gallon coating (less HZO)
Jbs/gallon coating (less H2O)
                               19-11

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        Problem Set  2—Storage Tank Calculations

Problem 2.1

A petroleum refinery has a 60,000 bbl external floating roof tank, equipped with
only a primary shoe seal. The tank is of welded construction.
   Compute the following:
   1. Present VOC emissions from the tank.
   2. VOC emissions after applying RACT (secondary seal).
   3. Dollar savings per year (gasoline 90
-------
   b. Withdrawal losses
                            0.943
                                  n
      [NOTE: Constant 0.943 has units of (1000 ft3 X gal/bbl2)

      Substituting in the given data
                       ,  _(0.943)(450,000)(0.0015)(5.6)
                       *->W — "     —   —   ---- -  ,.,..- ---
                                       100
                       L,v= 36 Ib/yr

   c.  Total emissions from the tank
                       LT = Lfc+ Lw
                       LT= 39,400 + 36
                       Lr= 39,436 Ib/yr
2.  VOC emissions after applying RACT (secondary rim mounted seal)
   a.  Standing losses
                       L, = KsV"P*DMKcEf
      Now K, is reduced to .2 and n is  1 from Table 2.
                       U = 2072 Ib/yr
   b.  Withdrawal loss
                       Lw=36 Ib/yr
      Same as 1-b since the annual throughput doesn't change
   c.  Total emissions
                       L,;- = L.J 4- LW
                       Lr=2072 + 36
                       Lr=2108 Ib/yr
3. Money saved by applying  RACT
                       39,436 Ib/yr before controls
                        2,108 Ib/yr after controls
                       37,328 Ib/yr reduction
                    37,328 Ib/yr ( J2L V ^^\ = $6000/yr
                              '  \5.6 IbA  gal /         y
                              19-14

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                        1
                              l
Problem 2.2
A chemical plant uses benzene in the manufacture of styrene. They store the
benzene in a small  25,000 gal fixed roof tank. The company plans to install an
internal floating roof with a secondry seal system to reduce the benzene losses.
ComputeThe following.           t^oul YYuxMr^ rt£iU«rA M V>«(

1.  Present benzene emissions from the tank.
2.  The emissions after installing the floating roof.
3.  The dollars saved per year assuming benzene is wo.
                                    Data

Tank capacity = 25,000 gal
Tank diameter  (D)= 12 ft
Tank height = 36 ft
Annual throughput = 800,000 gal/yr (approx. 19,000 bbl/yr)
Tank i§jaenilally  •H  iull,"assume a flat roof
        painted white
  lolecular weight of benzene (M) = 78^b./lb mole
 Jensity (Wf)= 7.4 Ib/gal ;
 Average wind speed (V) = 8 mph
 Cling factor (C) = 0.0015 bbl/1000 ft2
 Average daily temperature change (AT)= 18°F
                                                        v\
                                                        o.M
                                                                     1
                                                      1.2/14.1
0,0
                                     19-15

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Problem Set 2—Calculation Sheet
               19-16

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Problem Set 2—Calculation Sheet, continued
                    19-17

-------
               Lfl=6.19xl(r5 M

Where:     LB = Fixed roof breathing loss (Ib/day)
            M = Molecular weight of vapor in storage tank (Ib/lb mole)
            P = True vapor pressure at bulk liquid conditions (psia)
            D = Tank diameter (ft)
            H= Average vapor space height, including roof volume correction
                (ft); see note (1)
            AT = Average ambient temperature change from day to night (°F)
            Fp — Paint factor (dimensionless); see Table  1
            A = Adjustment factor for small diameter tanks (dimensionless);
                see  Figure 5
            Kc = Crude oil  factor (dimensionless); see note (2)
            Note:  (1) The vapor space in a cone roof is equivalent in volume to a
                     cylinder which has the same base diameter as the cone and is
                     one-third the height of the cone.
                  (2) Kc = (0.65) for crude oil, Kf-(l. 0) for gasoline and all
                     other liquids.

                     Figure 3. Fixed roof breathing loss equation.
                             Lw= 2.40 X l(T2MPrvvKc

Where:     Lw = Fixed roof working loss (lb/103 gal throughput)
            M = Molecular weight of vapor in storage tank (Ib/lb mole)
            P = True vapor pressure at bulk liquid conditions (psia)
            K^ = Turnover factor (dimensionless); see Figure 6
            Kc = Same as Figure 3

                      Figure 4. Fixed roof working loss equation.

From: U.S. Environmental Protection Agency. 1977. Compilation of Air Pollution Emission tutors.
Third Edition. AP-42.
                                      19-19

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               Table 1. Paint factors for fixed roof tanks

Tank
Roof
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray

color
Shell
White
White
Aluminum (specular)
Aluminum (specular)
Aluminum (diffuse)
Aluminum (diffuse)
Gray
Light gray
Medium gray
Paint factors (Fp)
Paint condition
Good Poor
1.00 .15
1.04 .18
1.16 .24
1.20 .29
1.30 .38
1.39 .46
1.30 .38
1.33 .44"
1.40 1.58"
"Estimated from the ratios of the seven preceding paint factors.
        1.00
     u
     a
     i
     •o
         .20
                            10               20

                           Tank diameter in feet



      Figure 5. Adjustment factor (A) for small diameter tanks.
                                19-20

-------
     1.0
I
u

-------
Where:     Lj = standing storage loss (Ib/yr)
            Ks = seal factor (Ib mole/[ft(mi/hr)"yr])  See Table 2
            V = average wind speed (mi/hr)
            n = seal-related wind speed exponent (dimensionless) See Table 2
            P* = vapor pressure function (dimensionless)
                       P
                      (K)
                 1+1
            P = true vapor pressure at average stock storage temperature (psia)
            P,, - average atmospheric pressure at tank location (psia)
            D = tank diameter (ft)
            M = average molecular weight of stock vapor (Ib Ib mole)
            Kc = product factor (dimensionless) see Note 1
            Ef = Secondary seal factor dimensionless see Note 2
Note: (1) Petroleum liquids are defined as mixtures of chemicals having dissimilar
          true vapor pressures (gasoline or crude oil). Volatile organic liquids are
          defined as mixture of chemicals with similar true vapor pressures
          (benzene or a mixture of isopropyl and butyl alcohols).

          Kc = (0.4) for crude oil

          Kc = (1.0) for all other petroleum liquids

          Kc = (10.0) for volatile organic liquids

      (2) EF = (1.0) for all petroleum liquids, E/=(1.0) for all (volitilejorganic
          liquids with only a primary seal,                   V-

          Ef = (0.25) for volatile organic liquids with  a primary and secondary seal
          system. However when selecting values of K5 and n from Table 2, one
          must use the primary only values.
             Figure 7. Standing losses from external floating roof tank.
                                      19-22

-------
                               L,= K.V"P*DMKeEjr

Where: the terms are defined the same as Figure 7, except:

 K,= 0.7 for all seal systems

 Kc = same as  Figure 7

 n = 0.4 for all seal systems

 EF = 1.0 for the storage of any liquid that has only a primary seal system on the
 tank

 Ejr= 0.25 for storage of any liquid that has both a primary and secondary
 seal system on the tank

                Figure 8. Standing losses from an internal floating roof tank.
                                          D

Where:     Lw = withdrawal loss (Ib/yr)
            Q= average throughput (bbl/yr)
            C = shell clingage factor (bbl/1000 ft2) see Table 3.
            Wf = average stock liquid density (Ib/gal)
            D = tank diameter (ft)

            [NOTE: Constant 0.943  has units of (1000 ft3Xgal/bbl2)


        Figure 9. Withdrawal losses from both internal and external floating roof tanks.
From: American Petroleum Institute (API). 1980. Evaporative Losses from External Floating Roof
Tanks. Second Edition. API 2517.
                                       19-23

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  Table 2—Summary of average seal factor (KJ and wind speed exponents (n)
                   Tank/seal type
K
Welded tanks
1.  Mechanical shoe seal
   a.  Primary only
   b.  Shoe-mounted secondary
   c.  Rim-mounted secondary
2.  Liquid-mounted resilient filled seal
   a.  Primary only
   b.  Weather shield
   c.  Rim-mounted secondary
3.  Vapor-mounted resilient "filled seal
   a.  Primary only
   b.  Weather shield
   c.  Rim-mounted secondary
Riveted tanks
   a.  Mechanical shoe primary only
   b.  Shoe-mounted secondary
   c.  Rim-mounted secondary
1.2
0.8
0.2

1.1
0.8
0.7

1.2
0.9
0.2

1.3
1.4
0.2
                        Table 3. Average cling factors (C)
                                  (bbl/1000 ft,)

Product
Gasoline
Crude Oil
Shell conditions
Shell Conditions
Light rust
0.0015
0.0060
Dense Rust
0.0075
0.030
Gunite-lined
0.15
0.60
                                     19-24

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      Problem Set 2.2—Storage Tank Calculations
                                    Name_
                                    Date	
Hand in Answer Sheet (to be handed in Thursday morning)


VOC emissions from fixed roof tank
VOC emissions from fixed roof tank after installing internal
     floating roof
Money saved
                               19-25

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
 EPA 450/2-81-011
                                                            3. RECIPIENT'S ACCESSION>NO.
 4. TITLE AND SUBTITLE
  APTI  Course 482
  Sources  and Control of Volatile  Organic Air Pollutants
  Student  Workbook	
                                                            5. REPORT DATE
                                                                Ma-rrVi  1 Qftl
             6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
  D.S. Beachler, J,A. Jahnke, J.T.  Joseph
  J.E. Maroney
             8. PERFORMING ORGANIZATION REPORT NO
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Northrop Services, Inc.
  P.O, Box 12313
  Research Triangle Park, NC  27709
              10. PROGRAM ELEMENT NO.

                 B18A2C      	
              11. CONTRACT/GRANT NO.

                 68-02-2374
 12. SPONSORING AGENCY NAME AND ADDRESS
  U.S.  Environmental Protection Agency
  Manpower and Technical Information Branch
  Air Pollution Training Institute
  Research Triangle Park, NC   27711
              13. TYPE OF REPORT AND PERIOD COVERED
              14. SPONSORING AGENCY CODE

               EPA - OANR-OAQPS
 15. SUPPLEMENTARY NOTES
  Project  Officer for this workbook is R,E, Townsend,  EPA-ERC, MDr-17, RTF, NC  27711
 16. ABSTRACT
     The  Student Workbook is  to  be used for the Air Pollution Training Institute
 Course 482,  "Sources and Control  of Volatile Organic  Air Pollutants",  This  publica-
 tion  contains chapters corresponding to each of the eighteen lessons and a chapter
 containing two problem sets.  Each chapter contains a lesson goal, lesson objectives
 and any  special reference that  would provide helpful  background material for the
 subject  area covered in the  chapter.  Each chapter contains important black  and white
 reproductions of selected slides  used in the training course.  This publication is
 designed to  be used as a student  aid for the training course.

     This publication is intended  for use in conjunction with the Instructor's Guide
 (EPA  450/2r*81-01Q) and the Regulatory Documents  (EPA  450/2^81-012) for APTI  Course
 482,
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS  |c. COSATI Field/GfOUp
  Air  Pollution Training
  Control of Volatile Organic  Compounds
 Training  Course
 Student Workbook
   13B
     51
   68A
 8. DISTRIBUTION STATEMENT
 National Technical Information Service
 5285  Port Royal Road
 finrlngfteld. VA  22161    	
19. SECURITY CLASS (ThisReportf
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21. NO. OF PAGES
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EPA Form 2220-1 (>-73)
                                         19-27

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