Un.ted States
Environmental Protection
Agency                                   1981

          OF

                               BY
                 for
      of

             1-10
                 by


                        NC 27711

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                 RESEARCH  REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination  of  traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental Studies

    6. Scientific and Technical Assessment Reports (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports

This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND  DEVELOPMENT series. Reports in this series result from the
effort funded  under  the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport  of energy-related pollutants and their health and ecological
effects;  assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
                       EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for  publication. Approval does not signify that the contents necessarily reflect
the  views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.

This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                                      May, 1981
                FINAL REPORT
                     on
          CONTROL OF EMISSIONS FROM
          RESIDENTIAL WOOD BURNING
         BY COMBUSTION MODIFICATION
                     by
      John M. Allen and W. Marcus Cooke
       Battelle Columbus Laboratories
           Columbus, Ohio  43201
         Contract Number 68-02-2686
             Task Directive 114
               Project Officer

               Robert E. Hall
         Combustion Research Branch
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina  27711
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA  27711

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                                 DISCLAIMER
     This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.

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                                ABSTRACT
          This report describes an exploratory study of the factors
contributing to atmospheric emissions from residential wood-fired com-
bustion equipment.  Three commercial appliances were operated with both
normal and modified designs, providing different modes of burning.
Operating conditions included up draft using a grate, up draft using
hearth, cross draft, down draft, and a high turbulence mode utilizing
a forced draft blower.  Fuels used were naturally dried commercial oak
cordwood, commercial green pine cordwood, oven-dried fir brands, and
naturally dried oak cut into reproducible triangular shapes.  Continuous
measurements of stack gases included 02, C02, CO, NO, S02, and total
hydrocarbons (FID) as an indication of the total organic species in the
stack gases during batch type operation.  Several combustion modification
techniques were identified which have an appreciable effect on emission
and therefore can be developed and applied to reduce emissions in consumer
use.  The more promising design modifications include:  prevention of
heating the inventory of wood within the stove but not yet actively burning
focus of air supply into primary burning area with high turbulence, and
increase the temperatures in secondary burning regions of the appliances.

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                                 CONTENTS
Abstract	    ii
Figures	    iv
Tables	     v
Acknowledgments	    vi

   1.  Introduction 	     1
   2.  Conclusions and Recommendations	     2
   3.  Wood as a Fuel	'	     8
            Properties of Wood	     9
   4.  Combustion Characteristics of Wood	    10
            Evaporation	    10
            Pyrolysis	    10
            Char Formation and Burning	    11 •
            Burning Progression 	    12
            Wood Constituents Resulting in Atmospheric Pollutants ....    12
            Production of PAH in Wood Combustion	    15
   5.  Wood Stove Design and Performance	    18
            Types of Radiant Stoves	    18
            Secondary Combustion	    22
            Commercial High Turbulence Burner 	    23
   6.  Experimental Program	    29
            Laboratory Facility 	    29
            Operating Procedures	    31
            Emission Measurements 	    31
            PAH Measurements	    33
            Data Processing	    35
            Fuel Wood Used	    35
   7.  Experimental Program Observations	    36
            Stove Design Factors	    39
            Operator Factors	    52
            Fuel Properties	    55
            Polycyclic Aromatic Hydrocarbon Emissions 	    61
            Commercial High Turbulence Burner 	    64

References	    66
Appendices

   A.  Emission Measurement Programs	    68
   B.  Examples of Recorded Test Data	    76
   C.  Polycyclic Aromatic Hydrocarbon Measurements in Flue Gas	    82
                                      iii

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FIGURES
Number
1
2
3
4
5
6

7
8
9
10
11
12
13
14
B-l
B-2
B-3
B-4
B-5
C-l
C-2


Pyro-Combustion to Produce Benzo(a)pyrene 	
Generic Designs of Wood Stoves Based on Flow Paths 	
Limits of Ignition at 20°C 	
Limits of Ignition at 270°C 	
Limits of Ignition at 250°C 	
Wood Fired Residential Boiler Utilizing High Turbulence
Burning 	
Laboratory Installation of Stove with Stack and Vent System. .
Continuous Gas Sampling System 	
Particulate and PAH Sampling System 	
Configuration of Stove Converted to Down Draft Mode 	
Air Preheat System 	
CO Emissions for One Stove, Three Modes of Burning 	
THC Emissions for One Stove, Three Modes of Burning 	
Effect of Wood Size on CO Emission Factors 	
Composition of Gas From Up Draft Burning with a Grate 	
Composition of Gas From Side Draft Burning 	
Composition of Gas From Down Draft Burning 	
Composition of Gas From High Turbulence Burning 	
Weight Loss During Side Draft Burning 	
Gas Chromatogram of PAH Standard Mixture 	
Gas Chromatogram of Particulate Associated Organic Compounds
From Seasoned Oak Combustion 	
Page
16
19
24
25
26

28
30
32
34
42
44
56
57
62
77
78
79
80
81
84

85
     IV

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                                 TABLES


Number                                                                   Page

  1      Typical Progression of Local Phenomena in Wood Log Burning .      13

  2      Emissions and Operating Conditions 	      37

  3      Emissions From Different Modes of Burning Fuel:  Oak 4x4.      41

  4      Effects of Preheated Primary Air on Emissions	      45

  5      Effects of Secondary Combustion on Emissions 	      50

  6      Effects of Size of Charge of Emissions	      53

  7      Effects of Wood Moisture Content 	      59

  8      Effects of Wood Size and Shape on Emissions	      60

  9      Emissions from Burning Green Pine	      63

 10      Emissions from High Turbulence Burner	      65

 C-l     Polynuclear Aromatic Species Quantified	      86

 C-2     Total PAH (mg) Emitted in Wood Stove Emissions	      87

 C-3     Comparison of Stove Operating Parameters and Emission Factors
            for PAH Compounds	      89

 C-4     Comparison of Reported PAH Emissions	      91
                                      v

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                               ACKNOWLEDGMENTS
     We wish to acknowledge the assistance of Mr. Robert E. Hall of EPA for
his encouragement and guidance as Task Officer of this program, and his
cooperative position concerning related research.

     Appreciation is also expressed to others on the Battelle staff who
contributed significantly to this program:  Paul Webb who assembled the
test facility and instrumentation, Dale Folsom who conducted many of the
experimental runs, and Abbott Putnam who developed the limits to combustion
in the secondary combustion region.  The authors would also like to express
their appreciation to Marcia Nishioka and Fred Moore for performing the PAH
analyses.
                                      vi

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                                  SECTION 1
                                 INTRODUCTION

          The use of wood for residential heating is certainly not a new
phenomenon.  However, this use of wood has increased appreciably in recent
years and the trend is expected to continue.  It has recently become in-
creasingly apparent that (1) the emissions from residential wood stoves can
in some instances constitute a serious environmental problem, and (2) that
the technology required to burn wood in small stoves without significant
emissions is not now available.  Because the use of this renewable energy
resource is to be encouraged, it is necessary to develop and apply the
technology necessary to make the stoves environmentally acceptable, rather
than restrict their use on environmental grounds.
          This study was initiated to explore the combustion modification
techniques that might be applied beneficially to wood stoves, and more
specifically to identify those techniques which show promise of providing
a significant improvement in emissions when adequately developed and applied,
The focus of the effort is on naturally-drafted, hand-fired radiant stoves,
as these constitute the majority of units used extensively for residential
heating.

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                                    SECTION 2
                          CONCLUSIONS AND RECOMMENDATIONS

          As the result of this study, there appear to be several combustion
modification techniques available to reduce the gas emissions from wood
stoves, with varying degrees of probable effectiveness, and different levels
of acceptability to residential stove builders and operators.  These techniques
are briefly summarized below, noting whether a modified stove design: is
required, special operator techniques are required, or specific as a guide
to indicate the more promising combustion modifications which should be
developed in more detail to justify extensive reduction to practice by
stove users.  Modifications are presented first which prevent gas composition
formation in the magazine (A), and in the primary combustion region (B),
followed by those which cause previously formed gas combustion to be
destroyed within the primary burning zone (c) or in the secondary combustion
zone (D).  Finally, a few add-on devices are identified (E) which may or may
not be incorporated into the stove, but can reduce gas composition from the
complete heating system.  In each category the modifications are presented
in decreasing order as to their expected likelihood of being effectively
reduced to practice.
          To apply most of the modifications noted below, and all those
involving destruction of previously formed pollutants, will require stove
design alterations.  These are generally beyond the ability of most
residential stove operators.  A few very significant gas composition
reductions by operator technique modifications can be obtained using
existing stoves, if the operators are sufficiently motivated to change
their procedures or characteristics of the fuel they burn.

A.   PREVENTION  OF  GAS  COMPOSITION  FORMATION
     IN FUEL MAGAZINE

          Wood  is placed within a wood stove in a  quantity to  support
burning for a prolonged period.  Considering that  the magazine receiving
this wood is usually an integral part of the combustion chamber,  the entire

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charge of wood can become heated, resulting  in pyrolysis off-gasing.  When

these gases leave the magazine and the  stove unburned,  they contribute

directly to the organic gas composition of the stove.   Several  techniques to

reduce this source of gas composition are as follows:
           (1)  All the wood inventory within the stove should be
                kept at a low temperature until active local
                burning is started.  This will preclude extensive
                pre-burning pyrolysis.  Primarily design modifi-
                cations are needed, possibly with an altered
                operator technique.

           (2)  Small charges of wood should be placed in  the
                stove at one time in order to prevent extensive
                pre-burning pyrolysis.  This is an operator
                characteristic which at first consideration is
                undesirable to an operator who wants long  burning
                periods with no attention.  It should be effective
                in most existing stoves as a means of reducing
                emissions.

            (3)  After combustion has been established, only large
                pieces of wood should be fired, consistent with
                desired burning rate maintenance.  This is a fuel
                characteristic that may require more frequent
                attention or demanding operator techniques.  By
                this means pyrolysis can be kept to a minimum in
                existing  designs of stove.

            (4)  Very  low  moisture  fuel, kiln dried, should be dis-
                 couraged, particularly when placed in large
                 quantities in  a magazine.  Pre-burning pyrolysis
                 is  more rapid  and  leads to high gas composition.
                 This  fuel characteristic is less of a problem with
                 conventional air dried cordwood, but imposes
                 special operator demands when very dry wood is to
                 be  burned in a low-gas composition manner.

            (5)   Devolatilized  wood such as charcoal is a highly
                 recommended  fuel,  generally producing low  gas
                 composition  of CO  and organic materials.   This
                 fuel  characteristic  is limited by fuel costs
                 to  the consumer, but  is suitable for use in some
                 wood  stoves.

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B.  PREVENTION OF EMISSIONS FORMATION
    IN COMBUSTION REGION

          The wood that is actively burning in a stove is subjected to a

restricted supply of air as a means of control of the burning rate.  This

deficiency of air can result in incomplete burning of the fuel constituents,

permitting the emission of reduced and incompletely oxidized materials into

the stack and ultimately into the environment.


              (1)   High burning  rates should  be maintained  as  an
                   operator technique to  reduce gas composition.
                   This may become objectionable to the  operator,
                   as being incompatible  with comfort  heating  when
                   considering the comfort heating demands  and the
                   heating capacity of the stove.

              (2)   Primary air should be  directed  specifically to
                   a limited burning region or volume, to preclude
                   widespread burning with the available supply of
                   air.   This is a design factor that  may be difficult
                   to accomplish with a fixed geometry design  suitable
                   for a wide range of burning rates,  but might be
                   accomplished  with simple discrete geometry  changes
                   made by the operator within design limits.

              (3)   A high turbulence level should  be maintained in
                   the active burning area, by using stove  design
                   techniques.  The use of an air  blower with
                   tailored air ducting should achieve this objective.
                   A "within-firebox" source  of air to the  blower
                   might be used to minimize  the hazards of blower
                   failure and to provide modulated operation  during
                   a batch type of burn.   The high turbulence  level
                   assures improved mixing and thorough  combustion
                   with less stratification of air and combustible
                   pyrolysis products.

              (4)   Excess fuel should be  eliminated from the primary
                   burning area as a means of preventing severely
                   fuel-rich combustion.   This situation could partially
                   be achieved by limiting a  continuous  flow of fuel
                   feed into the area to  match the desired  burning  rate.
                   This situation is generally not attainable  with  stick
                   wood but could be accomplished with a stove designed
                   specifically to burn a free flowing form of wood,
                   such as pellets.  This drastic design approach could
                   essentially provide fuel-controlled burning.

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          (5)   High temperatures should be maintained in the active
               burning area to promote rapid and complete burning
               of fuel.   This design characteristic should minimize
               incomplete combustion associated with quenching of
               partially burned fuel, and can be improved by use of
               insulating refractory materials enclosing the
               combustion chamber.

          (6)   An abrupt reduction in the rate of primary air supply
               to an operating stove does not simultaneously reduce
               the rate of pyrolysis of the wood being burned.  The
               sustained gas evolution by pyrolysis, coupled with
               the reduced supply of air, increases the gas composi-
               tion of unburned or partially oxydized fuels.  This
               phenomenon should be avoided, whether it be by an
               abrupt operator technique or by severe cycling of a
               thermostatic control device.


C.  DESTRUCTION OF EMISSIONS IN
    PRIMARY BURNING ZONE

           The flames in the area of active wood burning are fed by two

sources, combustible emissions from the adjacent wood surfaces, and any
combustible products carried into this area from elsewhere in the stove.
If this local burning is complete, it will consume all the organic materials
and combustibles which would otherwise be emitted. The following approaches

should  improve the completeness of burning in this primary burning zone.
            (1)   Increased turbulence in the primary burning
                 zone will promote the complete burning of
                 pyrolysis products released directly into
                 the flame region, thus eliminating some or
                 all of  the products of incomplete burning.
                 This  requires  a design change similar to
                 that  noted in  technique B-3 above.

            (2)   Increase the temperature in the primary burning
                 zone  as  in technique B-5 above.

            (3)   Increase the residence time at active combustion
                 conditions while maintaining temperatures and
                 turbulence levels.   This is a design approach
                 that  may also  become practical with a blower
                 system  as  in  technique B-3 above.

            (4)   Pyrolysis  products  from  the magazine region should
                 be ducted  only into  an active burning region
                 where adequate air  supply  and temperatures will
                 promote complete combustion.  This is a design
                 consideration.

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          (5)   Develop a down draft design of combustion
               chamber that will assure that all gas flow
               through the wood inventory travels in the
               direction contrary to the progression of the
               burning through the wood.  When down flow
               of air is used, a reduction in the bed
               area should accommodate reduced burning
               rates while maintaining the counter flow
               phenomenon.


D.  DESTRUCTION OF EMISSIONS IN
    SECONDARY COMBUSTION ZONE
          Most stoves include a region or zone within the stove where

secondary combustion can occur, and provide a supply of secondary air to

support this combustion.  When secondary combustion is achieved, a signi-

ficant reduction in emissions can be obtained.  The following procedures

include techniques to increase the liklihood of achieving this combustion,

and extend the range of conditions that will support it.

          (1)  The temperatures in the secondary combustion
               chamber should be kept high to broaden the
               range of gas mixtures that will permit com-
               bustion.  This is a design characteristic of
               the stove using insulation and proximity of
               the secondary air inlet to the inlet of
               the primary combustion chamber to improve
               chamber heat retention.
          (2)  The secondary air should be heated to provide
               the same effect as noted in D-l above, and avoid
               quenching secondary combustion that might other-
               wise occur.  This design factor can be acc-
               omplished by within-the-stove heating of secondary
               air prior to mixing with primary combustion products.

          (3)  The envelope of gas mixtures that will permit
               combustion of primary combustion effluents and
               secondary air can be widened by increasing the
               combustibles content of primary effluents.  This
               shift of operation towards gasification in the
               primary combustion chamber could ultimately result
               in clean burning with reduced emissions if the
               secondary combustion was maintained under all
               operating conditions.  This requires a major
               design alteration, possible with the operator
               exercising effective control over both primary
               and secondary air supply.

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          (4)  An auxiliary  ignition  source could be pro-
               vided in the secondary combustion space, possibly
               supplied by an auxiliary fuel, an electric
               ignition source (glow plug) or a "pilot light"
               fed from the primary combustion itself.  Such
               a device to assure ignition would be primarily
               a design oriented technique, which might be
               augmented by stove operator initiation,
               monitoring or control.
E.  ADD ON SYSTEMS FOR
    EMISSIONS CONTROL

          Modifications exterior to the fuel and firebox design  can  also  be

effective.  Two techniques are suggested which should  significantly  and directly

reduce emissions.  A third add-on device is possible that  can  indirectly  reduce

emissions.  These techniques can be applied as separate devices  between the

stove and stack, or by major design modification included  within a stove
envelope.

          (1)  Catalytic afterburners are being developed
               and applied to wood stoves with at least
               one new design stove currently being marketed.
               By reducing the temperature at which com-
               bustion can be initiated, and by conserving
               the heat released to maintain the combustion,
               the catalytic unit might significantly  reduce
               emissions under many but not all conditions of
               burning.  This constitutes a design modi-
               fication although visual monitoring by  the
               operator would be advisable.

          (2)  A separately fueled afterburner could be
               developed, preferably using a gaseous fuel.
               A significant increase in equipment cost,
               auxiliary fuel use, and heat delivery rate
               will probably result from such a design change.

          (3)  A greatly increased heat storage capacity can
               be added to a stove, permiting a higher burning
               rate operating for short time periods,  yet  still
               providing a near-steady delivery of heat to the
               living space.  This modification permits all
               burning to be at high rates, with the corres-
               pondingly reduced  gas  composition.  Heat could
               be  stored as  sensible heat  such as with water
                or  solids  (stone or metal), or as latent heat
                such  as with  Glauber's salts or other phase
                change material.

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                                  SECTION 3
                                WOOD AS A FUEL

          Currently wood combustion provides about 1.5 Quads*of energy to
this country yearly, with about 0.3 Quads used for residential heating.
This residential use of wood should increase to 1.0 Quad in the next 20
years, and actions are planned in support of this goal.  Practically all
of the residential wood utilization is now based on cordwood which is
widely available, with most of the burning in residential stoves and fire-
places.  Wood stoves are increasingly being recognized as the more efficient
device, and the use of wood stoves has increased rapidly in recent years as
the prices of other residential fuels, especially oil,  have increased at a
very high rate.  Central furnaces will probably become more prevalent as
commercial distribution of wood is developed, especially processed wood such
as pellets.  Probably most of this residential wood is now burned in stoves
and enclosed fireplaces, instead of open fireplaces due to the increased
efficiency and longer burn times for stoves and forced air units.  It has
been estimated (1)  that  the^residential heating with wood might grow from the
present 4 million homes to as many as 15 million by 1985.  Due to the general
recognition that airtight stoves provide higher efficiencies than open fire-
places, the increase will probably be primarily in this type of stove.
          Various other forms of wood are available commercially in limited
quantities and in limited areas of the country.  These include sawdust as
an industrial waste product, wood chips, and wood processed into pellets or
densified logs.  Although growing, the use of these other forms is still con-
sidered to be small compared to conventional cordwood, for hand fired
appliances.
          The environmental aspects of increasing residential wood burning
fall into two arenas: harvesting with resource depletion considerations, and
burning with objectionable atmospheric emission considerations.  The former
  *  1 Quad = 10   Btu

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can be controlled by using proper silvaculture or  forestry management tech-
niques which have been demonstrated by  the  forest  products industry and
local farm agents for many years.  The  objectionable  emissions, however,
are not widely recognized, and  the technology for  reducing or  eliminating
objectionable emissions is not  well developed. Both health and visibility
aspects of the emissions are significant.

PROPERTIES OF WOOD
          Wood  is available  as  a fuel in most parts  of the country,  usually
 in the  form  of  split  logs  and/or sticks, known  as  cord wood for residential
 applications.   The  principal variables  in cordwood are hard-wood species or
 soft-wood species,  and  air dried (cured) or green  (freshly cut).   Dry hard-
 woods have a slightly lower heating value than  dry soft-woods which generally
 have a  higher  resin content.  More  important to  heating value is the moisture
 content,  which varies between  about 5 percent  for  very dry wood to over 50
 percent for  freshly cut wood, with  20 percent being  typical for air dried wood.
           The chemical composition  of dry wood  as  measured in percent carbon,
 hydrogen and oxygen is very similar  for hardwoods  and softwoods.  The elemental
 content is typically about 40  to 52 percent carbon,  about 6 percent hydrogen,
 and 40 to 44 percent oxygen.  The cellulose content  does vary as follows:

                                             Hard Woods         Soft Woods
                      Cellulose                 43                  43
                      Hemicellulose              35                  28
                      Lignin                    22                  29
 When the woods are pyrolyzed the cellulosic materials break down most easily
 into volatiles whereas the lignin materials are  more char forming.
           Cellulose is a high molecular weight  polymeric carbohydrate con-
 taining nonaromatic glycoside rings joined by oxygen.  Cellulose
 products thus do not directly contain aromatic  species, but can contain many
 simple hydrated species.  The formation of long chain or fused ring species
 may  require more severe conditions than those required to initiate simple
 pyrolysis.
  *  The moisture content of wood is measured and reported on either of two
    bases: weight of moisture per weight of dry wood, and weight of moisture
    per weight of moist or as-fired wood.  The latter is used in this
    discussion.
                                         9

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                                  SECTION 4

                      COMBUSTION CHARACTERISTICS OF WOOD

          The combustion of wood is generally recognized as involving three
processes or phases: moisture evaporation, pyrolysis with subsequent space
burning, and surface char burning.  These processes occur successively on
any local particle of wood, but in normal combustion systems there is an
overlap with all three processes occurring simultaneously within the com-
bustion chamber.  This overlap is especially significant when prolonged
burning eliminates water early and the other two continue.

EVAPORATION
          The amount of moisture evaporation depends on the moisture content
of the fuel as fired, which can vary from over 50 percent for some green wood
to essentially zero for oven-dried wood.  As the wood is heated this moisture
is evaporated, beginning at the outer surface where the heat is applied.  As
heating progresses the moisture from the center of the piece diffuses as vapor
through the outer material.  In large pieces this outer material may have been
heated appreciably above the steam point, even to temperatures at which py-
rolysis or char burning occurs.  This efflux of water vapor to the surface of
•the wood retards heat flow into the wood, both from the steam's sensible heat
gain and by a thickening effect on the gaseous boundry layer through which
the initial convective heating usually occurs.  This type of cooling thus
retards the burning of wood, especially when large pieces are used and when
moisture content of the wood is high.

PYROLYSIS
          Pyrolysis of the wood starts as the local temperatures rise above
100°C, with low temperature pyrolysis being endothermic.  These product
gases contain H20, C02» CO, CI^COOH, HCOOH, and others.  Although the off-gas

                                        10

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has a positive heating value,  the  steam  and  C02  content of this  initial  dis-
charge reduces the heating  effectiveness.  As  the  local temperature exceeds
about 280°C, the pyrolysis  becomes exothermic,  temperatures  increase with-
out local oxygen consumption,  and  larger quantities  of gas are obtained.
This off-gas contains additional heavy organic molecules  and entrained
particles (droplets) of wood  tars.   The  rate of pyrolysis, especially  at the
lower temperatures,  is closely dependent on  the rate of heat transfer  to the
pyrolyzing wood.
          The quantity of pyrolysis off-gas  (including  entrained organic
liquids)  is  increased appreciably  by the rate of pyrolysis.   Very slow
pyrolysis leaves half of the  original dry weight of  the wood as  a char,  whereas
very  fast pyrolysis  reduces the char residue to 13 percent of the original dry
weight (2) .   The  total heating value of the off-gas (Btu/lb wood) from rapid
pyrolysis is thus  much higher than that  from slow pyrolysis.  The ignition
 temperature  of  this  off-gas from wood pyrolyzing is  about 600°C  after being
mixed with  air.   Thus, burning requires  either (a) an adjacent  flame or  hot
 surface,  such as  other localized burning,  or (b) a surface layer through which
 the gas  diffuses  which  is  sufficiently hot that the  600°C ignition temperature
 is retained after mixing with adequate air.   The latter is likely only when
 the gas  evolution rate  from internal evaporation and pyrolysis  is relatively
 low and/or  the radiant heating of  the surface is sufficiently high.
           This off-gas burns  vigorously  in a flame when it passes through the
 surface of  the wood allowing  reaction with the oxygen supporting the combustion.
 Should there be insufficient  oxygen, insufficient turbulence to  assure
 thorough mixing,  or inadequate residence time at flame  temperatures,  some
 fraction of these pyrolysis off-gases can leave the  combustion  area in-
 completely burned.  This  incompletely burned fuel can contain either the
 original off-gas species  or original species thermally  altered  into other species.

 CHAR FORMATION AND BURNING
           The third phase of wood  burning occurs when the local  wood has been
 thoroughly pyrolyzed,  leaving a porous  carbonaceous  char. This  char burns at its
 surface when temperatures are adequate  and sufficient oxygen diffuses  to the
 surface.  This char burning is essentially flameless except  for  (a)  slight
                                          11

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 gaseous  hydrocarbon evolution from the small amount of hydrogen residual in
 the  char,  (b)  the partial oxidation to CO by oxygen at the exposed active
 surfaces and subsequent burning of the CO, and (c) the watergas reaction with
 steam from internal moisture vaporization.  Although the ignition temperature
 of pure  carbon is high,  fresh charcoal can sometimes ignite at much lower
 temperatures than the pyrolysis off gases (2).
           The char has a lower thermal conductivity than the original wood.
 Thus,  slow burning of a large piece of wood, resulting in a thick outer char
 layer, is  made even slower by the reduced heat flux to the interior.   The hot
 char layer may also change the effluent gas composition, as noted above,  by
 reacting with the water vapor to form CO and H2 (water gas reaction), and also
 by  cracking some of the heavier hydrocarbon gases and liquids from the
 pyrolysis  zone.

 BURNING  PROGRESSION
           Table 1 shows .the progression of the several phenomena that
 typically  take place during the progressive burning of a piece of wood.  The
 sequence of events vary in relative timing at different locations in the
 wood depending on many factors.  The whole process is accelerated by high in-
 cident heat flux, small piece size, and low moisture content.  Wood size and
 moisture content particularly affect interior change rates.  The surface
 phenomena are predominantly affected by radiant heat flux, oxygen supply con-
 ditions, and gas evolution rates (moisture and pyrolysis products).

 WOOD CONSTITUENTS RESULTING IN ATMOSPHERIC POLLUTANTS
           There are no constituents in wood in large quantities that are
recognized as being inherently objectional sources of pollution.  The S and
N contents are generally less than 0.01 and 0.1 percent, respectively.  With
complete conversion to S00 and NO, the emissions would be below 0.025 and
          g              ^
0.27 lb/10  Btu  (12 ppm SO  and 276 ppm NO), respectively.  Toxic metals such
as lead and mercury 'do not occur in large enough quantities to constitute a
hazard.  Wood ash is normally considered a beneficial soil additive, but must
be disposed of with care due to its alkalinity.
                                         12

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                   TABLE  1.    TYPICAL  PROGRESSION OF  LOCAL  PHENOMENA
                                   IN WOOD  LOG  BURNING
LOCATION OF PHENOMENON


DISTANCE FROM SURFACE


NEAR TO SURFACE
Log Introduction
                                          Time  Progression
Radiation influx

Convection influx
                     Radiation influx    Radiation influx
                                                               Radiation influx
                      Convection influx   Convection influx  is   Convection influx
                      reduced by steam    reduced by efflux of  Unattached luminous
                      efflux              pyrolysis products    flame
                                          and steam
SURFACE PHENOMENON
SURFACE MATERIAL
                           Heat influx
                           Sensible heating
                                                 Heat  influx
                                                 Steam efflux
                     Moisture
                      evaporation
                                         Heat influx
                                         Steam and pyrolysis
                                          products efflux
                                          Increased heat influx
                                          Steam, pyrolysis gas,
                                           and liquids efflux
                                                                    Low temp, pyrolysis    Exothermic  pyrolysis
SUBSURFACE MATERIAL

INTERIOR MATERIAL
No jchange

No change
Sensible heating   Moisture evaporation   Low temp, pyrolysis

No change          Sensible heating       Moisture evaporation
 CORE, CENTRAL MATERIAL
                           No change
                                                 No change
                                                                    No change
                                                                                           Sensible  heating
                              Time Progression
                                                                                                           Burnout
 Radiation flux near balance    High radiation outflow    High radiation outflow    High radiation outflow    Radiation cea
 Intense luminous flame
                              Decreasing luminous
                               flame
                            Reduced flames  less
                             luminous
                                Diffusion control  of
                                 surface burning
 Radiation much increased
 Large gas efflux
 Char  formation



 Exothermic pyrolysis

 Low temp, pyrolysis


 Evaporation
   Highly radiant  surface
   Gas efflux reduced
       Char burning
       Attached blue flame
       Highly radiant surface
   Pyrolysis products crack- Surface lost
    ing and steam dissocia-
    tion within char layer
   Pyrolysis products

   Exothermic pyrolysis


   Low temp, pyrolysis
       Char burning

       Pyrolysis products
        cracking

       Exothermic pyrolysis
Char burning
No flame
Highly radiant surface

Surface lost
Surface lose

Char burning


Char burning
Surface



Surface lost

Surface lost


Char burnout
                                                       13

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          The organic constituents of wood, cellulose and lignin, are
themselves considered non toxic, but their thermal decomposition or pyrolysis
products contain several objectional species including aldehydes, phenols,
and creosols.  In some cases polycyclic  aromatic hydrocarbons (PAH) can be
formed.  All of these are of concern in the atmospheric emissions.
          Two mechanisms for formation of objectionable emissions from wood
burning are
          •  Pyrolysis product release from the wood which never
             encounters conditions of temperature and oxygen
             concentration between the pyrolysis site and the
             stack which satisfy the requirements of complete
             combustion.
          •  Incomplete burning due to excess fuel and insufficient
             oxygen in active areas of burning.
It is to be noted that both mechanisms can occur at high temperatures, and
both mechanisms can occur while appreciable oxygen remains in the flue gas.
When the temperatures are high enough to initiate combustion, and sufficient
oxygen is present, the combustion can go to completion, consuming all of the
organics.  The contribution of secondary combustion to eliminate these
objectional species is discussed later.
          Organic emissions resulting from incomplete burning of the wood and
its pyrolysis products thus consist of a mixture of chemical species.  Some
may leave the stove in condensed form, and additional species becomes con-
densed into and onto particulates or onto the walls of the stack as the
gases cool.  The particulate mass in the stack at any point of sampling
depends not only on the quantity and distribution of organic species carried
in the flue gas, but also significantly on the stream temperature at the
point of particulate separation from the gas.  The logical mechanisms of ash
carry over into the stack, suspension burning of fine solid wood particles
and aerodynamic entrainment from the bed, are both expected to be ineffective.
Thus, the condensed organic species are presumed to constitute the bulk of
the stack particulates.
                                         14

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PRODUCTION OF PAH IN WOOD  COMBUSTION

          Polycyclic aromatic hydrocarbons  (PAH) have been identified in
wood combustion products.  Mechanisms  proposed for  PAH  production  from  pyro-
synthesis and combustion include:  (1)  polymerization of small organic
fragments under reducing conditions:  at temperatures above about 400°C
(750°F) organic compounds  are  "cracked" to  small reactive fragments that
condense into aromatic  species with a subsequent gain in free energy over
condensation into their paraffinic analogs, (3-5)  and also,  (2) a pyrocombustion
synthesis of PAH can occur from  condensation and rearrangement of poly-
acetylenes  (6).  Figure 1  shows  a  primary pyre-combustion mechanism proposed
for  PAH production  from "cracked"  organic molecules.
          Several researchers  have also investigated the pyro-combustion
reactions of cellulose  and lignin. These reactions in  tobacco leaf materials
have been extensively studied  and  give a valuable  literature base to show how
a species similar  to wood  fuel behaves at flame temperatures.  In the tobacco
 case,  large weight  losses  are  observed at temperatures  nearing the ignition
 temperatures  (400-450°C)  (750-840°F)(7^8).   Tobacco research has shown that
yields of  condensible organic  material regularly decrease from 400-1000°C
 (750-1800°F)  in pyrolyzed  tobacco  while recovered  PAH increase as the temper-
 ature is  increased  in  this temperature range  (9).   Pyrolysis of cellulose at
 800°C (1620°F)  (approximately  the  maximum cigarette burn temperature) produces
 1000 times  more benzo(a)pyrene  (BaP)  than  the  amount measured  in main  stream
 cigarette smoke (10)-   The production of benzo(a)pyrene and other PAH from the
 cellulose in tobacco has  led to  several studies (10,11,12).
           On warming wood  there  is a  loss of water and  volatile species
 at 60-100°C (140-212°F) and loss of water of hydration  at 160-170°C
 (320-340*F) (13).   During  the  combustion of wood,  cell  disruption occurs with
 volatilization, sublimation, pyrolysis, fragmentation and chemical con-
 densation occurring in and around the flame zone.   That significant amounts
 of neutral polycyclic compounds  are measured in wood flame effluents is
 indicative of chemical reactions which have generated the PAH, principally
 from starting materials of cellulose and lignin which do not originally
 contain the PAH species measured.   Lignin pyrolyzed at  700°C (1290°F) in
 nitrogen,  yields higher levels of phenols and cresols than cellulose under

                                        15

-------
FIGURE 1.  PYRO-COMBUSTION TO PRODUCE  BENZO(A)PYRENE (2)

-------
the same conditions (14) .  The maximum phenol formation from lignin is found
at 500-600°C  (930-1110°F)  (15).  Studies on  the pyrolysis of cellulose have
shown that temperatures of 475-420°C (890-790°F) yield low-molecular weight
aldehydes, ketones, and aliphatic acids (16,17).
           It is important to note that both pyrolysis and combustion of
cellulose and lignin lead to the production of PAH, aldehydes, ketones, and
cresols.  These processes occur at temperatures as low as 400°C (750°F) (3).
Since these compounds are not original constituents of wood, their manufacture
during the combustion process must be considered under the conditions of
available oxygen, temperature, and wood types used in home wood combustion.
Further study of this phenomenon might establish conditions of pyrolysis
and/or burning at which the PAH species are reduced or not formed.
                                           17

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                                  SECTION 5

                       WOOD STOVE DESIGN AND PERFORMANCE

        There are many designs of wood stoves for residential heating.
The radiant heater designed for use in the living space and hand fired  with
cordwood is the most popular and is the focus of this study.   One design of
residential wood burning furnace has been developed with improved performance,
especially relative to efficiency and emissions.  This high turbulence  burner,
described later, has been included in the study because many combustion
modifications have been effectively included in its design.

TYPES OF RADIANT STOVES

        There are several options of air flow and fuel flow patterns within
the stove that have been adopted in commercialized designs.  Figure 2 shows
the four generic systems in simplified form.  These are described below
according to the draft (flow) of primary air.  The significance to air
pollution emissions is also noted qualitatively for each generic system.

Up Draft

        In this conventional system, the primary air flow passes upward
through the burning wood.  In some stoves the wood, sticks or logs, rest on
andirons or on a horizontal air-permeable grate.  More often the fuel support
(hearth) is inherently not permeable or else the grate openings are effec-
tively plugged with ash.  The primary air flow is then introduced near the
base of the combustion chamber, i.e., at the wood support level.  Buoyance
effects resulting from the heating of gases in the burning region induce
the flow into the bottom of the wood charge where the primary combustion
takes place.  The heated gases then move upward through the wood charge.
Such stoves can be referred to as true up-draft or diagonal draft, and are
characterized by the combustion products moving upwards through the burning
                                     18

-------
J
S'— *-
•>


p-*^
p-^>





J
p->-
"^
r
SC
I/}
/tf
Y/ 	 .
B B B
1
k
Underfire Air
Or Up Draft
£- 	 ^
/P \
Q I
l\ 	 ^
(JB B B ]


\
)
	 )
~r

i
!

SC


/
^. P^
f >




P — Primary Air Supply
S — Secondary Air Supply
E - Exhaust to Stack
B — Primary Burning
>C — Secondary Combustioi
I - }
— *-E S— *-
s- ^



<. J
-*— S P-*-
r -v
\
^ /7) 7
0 >
w -i su
flB B B J
1
Down Draft
i
I
SC

B ft 	 • 	 ,
tiJlLL 1
^/f ^

    Cross Draft
                                                      S-Flow
FIGURE 2.   GENERIC DESIGNS OF  WOOD STOVES BASED  ON FLOW PATHS.

-------
pieces of wood, and exiting from the upper parts of the combustion chamber.
The products of the primary combustion thus pass through or among the re-
maining or more recently fed wood.  This results in heating and pyrolysis
of some of the wood in an oxygen deficient environment.  The rate of wood
consumption is effectively controlled by the flow rate of this primary air.
          A secondary air supply for secondary burning is often provided
with the intention that it burn the pyrolysis products either in the portion
of the combustion chamber above the charge of wood, or in a separate,dis-
tinct secondary combustion chamber.  The primary combustion products may be
cooled or quenched by the newly fired wood or by heat transferred to the side
walls.  Even with active flames low in the burning wood, combustion may not
be attained in the secondary combustion space.
          Simple box stoves are often: of this design, especially those which
have the primary air inlet at one side (front) of the bottom of an open com-
bustion chamber, and the vent to the stack at the top (rear) of the same open
chamber.  Although the natural convection within the burning wood charge
induces the primary air flow upward through the wood charge, some air can
usually bypass this route and support secondary combustion.  Simple box
stoves and air-tight stoves often have an additional air inlet higher in the
stove wall or door to assure this supply of secondary air.  As described
later this supply of secondary air does not assure secondary combustion,
and may actually quench combustion.
Down Draft
          This design approach has an historical basis and is used in some
stoves today in modified forms.  The wood is supported on a grate, with the
primary air flow downward through the wood and combustion taking place low
in the charge, i.e., at the grate.  The principal characteristic and ad-
vantage is that the gas flow through the wood is in the opposite direction
                                                         *
to the progression of burning through the charge of wood.   Thus, the
pyrolysis off-gassing is into the primary air stream as it approaches the
hotter, active burning region.  This design assures that these pyrolysis
products pass through the burning region, and thus promotes burning of the
organic compounds.,   The admission of secondary air immediately down stream
of the burning wood thus can aid in the complete burning of pyrolysis gases,
*  Some stoves not meeting this description are described and/or  advertised
   as being "downdraft".
                                        20

-------
as high temperatures can be maintained in this secondary combustion area.
          The Vermont Downdrafter stove  is a variant of this design, in
which the combustion zone is kept small  in a fixed  location, promoting
high temperature burning of all  the pyrolysis products.  A true downflow
combustor is the "Tasso", a residential  handfired boiler currently made
in Denmark  (.18) .

Side Draft

          In the side draft, or  cross flow design,  the  primary air  is
supplied  to one side of the base of the  burning wood charge  and  leaves  the
primary burning area also at the base of the wood charge.  Thus,  the
evaporated moisture and initial  pyrolysis products  from the  wood  prior  to
its active burning are not released directly into the primary  air flow.
They  are  released into a more  stagnant region which also serves  as  a  fuel
magazine.  The  convective and  radiant heating of the freshly fired  wood  in
 this  magazine  is less than it  would be in the main  gas  flow  from  the  active
burning  region.  By directing  the off-gas products  only through  a hot active
 burning  region,  they  can be burned when  adequate air is supplied  and  thus
 are prevented  from  'escaping'  directly into the stack.  This can  be either
 in the primary  combustion region or a hot secondary combustion region
 supplied with  additional  air.

 S-Flow

           A large  number  of  small stoves utilize an air flow pattern which
 involves primary air  supply  along the surface supporting the wood charge
 from one end of the combustion chamber,  with  combustion products  leaving the
 top of the primary combustion  chamber at the  same side.  This  design permits
 slow end-burning of the wood  sticks,  starting near  the  air source and pro-
 gressing slowly away  from the  source.  This flow pattern within  the primary
 chamber is often produced by placing  a baffle above the wood charge,  directing
 the products of primary  combustion  through  a  restricted area near the air
 source before entering the stack.   Secondary  air can be supplied  here to
 support secondary combustion.   The  location,  shape, and size of  the baffle
                                        21

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varies among different designs, providing higher velocities and turbulence,
and a longer gas flow path but not a longer average resistence time within
a given stove envelope.
          Many designs of Scandinavian stoves are of this type.  These are
often called cigarette burning designs, and are conducive to very slow burning.

SECONDARY COMBUSTION

          The wood pyrolysis products are released into the primary air stream
passing through the wood charge.  The pyrolysis rate often exceeds the equiv-
alent air supply as determined by the stoichiometric fuel: air ratio.  This
results in fuel gases being carried away from the solid fuel in an unburned
or partially burned form containing appreciable CO and many organic gases.
Most stove designs provide for a secondary air supply to be mixed with the
primary stream after the primary stream leaves the wood.  Ideally, in this
manner the secondary air stream should support complete combustion of all the
pyrolyzed fuel, without appreciably increasing the rate of wood consumption.
          Figure 3 shows the typical locations for secondary air supply, and
the regions where the secondary combustion is intended to occur in each
generic design.
          This ideal situation is hindered by several phenomena which result
in unburned organics and CO leaving the stove unburned:
          1.  The mixing rate and turbulence intensity are limited
              in natural draft stoves impeding complete secondary
              burning.
          2.  The temperatures in the secondary combustion area may be
              below that necessary for ignition and burning, especially
              at low rates of burning and in locations in the stove
              where relatively cold walls quench the flames from the wood.
          3.  The rate of secondary air flow that would be required to
              burn the excess fuel gases in the primary flow varies
              during a burn.  Early in the burn period when large
              amounts of pyrolysis gases are being evolved, insufficient
              secondary air leaves unburned fuel in the flue gas.  Later
              when the primary burning is largely char burning, excess
              secondary air might quench the flue gas, resulting in temper-
              atures below those required for ignition.
                                       22

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          Considering that essentially all stack particles are organic
species and therefore combustible,  the occurrence of afterburning or
secondary combustion must be recognized as a means of consuming these
particles in addition to the gaseous organic species still in the gas phase
and the carbon monoxide.  This phenomena, when  achieved  in the stove, not
only would reduce emissions, but  correspondingly increase the amount of  heat
released and recoverable from the fuel.  Considering these advantages, most
stove designs provide for the admission of air  to support secondary combustion,
and provide a volume or chamber within the stove in which this combustion
can occur.
          Figures 3,  4,  and  5 show the combinations of  temperature,  CO,
organics  (calculated as being propane), air, and inerts  that satisfy  the re-
quirements  for  ignition and burning.  The curves on the  tri-axial  coordinates
bound  the region where combustion can occur.  It is evident  that increased
 temperatures widen  the bounds making combustion more likely, and that increased
 inerts  narrow  the bounds making combustion less likely.  These calculations
 discount  the effects of moisture  on the burning and assume that the propane
 ignition  characteristics are representative of  the mixture of organic species
 pyrolyzed from the  wood and released from incomplete burning of wood.
 Neither assumption  is  entirely valid, but the results  are indicative  of  the
 combustion  limitations  involved.

 COMMERCIAL HIGH TURBULENCE  BURNER
           A residential wood burning appliance  has been  developed  under  a  DOE
 contract by Professor  Hill  at University of Maine.  The  burner demonstrates
 that increased efficiencies can be obtained with an improved design of  the
 combustion and heat recovery system.  The burner is a  residential  boiler
 (water heater)  for  a central heating system that incorporates several factors
 beneficial in controlling  air pollution emissions.  The  combustion is sup-
 ported by both forced  draft of  combustion air and induced draft of  flue
 gases,  such that a  high turbulence level can be maintained in the  burning  areas,
 yet not develop a firebox  pressure exceeding ambient.  It operates only  at a
 fixed,  relatively high burning  rate ("o  150,000  Btu/hr) comparable  to  one of
 the large radiant heaters.   Several characteristics of this  design favor low
 organic and CO emissions:
                                       23

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                                                                                      C3H8
                              Inert Ratio =
 Inert Fraction
Active Fraction
                              N2 in the inert fraction is the nitrogen
                              in excen of that corresponding to the
                              oxygen in the air in the active fraction
The air. CO, and C3Hg are plotted as
volumetric percents of their sum in the
total gas stream. This sum ii considered
to be the active fraction. The inert frac-
tion contains CC>2 and the N2 in excess
of that associated  with the air in the
active fraction at room temperature.
ro
-P-
                                                                                                                                                                 10
                                                                                                                                                                   C3H8
                                                                                                                                      80
                                                                                                                                                      90
                                                                                                                                                                      100%
                                                         FIGURE  3.    LIMITS  OF  IGNITION AT  20 C.

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                               Inert Ratio
 Inert Fraction
Active Fraction
                               N2 in the inert fraction is the nitrogen
                               in excess of that corresponding to the
                               oxygen in the air in the active fraction
The air, CO, and C3H8 are plotted as
volumetric percents of their sum in the
total gas stream.  This sum is considered
to be the active fraction. The inert frac-
tion contains CC>2 and the IM2 in excess
of that associated with the air in the
active fraction at room temperature.
                                                                                               CO
                     85
                              80
                                               70
                                                                60
                                                                                  50
                                                                                                   40
                                                                                                                    30
                                                                                                                                     20
                                                                                                                                                       10
Ul
                                                                                                                                                                               10
                                                                                                                                                                                  C3HB
                                                                                                                                                  80
                                                                                                                                                                    90
                                                                                                                                                                                    100%
                                                                                 LIMITS  OF  IGNITION  AT  27O  C.

-------
                                                                                     C3H8
                             Inert Ratio =
 Inert Fraction
Active Fraction    CO + Air + C3H8
                             N2 in the inert fraction is the nitrogen
                             in excesi of that corresponding to the
                             oxygen in the air in the active fraction
The air, CO, and C3Hg are plotted as
volumetric percents of their sum in the
total gas stream. This sum is considered
to be the active fraction. The inert frac-
tion contains CC>2 and the N2 in excess
of that associated with the air in the
active fraction at room temperature.
N>
                                                                                                                                                              10
                                                                                                                                                                C3H8
                       10
                                       20
                                                      30
                                                                      40
                                                                                     50
                                                                                     Air
                                                                                                     60
                                                                                                                    70
                                                                                          80
                                                                                                          90
                                                                                                                         100%
                                                       FIGURE  5.    LIMITS  OF  IGNITION AT  520*C.

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          •  High  turbulence  level in primary  burning  area
          •  Primary  combustion products  isolated from inventory
            of wood
          •  Inventory  of  wood cooled by  water-jacketed chamber
          •  Burning  confined to small portion of the  wood  inventory
          •  Refractory lined primary combustion area
          •  Refractory lined secondary combustion area
          •  Large pieces  of  wood utilized to  reduce excessive
            pyrolysis  early  during burning cycle
          •  Burning  restricted to high rates,  with heat storage
            provisions to accommodate lower heating requirements.

          Figure 6 shows a schematic sketch of the furnace,  showing the
principle components.  A commercial production version (Dumont) of  this wood
burner was obtained for operation and analysis in the  laboratory.
                                        27

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                    " •**_**. **
                iiL
                                                                       8
                                                    7   /   / 1
                                                     /   /
                                                    /   /   /i
1 - forced draft fan
2 - secondary air
3 - refractory base
4 - stacked wood
5 - refractory tunnel
6 - low velocity ash chamber
7 - fire tube heat exchanger
8 - induced draft fan
9 - water jacket for wood charge
            FIGURE 6.   WOOD FIRED RESIDENTIAL BOILER
                       UTILIZING HIGH TURBULENCE BURNING.
                                28

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                                  SECTION 6
                             EXPERIMENTAL PROGRAM
 LABORATORY FACILITY
          The test facility assembled at Battelle for this program consists
of three test sites, each with an independent, prefabricated, insulated
chimney exhausting within a high bay area in the building.  Thus, the
chimney effects on draft are not affected either by outside wind or by
the building's transient pressure fluctuations.  Radiant stoves are mounted
on electronic scales, such that total weight losses associated with fuel
burning are continuously monitored.   Figure  7 shows the  facility  arrangement
and  dimensions of  a  one  stove  and stack system.
          The gases being continuously monitored are CO, C02, NO, 02, S02,
and  total hydrocarbons (THC). The Q£ analyzer is a Taylor Servomex Type
OA272 paramagnetic analyzer, the THC analyzer is a Beckman Model 402 high-
temperature flame ionization detector analyzer.  The C02, CO, and NO analyzers
are  Beckman nondispersive infrared analyzers.  The S02 is measured by an
electrochemical analyzer.  The THC instrument provides a continuous indication
of organic content in the flue gas.   Because the specific composition of
these organic species is constantly changing, a definitive calibration of the
instrument for actual flue gas is not possible, although calibrated using
methane, the instrument reading is  interpreted as a semi quantitative
measurement of all organics.  All instrumentation is kept in a positive air
pressure room where the air is supplied through an activated charcoal filter.
The  room is kept closed and is cooled by two air conditioning units.
          The permanent gas sampling system pulls the flue gases from the
stack at the point where the hot combustion products leaving the stove enter
the  stack.  There is a 5/8" tube probe that extends the entire diameter of
the  stack.  This probe is filled with pyrex wool and has two rows of 1/8"
                                          29

-------
8%'
 6'
                              Frictionless
                                Rollers
                        f
                   PAH Sampling
                  Sampling Line
                (Heated Stainless)
    To Instrument
       Room
                                       r
                                                    \
                                                     8"ID
                                STOVE
                             Electronic Scale
                                                        Platform
        Fire Control
        Water Line
        To Exhaust
          Blower
Water
 Trap
     FIGURE  7.   LABORATORY INSTALLATION OF STOVE WITH STACK AND  VENT  SYSTEM.

                                                 30

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holes the length of the probe.  After the gases are filtered in the probe
they are pumped through a short heated flexible teflon line to a longer
heated stainless steel.line to the control room.  The gases then pass
through a Teflon bellows pump, after which the gas stream is split.  Part
of the sample stream is sent directly to the THC analyzer, the rest is
passed through a cold trap and cold filter to remove excessive water vapor
and heavy organic vapors before entering the other analyzers.  Figure 8
shows a schematic diagram of this system.

OPERATING PROCEDURES
          In preparation for a run, the gas sampling lines are flushed with
acetone to remove oils and tars from the sample lines.  The pump is also
cleaned.  The gas sampling probe is removed from the stack and the glass wool
replaced.  The cold traps are cleaned and then placed into operation.  The
instruments are purged with nitrogen and spanned with appropriate span gases.
Any adjustments to the instruments are done at this time.  Once the sampling
system and the instrumentation is working correctly, a charge of kindling is
placed in the stove and ignited.  The kindling burn heats the stove and
generates a bed of hot coals.  When 80 percent of the scrap wood is consumed
the pretest burn is started by charging the desired quantity of wood.  The
pretest burn is used to assure the stove is operating at the desired con-
ditions.  As soon as 90 percent of the pretest wood is burned the actual test
is started while not changing any conditions of the stove.   In  unusual  cases  not
 requiring hot starts the pretest at  the  identical operating  conditions
is omitted.  A test run consists of the burning of a given charge of wood
in a batch process immediately following the pretest burn.  The test run
lasts until 95 percent of the added wood is lost as measured by the scale.
          At the end of the day, the sampling system is turned  off and
nitrogen is passed through all the instruments  to recheck their zero and
remove combustion gases from  the instruments.

EMISSION MEASUREMENTS

          During all tests the millivolt signals  from  the  instruments  are
recorded on strip chart recorders and  once  every minute  a Doric Digitrend

                                         31

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                                     STOVE
                           Sample Line
                         (Heated Stainless)
                                                                      THC
                                                                  Beckman 402
                                                                      FID
                                               Heated Stainless
  Dry-Ice
   Trap
    NO
Beckman 315
  (NDIR)
      02
Taylor Servomex
 (Paramagnetic)
Beckman 315 B
   (NDIR)
     CO2
Beckman 215 B
   (NDIR)
     S02
  Envirometics
(Electrochemical)
               FIGURE 8.   CONTINUOUS  GAS SAMPLING  SYSTEM.
                                        32

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220 Datalogger scans the data from the gas analyzers and the thermocouples
in the stove.  The Datalogger prints this information and also records it
on a cassette tape by a data link with a Tecktran 815 data cassette recorder.
Notes are taken manually during the runs such as the amount of wood,  type
of wood, stove operating conditions, the time of start and end of test,
and other observations.  Also a log sheet of data is taken at intervals
during operation in case the Datalogger goes down, and it also shows trends
during the test.

PAH MEASUREMENTS

          During some test runs, the flue gas is sampled to determine the
concentration of PAH.  Figure 9. shows the sampling equipment used: a  modified
EPA Method 5 apparatus.  This allows the collection of particulate emissions
using filtration, followed By collection of the gas phase material by adsorption
on the XAD-2 resin.   The sampling rate is maintained constant at about 20 1/min
(^0.75 cfm) during the entire sampling period with the probe inlet at the stack
center.  The sampling probe Inlet velocities have been appreciably higher than
stack gas velocities.  However, the effects of non-isokinetic sampling are
considered insignificant because of the small particle sizes.  Using an
electric aerosol analyzer, the mass median diameters of suspended particles
were measured as 0.22 and 0.39 at the PAH sampling location during two runs
in this facility.   Fuchs  (19) has shown that for particles smaller than  5 mm,
excessive sample withdrawal velocities result in collection efficiencies still
above 95 percent Because the smaller particles follow the gas stream lines.
          Following sample collection,  the organic materials are extracted
from the column and probe system and analyzed for PAH compounds.   The probe
wash and extract from the filter are combined into one sample for analysis,
and the column extract constitutes a second sample.   Although the sample
collected on the probe walls and the filter can be defined as particulate,
it must be recognized that they consist essentially of condensed organic
species.  The distribution between gaseous organics as retained by the XAD-2,
and particulate organics caught on the filter,  must be recognized as depending
primarily on the temperature of the stream at the point of collection on the
filter and walls.  Appendix B presents details of the PAH analysis procedures.
                                        33

-------
                    tf
Heated Probe
U)
                  Thermostatically
                     Controlled
                       Oven
                                                                           Impinger Train
                                                                            Or Backhalf       Check Valve
                                                                                         "If
                                                                    •        iue Odin        I
                                                                       Bypass Valve   Vacl|um
                                                                                                Vacuum Line
                                  FIGURE 9,   PARTICULATE AND PAH SAMPLING SYSTEM.

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DATA PROCESSING

          After each day of testing, taped raw data from on-line gas
composition instruments and the scale weight are calculated and ultimately
read out as volume fraction of the flue gas at each minute of burn, and
weight of wood remaining unburned at each minute.  These one-minute recordings
are subsequently machine averaged for the entire test run, and this average
reported as the time-averaged gas composition for that run.  The emissions
have thus not been normalized to an arbitrary flue gas 0  and moisture
content, such as 3 percent dry.  Such a normalization would in all cases
increase the numerical pollution concentration.  These time averages are
then manually converted to emission per weight of wood burned using a
calculated weight flow of flue gas for the entire run and the weight of
wood burned as measured by the platform scale.  The volumetric composition
of the flue gas is also machined plotted against time, such that trends,
anomalies, and relative values can be easily identified.  The calculated
emissions provide the basis for evaluating the effects of imposed variables
on total emissions for a test, and the flue gas composition plots provide a
basis for diagnosis of the phenomena occurring and demonstrate the real-time
effects of changes imposed on a stove during operation.

FUEL WOOD USED

          Four types of wood fuel have been used, as follows:
          •  White oak cordwood, air dried, 20.7 percent moisture.
             Normally split and round pieces were fired together.
          •  Pine cordwood, not air dried  (i.e., green),
             42 percent moisture.  Normally split and round
             pieces were fired together.
          •  Douglas fir brands 3/4 inch on 1  inch centers,
             oven dried, null moisture.
          •  Oak lumber, nominal 4  inch x  4 inch, cut diagonally
             into triangular pieces, thoroughly  air dried,
             12.4 percent moisture.  These 4 x 4s were  fired  only
             in this form, with all surfaces  sawed.
The moisture contents of the oak and pine  were determined by  weight  loss upon
storage in a  100+°C oven for 48 hours, and is  stated  on the wet basis.
                                      35

-------
                                    SECTION 7

                        EXPERIMENTAL PROGRAM OBSERVATIONS

          Table 2 lists the averaged flue gas compositions and emissions
obtained during this program.  The burning rate,  fuel,  and burning mode
have been identified for each test run.  The gas  compositions which are
mechanically recorded each minute are machine plotted,  and several repre-
sentative plots are reproduced in Appendix B.  Notes have been added to
identify the burning phenomena occurring at each time.   All tests of the
radiant stoves were started when a charge of wood was inserted into hot
stove with a bed of burning embers.  The high turbulence burner was started
cold in each test.  These averaged data are presented only for tests during
                                                                 *
which no changes were imposed on the stove operation or controls.
          The combustion in wood stoves, and the resulting emissions,  can be
modified in many ways.  In this experimental program several modifications
were made in stove operation in attempts to correlate specific changes in
emission factors with a specific combustion modification.  Synergistic effects
of several simultaneous modifications were not specifically sought.  However,
each set of tests conducted to demonstrate the effects  of a specific modifica-
tion necessarily depends on the stove design and  operating parameters in use
at the time.  The effects of a specific modification under different design
and operating conditions can only be assumed, and the synergistic effects
determined by inference.
          The modifications conducted in this laboratory program were of three
types; stove design, fuel properties, and operator techniques.  The uses of
non-wood fuel and combustion additives were not considered.  The use of processed
wood, such as pellets, was also not considered, as this fuel can most effectively
be burned in equipment specifically designed for its use.
   A group of 32 test runs was also conducted for TVA in a similar manner and the
   detailed results of these tests will be separately reported by that agency,
   including overall thermal efficiency calculations.
                                        36

-------
TABLE 2.  EMISSIONS AND OPERATING CONDITIONS
Test
Run
Number

77
78
91a
92
93
94
95
Wood
Specie

Oak
Oak
Oak
Pine
Pine
Oak
Oak
Piece
Shape
Up
Split
Split
4x4
Split
Split
4x4
4x4
Burning
Rate
Ib/hr
Draft Burning
14.4
31.8
16.5
20.7
21.6
20.9
27.1
Fuel
Time Averaged
Gas Composition, as measured
Burned Percent by Volume
Ib/test CO C02 02
Mode with Grate
25.3
33.9
21.0
18.2
30.3
24.0
25.8
Up Draft Burning Mode
18
19
20
Oak
Oak
Oak
4x4
4x4
4x4
5.8
14.4
19.5
6.3
10.2
14.4
2.5
2.3
3.6
3.9
2.0
2.7
5.4
(Modified
11.0
10.9
13.8
15.3
13.3
10.6
13.0
Parts Per Million
THC
NO
S02
Riteway)
9.
9.
6.
5.
8.
9.
6.
1
3
8
6
2
2
1
6700
6400
7100
9100
7100
5900
9900
110
80
120
180
100
90
130
60
50
50
70
50
40
50
with Hearth (Defiant)
0.1
0.2
0.3
Side Draft Burning Mode
37
36
34
35
38
82
83
84
85
86
87
88
89
90
Oak
Oak
Oak
Oak
Oak
Oak
Oak
Pine
Oak
Oak
Oak
Oak
Oak
Oak
4x4
4x4
4x4
4x4
4x4
Split
4x4
Split
Solit
Split
Split
Split
Split
Split
6.3
11.8
17.4
19.2
12.3
16.7
18.7
18.4
16.5
13.0
16.6
15.6
14.6
15.0
5.9
9.8
12.9
41.9
26.4
24.0
23.4
26.1
15.2
15.0
14.9
14.6
14.6
15.5
High Turbulence
51
52
53
91

42
43
60
61
63
64
80
81
65
70
71
76
46
47
48
49
50

68
69
72
73

66
67
Oak
Oak
Fir
Oak

Oak
Oak
Oak
Oak
Oak
Oak
Oak
Oak
Fir
Fir
Oak
C
Fir
Oak
Oak
Fir
Pine

Oak
Oak
Oak
Fir
Down
Oak
Oak
Split
Split
Split
Split

Split
Split
4x4
Split
Split
Split
4x4
Split
Split
Split
Split
Split
Split
Split
Split
Split
Split
Down
Split
Split
Split
Split
21.9
22.1
20.9
24.1
Down Draft
7.3-
10.3
18.4
19.1
12.8
11.3
13.7
20.4
10.7
18.0
9.8
8.0
14.0
13.2
15.6
14.5
10.1
Draft Burning
15.1
16.0
21.6
24.6
37.3
35.9
21.6
39.3
Burning
13.6
16.2
15.4
16.2
15.8
14.9
16.2
25.5
15.0
16.8
14.7
8.0
14.0
23.8
23.5
12.0
12.4
Mode -
13.4
12.0
15.8
9.0
1.8
0.6
1.2
2.5
1.8
0.5
2.5
0.5
0.5
1.5
1.1
0.9
0.4
0.8
Burner
0.3
0.6
1.6
0.1
1.9
5.9
8.5
19.
15.
12.
6
4
2
1800
1600
1100
40
80
120
20
20
10
(Defiant)
6.2
10.1
11.9
11.7
9.6
10.1
13.0
8.6
13.0
12.5
12.9
13.9
13.8
12.5
(Dumont)
9.6
6.2
8.3
2.1
15.
10.
8.
7.
11.
10.
6.
11.
9.
9.
9.
8.
8.
9.

10.
14.
11.
18.
1
7
1
8
1
6
6
9
4
7
4
5
8
9

9
2
2
9
8300
1900
2800
5300
7600
1800
6200
1800
1200
3400
2400
1100
400
800

300
2000
1900
200
100
50
80
90
120
90
80
70
110
90
80
50
50
60

140
70
50
20
40
20
20
40
60
10
30
10
10
20
20
10
10
10

20
40
10
Mode (Modified Defiant)
0.2
0.2
0.5
1.0
0.1
0.3
0.4
0.1
0.4
0.4
0.1
+
0.3
0.3
0.3
0.4
0.1
3.4
3.4
9.4
8.7
5.4
4.9
7.4
8.5
6.3
6.9
2.5
7.5
5.0
5.9
6.0
8.1
2.3
Heated Air Supply
0.2
0.2
0.1
0.7
8.3
9.9
7.0
12.2
Draft Burning Mode, Reduced Area and Insulated
Split
Split
12.9
13.0
13.8
14.6
0.1
0.0
4.5
5.3
17.
17.
11.
11.
15.
15.
13.
12.
14.
13.
18.
13.
15.
15.
14.
12.
18.
5
6
3
6
5
8
2
3
3
9
7
4
8
1
9
6
9
(Modified
12.
10.
13.
8.
Bed
14.
15.
3
6
9
0
3100
3100
1000
1600
600
900
600
200
900
2000
1500
100
1100
3200
1000
600
1200
70
80
80
210
110
50
40
90
30
40
20
60
20
80
220
130
100
60
60
20
20
10
10
10
<10
10
20
10
<10
<10
10
10
10
20
Defiant)
300
200
1300
1600
(Modified
4
4
900
800
260
220
70
80
Defiant)
70
200
<10
<10
10
20

<10
<10
                       37

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TABLE 2.  (Continued)
Test
Run
Number

77
78
91a
92
93
94
95

18
19
20

37
36
34
35
38
82
83
84
85
86
87
88
80
90

51
52
53
91

42
43
60
61
63
64
80
81
65
70
71
76
46
47
48
49
50

68
69
72
73
Excess
Air,
percent

80
80
40
30
70
80
30

2050
290
140

340
110
60
60
120
110
40
130
90
90
80
70
80
100

110
220
120
920

560
560
120
130
290
330
180
140
220
200
880
180
320
280
250
150
1000

140
100
200
61
Stack Emissions
Temp. lb/1000 Ib Wood
°F THC CO NO Comments
Up Draft Burning Mode with Grate
710 34 220 1.1 Small pieces
720 33 200 0.8 Small pieces
950 32 280 1.0 PAH sample
970 44 330 1.6 Oven dried wood
760 25 120 0.7 Green Pine
990 34 270 1.0
960 42 400 1.0
Up Draft Burning Mode with Hearth
560 113 90 4.9 Low rate
760 19 33 2.0 Medium rate
1080 8 37 1.7 High rate
Side Draft Burning Mode
270 112 420 2.6 Low rate
580 12 63 0.6 Medium rate
680 15 100 0.8 High rate
660 26 220 0.8 Large load
450 53 210 1.6 Thermostat control
620 10 50 0.9 All split wood
700 28 190 0.6 PAH sample
590 9 40 0.6 PAH sample, all split
640 6 44 1.1
630 18 140 0.9
620 13 100 0.2
700 5 75 0.1
670 2 34 0.1
620 4 74 0.1
High Turbulence Burner
330 2 30 1.6 Many small pieces
250 18 97 1.2 4 large pieces, 1 unburned
290 16 222 0.8 Brands only
340 5 25 1.2 Large pieces, normal run
Down Draft Burning Mode
340 56 67 2.5 Low burn rate
370 56 64 2.7 Medium burn rate
800 7 61 1.0 Sawed 4x4
770 10 110 2.5 Small split pieces
610 7 19 2.2 4" round wood
570 11 48 1.1 Medium splits
710 5 59 0.6 PAH sample
740 2 6 1.1 Frequent additions
640 9 74 0.6 14% moisture
660 16 49 0.6 28% moisture
410 34 39 0.9 31% moisture
720 1 3 2.0 Charcoal fuel
620 16 67 0.6 Secondary air valred
510 33 54 1.6 Normal bed area
500 10 44 3.8 Reduced bed area
600 5 60 2.3 Reduced bed area
330 26 28 4.1 Reduced bed area
Down Draft Burning Mode - Heated Air
630 2 20 3.3 370 F primary air
680 1 15 2.3 370 F primary air
600 11 19 1.1 440 F secondary air
980 10 71 0.8 440 F secondary air
Down Draft Burning Mode, Reduced Area and Insulated Bed
66
67
380
280
540 11 25 1.6 Bed channeling
600 8 4 3.9 Ho bed channeling
           38

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          The following paragraphs describe various modifications investi-
gated with the observed effects on emissions.  For some modifications the
emission factors resulting from complete tests are presented, and in some
modifications, visual and instantaneous results are more appropriate.
          This section is a discussion of stove combustion modifications.
In each case the objective or basis of the modification is presented,
followed by experimental technique, observed results, and appraisal of
the results.
          The very significant effects of burning rate on flue gas composition
and emissions must be considered in any comparison between stoves or between
the same stove in different tests.  These effects will be discussed later in
this section.  Most of the data reported here are from tests conducted at
medium and high rates for the size of stoves used.  The two basic radiant
stoves modified and used in this study have manufacturers nominal ratings
of approximately 13 pounds wood per hour,  assuming 20 percent moisture in
the wood and 60 percent overall thermal efficiency.  The test program included
operation at burning rates both greater and smaller than these nominal ratings.
Sustained burning at hold-fire conditions (closed dampers)  would naturally be
much below these burning rates.


STOVE DESIGN FACTORS

          An operator has little control of the design of the stove except
at the time of stove purchase.  At that time the operator decides which
type and design to buy, depending on personal preference and the designs
that are available.  Some stoves however,  have limited capabilities to
operate in different modes, such as by use of an internal damper.

Air Flow Path in Stove

          Three of the four generic designs of air flow path were incor-
porated into one stove (Defiant) for a direct comparison of emissions.  The
up-draft mode with the hearth was achieved by opening the damper thus
                                       39

-------
permitting the primary combustion products and pyrolysis products to pass
directly upward and out of the stove.   In the side draft mode all primary
combustion products passed under the side arch or baffle, and through the
more extensive internal passages before leaving the stove.  In both of these
modes the fire rested on an impervious hearth and primary air was supplied
through tuyeres at the hearth level.  The Defiant was also modified to burn
in the down draft mode as shown in Figure 10.  In this mode the fire bed was
entirely supported on a grate, with the bed area reduced by about one third
by a retaining firewall composed of bricks.  The primary combustion products
passed downward through the grate, under the arch, and then through the
same passages as used in the side flow design.  In this mode, the primary
air was supplied through an opening in the end door.
          The up-draft mode with the grate was obtained in another stove
(Riteway) modified to provide all air supply upward through the grate and
leaving the top of the combustion chamber.
          The results of the tests are shown in Table 3.  As can be seen
from the data, there is no large difference between the three modes of
operation of one stove.  Both gas composition and emissions are shown for
the three different modes of burning for various burning rates.  The down-
draft mode at high burning rates is consistently low in THC emissions.
When the burning rate is low the thermal buoyancy forces result in a local
updraft flow  (countercurrent) within parts of the bed, overcoming the
overall average down flow through the bed.  This results in channeling and
flow recirculation within the bed, and rapid pyrolysis of wood throughout
the bed.  Extensive pyrolysis products can thus be released into the counter
stream and ultimately pass with the channelled down flow out of the bed without
burning.  The effects of Bed channeling on the CO and the emissions is also
evident when comparing tests 66 and 67 (>ee Table 2).  Using several windows
in the stove permitted observations of gas flow through  the bed.  In test  66
extensive counterflow and channeling were observed, whereas  in test 67
uniform downflow throughout the bed was maintained.
          The up draft burning mode using the grate produced higher THC  and
CO emissions  than the other modes at comparable burning  rates, although  the
PAH emissions do not support this trend.
                                        40

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TABLE 3.  EMISSIONS FROM DIFFERENT MODES OF
          BURNING FUEL: Oak 4x4
Test
Run
Number

37
36
34
83
84

42
67
80
60

18
19
20
Gas Composition
THC, CO,
ppm percent
Side Draft
8300 1.8
1900 0.6
2800 1.2
6200 2.5
1800 0.5
Down Draft
3100 0.2
800 0.0
600 0.4
1000 0.5
Up Draft Mode
1800 0.1
1600 0.2
1100 0.3
Emissions
lb/1000 Ib wood
PAH THC CO
Mode (Defiant)
ND 112 420
ND 12 63
ND 15 100
0.035 28 190
0.045 9 40
Mode (Defiant)
ND 56 67
ND 84
0.050 5 59
ND 7 61
with Hearth (Defiant)
ND 113 90
ND 19 33
ND 8 37
Excess
Air,
percent

340
110
60
40
130

560
280
180
120

2050
290
140
Burning
Rate,
Ib/hr

6.3
11.8
17.4
18.7
18.4**

7.3*
13.0
13.7
18.4

5.8
14.4
19.5
Up Draft Mode with Grate (Riteway)
77
91a
94
95
78
6700 2.5
7100 3.6
5900 2.7
9900 5.4
6400 2.3
ND 34 220
0.018 32 280
ND 34 170
ND 42 400
ND 33 200
80
40
80
30
80
14.4*
16.5
20.9
27.1
31.8*
High Turbulence (Dumont)
91
51
* = Oak
200 0.1
300 0.3
Logs
0.011 5 25
ND 2 30

920
110

24.1*
21.9*

** = Green Pine
ND = Not
determined



                      41

-------
                    Gas Flow Sequence  in Down Draft Mode
1.


2.



3.




4.


5.
Primary air enters through
door at left side

Rises to go over top of brick
firewall staying in front of
the closed bypass damper.

Descends on the right of the
firewall, passing first down-
ward through the inventory of
unburned wood.

Continues descent downward
through the burning wood.

Continues downward through
the grate.
6.   Passes horizontally under the
    baffle into the secondary
    combustion chamber.

7.   Mixes with secondary air as it
    rises through the secondary
    combustion chamber.
8.   Passes behind the closed bypass
    damper to rear center of stove

9.   Passes upward through top rear
    of stove into fluepipe.
                            Oval
                           Flue Pipe
                                                    Bypass
                                                    Damper
                                                   Thermo-
                                                   couples
                             Front
                                                              Side
           FIGURE 10.   CONFIGURATION OF STOVE CONVERTED TO DOWN DRAFT MODE.
                                          42

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          The Dumont high turbulence burner produced lower emissions than
the up draft or side draft modes when burning oak fuel.  The emissions
were comparable to the lowest values obtained with good down draft burning,
as obtained in test 67.

Primary Air Preheat

          One purpose of preheating the primary air is to increase the rate
and completeness of the primary combustion of the wood.  The combustion
products will hopefully be more completely oxidized because the air entering
the combustion zone is heated, thus raising the temperature of the reaction
and thereby the reaction rate.  The combustion products are also less cooled
or quenched by the air supply.
          Using a stove operating in the downdraft mode, tests were conducted
in which the incoming primary air was preheated to 188°C (370°F).  Air flow
rate  into the stove from a pressurized source was controlled so that the
rate  would be similar to other tests, i.e., 850 1/min  (^30 scfm).  The pre-
heating was done by passing the primary air through an electrically heated
pipe  and blowing this into the inlet of the stove.  This arrangement is
schematically shown in Figure 11.  The heated air was the only primary
air source of the stove, and used a large pipe in the stove's door side
to reduce the air velocity and to distribute the air evenly in the stove.
Oak logs, round and split, were used during these tests.
          Even with the low emissions inherent with downdraft burning,
reductions in emissions were obtained when the primary air was preheated
with  the outside source.  The time averaged gas compositions from four entire
tests were converted  to emissions and are shown in Table 4.  It is not certain
if this effect would  be observed to the same degree with other modes of
burning, as the heated incoming primary air could promote early and extensive
pyrolysis of the wood thus adversely affecting emissions.  However, in down-
draft burning these pyrolysis products cannot easily bypass the active
burning area at the downstream edge of the bed, especially in the early
stage, when there is  a good bed of hot coals that the gases must pass
through.
                                          43

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1
Filter
i | i
1
1
1
1








V


••M





T



Rotometer
3/8 Inch Copper Tube
     (Insulated)
                                Electrically Heated Pipe
        FIGURE 11.   AIR PREHEAT  SYSTEM.

-------
TABLE 4.  EFFECTS OF PREHEATED
          PRIMARY AIR ON EMISSIONS
            Down Draft Burning of Oak Logs

              Ambient              Heated
            Primary Air         Primary Air
               (80°F)             (370°F)
Test Run Number
Burning Rate Ib/hr
Gas composition
as measured,
CO, percent
THC, ppm
Emissions,
lb/1000 Ib wood
CO
THC
48
15.6


0.3
1000


44
10
64
11.3


0.3
900


48
11
68
15.1


0.2
300


20
2
69
16.0


0.2
200


15
1
              45

-------
          The preheating of primary air was thus shown to offer possi-
bilities in reducing emissions in a wood burning stove.  A main design
problem to overcome is the location of the heat-transfer surfaces to preheat
the air, while keeping the pressure losses low enough to prevent serious re-
strictions to the flow of air.

Secondary Air Preheat
          Preheating of the secondary air is important to prevent cooling
or quenching of the combustion products before leaving the stove so that
secondary combustion can occur.  An increase in the secondary air temperature
broadens the flammability limits allowing initiation of secondary combustion.
          The heating of the secondary air was accomplished by using the same
preheater used for the primary air.  The air supply temperature was 228°C (442°F)
and the flow was controlled to about 2 I/sec (5 scfm).    The heated air was
introduced through the stove's own internal secondary air ducting before
entering the secondary combustion chamber.   This ducting provided inherent
and additional heating of the secondary flow.
          The preheating of the secondary air is assumed to have no effect
on emissions unless secondary combustion has been established or can be
initiated by the preheat.  This is evident from a test burning wood which
emitted large quantities of combustibles early in the burning cycle (dry
fir brands).   Secondary combustion started  only when the heated secondary
air was introduced into the stove.   It is uncertain whether the preheat or
just an increase of total air was the cause of secondary combustion.  The
secondary combustion was evident from the increased intensity of the flames
in the secondary combustion chamber observed through a pyrex window.
          The preheating of secondary air can achieve reductions in emissions
by supporting secondary combustion, however, the achievement of secondary
combustion is so strongly dependent on the gases present that the effect
of preheating by itself is overshadowed.
                                       46

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Secondary Combustion

          Secondary combustion is the combustion of the combustible materials
not burned in the primary combustion or immediate vicinity of the wood.
These materials can result from quenching of the primary combustion products
or from  pyrolysis  of wood without burning downstream  of  the  primary  com-
bustion region.  This secondary combustion is achieved by mixing the gases
from the wood and from the primary combustion with suitable oxygen at a
temperature sufficient to ignite the mixture.  In some stoves this is
attempted directly above the burning wood and in other stoves the primary
combustion zone is separated from the secondary combustion zone by a physical
barrier, with the secondary air entering at a different location than the
primary air.  For secondary combustion to take place the gas composition must
be within the flammability limits of the gases.  Therefore the addition of
secondary air could dilute the combustion gases to a fuel concentration below
the flammability limit, or quench the mixture to  below ignition  temperatures.
           The flammability limits calculated for CO and propane with air
 are shown in Figures 3, 4,  and 5.   Propane  was chosen as being  representa-
 tive of wood pyrolysis gases realizing that the composition of  the actual
 pyrolysis gases is extremely complex and varies during burning  in actual
 cases.  As can be seen from the triangular  graph,  the flammability region
 is very narrow and would explain the difficulty in obtaining and maintaining
 secondary combustion especially at low temperatures.   The amount of inerts
 from completed combustion also affects the  flammability as shown in Figures
 3, 4, and 5 by making the range narrower.   As the temperature of the combus-
 tion products increases, the flammability limits broaden, making secondary
 combustion easier to initiate.
           The stove used for these observations has a separate  secondary
 combustion zone.  For the observation and determination of secondary com-
 bustion a pyrex window and a thermocouple were placed in the secondary
 combustion chamber.  Different woods were burned so that different burning
 rates and emissions could be tested for secondary combustion.   The tests
 were conducted in the downdraft mode permitting flames to persist the short
 distance from primary to secondary zones,  but essentially precluding
 burning ember carry over.  Secondary air was supplied through internal
 stove ducting which provided air preheat before mixing with the primary
 products.
                                          47

-------
          During the test program there were very few occurrences  of  dis-
tinct secondary combustion when it was not being deliberated  promoted.   Even
when secondary combustion was attempted, if and when it was obtained, it
occurred only at high burning rates and for only a short period  of time  (less
than five minutes).  During one test the secondary air flow was  intermittently
stopped.  With the secondary air inlet closed, emissions were high (CO:  2.3
percent, THC: 8200 ppm, and the oxygen: 3.6 percent).  The inlet was  then
suddenly opened.  One-minute data extracts from this test are shown in
Table 5.  When the secondary air inlet was opened an audible  noise was heard,
and  the initiation of secondary combustion was indicated by the  thermocouple
located in the secondary combustion chamber.  The initial pulse  of secondary
air  was presumably heated above the equilibrium inlet temperature, as the
supply duct was surrounded by the hot gas.  Along with the indicated  temperature
increase of about 100°C (170°F), there was a decrease in emission  levels.
Later during that test when secondary combustion was still apparent,  the
secondary air inlet was suddenly closed.  The results were a  decrease in
temperature in the secondary combustion zone and a sharp increase  in
emissions.  Secondary combustion was not reobtained upon reopening of the
air  inlet after several .additional minutes.
          High  temperature  of  the  primary combustion  products encourages
 secondary combustion by preventing quenching by  the cold   secondary air
 with primary products above  800°C  (1500°F),  large  quantities  of unheated
 secondary air still support  secondary combustion.  This was confirmed when
 a sight  glass  (2  1/2 inch, diameter)  in  the  secondary  combustion chamber
 inlet was removed, permitting a large influx of room  air.  The associated
 initiation and maintenance of secondary combustion was very evident:  CO
 concentrations dropped reversibly  from 4 percent to below  1 percent,  and
 THC  concentrations dropped reversibly from  9000 ppm to about  1000  ppm as
 the  window was opened and closed.  However, these tests were  run at very
high burning rates to obtain the temperatures desired; the burning rates
were over 20 pounds per hour.  This  is appreciably higher  than a homeowner
would normally operate a stove.
                                         48

-------
          The concept of secondary combustion is very effective for the

reduction of emissions.  However, it is very difficult to attain when the

stove is operated at lower burning rates more typical of consumer operation,

where both the temperature and the turbulence level  are lower.


Afterburning with Auxiliary Fuel

          The purpose  of an afterburner is  to burn the emissions before  they

exit  the stove.  This  is done by  introducing fuel into the  flue gas already

containing sufficient  air  to burn the  fuel  and  the combustible emissions.

The fuel source  could  be external to the stove  and could be a gas  such as

methane, propane or  butane.
          To  observe the effects  of an afterburner,  a quarter inch stain-

 less  steel  tube  with 1/6 inch holes every inch  was placed in the stove

 directly below  the  secondary air  distributor tube while the stove  was operating

 in the downdraft mode.  Propane  was- used as the auxiliary  fuel and was  fed

 through a  rotometer to monitor  flow.   The flowrate was from 2 to 3 cubic

 feet per minute into the secondary  combustion  chamber.

           The introduction of  propane  directly into  the secondary  combustion

 chamber usually resulted in at  least partial burning as indicated  by  gas

 temperature increases.  Three  example  observations are cited in which at
 least some burning of  propane  occurred:

           1.   When the initial  flue gas  temperature  was low
               (450°F,  230°C) and the oxygen content  high
               (18.9 percent 02),  the introduction of propane
               increased the CO  from 0.2  to  1.2  percent and  the
               THC  from 3100 to  7400 ppm.  With this  low
               initial  temperature in the flue,  the combustion
               of propane was evidently not  completed as the
               gas  left the stove, even though  the oxygen content
               remained above 10  percent.

           2.   At a higher  temperature  in the secondary combustion
               chamber  (810°F,  430°C),  the introduction of a larger
               amount of propane  was more effective.  The CO level
               of 0.5 percent did not change appreciably, but the
               THC  was  reduced  from  4100  to  1600 ppm, and the
               oxygen content was reduced from  16.0 to 6.4 percent.
               The  propane  burning was  apparently essentially
               completed.
                                         49

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       TABLE 5.   EFFECTS OF SECONDARY COMBUSTION ON EMISSIONS
                 Burning Fir Brands at Approximately 30 Ib/hr
                           Prior to
                          Secondary
                           Burning
            After
          Secondary
           Burning
         Initiation
           During
          Secondary
           Burning
            After
          Secondary
           Air Flow
           Stopped
Time, hr. min.

Flue Gas Composition,
as Measured
  02, percent
  C02» percent
  CO, percent
  THC, ppm

Temperature in °C
2nd Comb Zone, (°F)
 15:10
  3.6
 15.1
  2.3
 8200

  613
(1135)
 15:13
  4.6
 14.6
  0.1
  680

  712
(1314)
 15:59
  7.6
 13.0
  0.1
  430

  656
(1212)
16:01
 5.37
14.3
 1.51
 4100

  617
(1143)
                                   50

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          3.   At very high temperatures in the secondary combustion
              chamber (1400°F, 760°C), the introduction of propane
              was even more effective.  The CO level was reduced
              from 1.5 to 0.3 percent and the THC was reduced from
              2400 to 400 ppm.  The quantity of propane required to
              produce these reductions was small, resulting in only
              a 90°F (50°C) temperature increase and a slight 02
              reduction to 6 percent.

          The stove conditions during these observations were not very stable,
with appreciable gas composition and temperature fluctuations.  Because of
this, the data noted above are each averages of 5 one-minute readings taken
just before or just following the initiation of propane introduction.  Though
crude and preliminary data, these do show that auxiliary fuel can in some
situations reduce the emission of CO and organics.
          The use of an afterburner with an external air source would reduce
emissions if the gas and air flow rates were high (compared to the total
wood emissions flow rate).  This combustion would be very uneconomical if
it is placed near the exit of the stove.  Another option would be to have
a control system that would regulate the amount of fuel and air.  This would
be an expensive installation and might have high maintenance costs.

Thermostatic Control

          Many stoves on the market today have a thermostatic control.  The
thermostat consists of a coil of a strip of bimetal linked with the primary
air damper.  This permits  the operator to set the stove at desired and re-
producible operating condition for unattended operation.  As the stove heats
up the coil will deform, lowering the damper and cutting back on the primary
air, thus reducing the temperature.
          A stove with a thermostat was loaded with a large charge of wood
and monitored for two hours.  The thermostat was set at the medium setting
and allowed to operate without any disturbance.
          During the first hour everything was fairly steady.  After which
time the control system started to cycle.  The thermostat closed the primary
air damper, lowering the oxygen level and raising CO and THC emissions,
                                        51

-------
and lowering the outlet temperature of the stove.  After 10 minutes the damper
opened allowing temperatures to increase and emissions to decrease.  The
thermostat again started to close the damper as the wood was depleted.  Even
though the emissions and temperature were starting to oscillate the last hour
of the test, the burning rate was steady.

OPERATOR FACTORS

          During the operation of a wood burning stove, there are factors
that effect emissions over which the operator has direct control.   These
are the amount of wood placed into the stove, the way the wood is placed in
the stove, and the burning rate at which the stove is operated.  The effects
of mass of charge and burning rate on emissions have been reported by
Butcher (19).

Amount of Wood Charged

          The  amount of wood placed into the stove at one loading will have
a large influence on the amount of pyrolysis products leaving the stove.
The emissions  go up when more wood is within the stove, even at the same burning
rate, due to the increased quantity of wood exposed to the heat and thereby
subject to preburning pyrolysis.
          To demonstrate the effect of increased wood inventory in a stove
two tests were run.  In one test, 12.9 pounds were burned and  the other
test burned 41.9 pounds of wood.  The same triangular wood pieces  were used
(oak 4 x 4's)  and the stove was operated at the same air setting during the
same day.  The tests were run using the sidedraft mode of burning discussed
earlier in the text.
          Table 6 shows the comparison of the two tests, demonstrating that
as the wood inventory is increased the emissions increase.  The burning rates
for the two tests were essentially the same but the large charge resulted
in approximately doubling the emissions.
                                       52

-------
TABLE 6.  EFFECTS OF SIZE OF CHARGE ON EMISSIONS
          Side Draft Burning of Oak 4 x 4's
Test Run Number
Mass of Charge, Ib
Burning Rate, Ib/hr
Excess Air, percent
Stack Temperature, °F
(°c)
Gas Composition as Measured,
CO, percent
THC, ppm
Emissions, lb/1000 Ib wood
CO
THC
34
12.9
17.4
62.9
680
(360)

1.2
2800

100
15
35
41.9
19.2
58.1
660
(350)

2.5
5300

220
26
                            53

-------
          Any approach that keeps the wood from pyrolyzing while it resides
in the stove prior to active burning should reduce emissions.  The only course
open to the operator to reduce emissions from this mechanism is to add small
quantities of wood more frequently.

Wood Placement in Stove

          How densely and where the wood is placed in the stove can affect
emissions and are controlled by the operator at the time of loading.  The
wood placement in the stove controls the path of the primary air within
the stove.  If the wood is packed densely, the primary air cannot reach the
internal surfaces of the wood in the pile, allowing the pyrolysis of the
wood to take place without sufficient air to burn.  The location of the
wood with respect to the entrance of the primary air can allow the air to
bypass the combustion zone and exit the stove resulting in high excess air
and high emissions.
          There were no quantitative tests conducted to determine the effect
of location or loading density on emissions.  However, it was observed in
tests where the primary air entered through openings in the side of the
stove and the wood was placed over a bed of hot coals in a manner that reduced
the surface area exposed to the incoming air, the wood burning rate was low
and the excess air was high, as indicated by 02 content in the flue.  The
wood that was left unburned late in the burning cycle was the wood in the
area where the wood had been the most densely packed.  In stoves where the
wood was placed directly on a hearth with no provision for air to get under
the wood, it was found that the wood had to be piled loosely so that air
could get through the wood to allow for complete combustion of the pyrolysis
products and to achieve the desired burning rates.

Burning Rate

          The rate at which the wood is consumed in a stove is known as the
burning rate and in this report refers to actual weight of wood as fired, not
the dry weight.  Higher stack temperatures usually accompany higher burning
                                           54

-------
rates, and this observable characteristic may be used to correlate burning
rates on different stoves.  Most stoves are designed to operate over a
wide range of burning rates.  In this program, as in conventional service,
the wood burning rates in the naturally drafted stoves were arbitrarily con-
trolled by restricting the primary air inlet to the stove, i.e., closing the
air inlet damper to reduce the rate of burning.  At the lower burning rates
the oxygen concentration in the flue gas in many stoves is higher than at
higher burning rates, indicating a larger amount of excess air for the fuel
that actually burned.  This seemingly anomalous trend presumably results
from a larger fraction of the total air bypassing the active burning at the
low burning rates.  Thus, at the lower rates the primary burning is even more
severely air limited than the stack gas analy&es would indicate.  This results
in the lower temperatures and the increased emissions of combustibles.
          It became evident early in the program that the emissions of CO and
organics (as indicated by THC) were very dependent on burning rate.  Figures
12 and 13 show this effect for three modes of burning in one stove (Defiant).
The data plotted for the downdraft mode have not been connected by lines to
form a curve, but the similar effect is evident.  This effect has been noted
by others (19).  Very high emissions associated with low burning rates (hold-
fire conditions) were observed in this program and a related TVA program
when average burning rates were maintained below about 10 pounds per hour.
Presumably, the same effect would be observed in smaller stoves when
operated at correspondingly lower rates of burning.

  FUEL PROPERTIES

           An operator has  some control over  the fuel properties of  the wood
  that is used.  The  wood can  be bought seasoned or  the operator can  season
  it.   Where  and how  the  wood  is stored is also under the influence of the
  operator.   The size of  the wood  can be decreased by splitting  or  sawing.
  The type  of wood is controlled by  its availability in the area.   The effects
  of  the fuel properties  are discussed in  the  following paragraphs.
                                         55

-------
   500
   400 .
o

§

,fl
H

O
O
O
01
13
•H
x
o


I
 i-i
 cd
 o
   300 .
    200 -
    100 -
                                               LEGEND



                                            = Up Draft Mode



                                            = Side Draft Mode



                                            = Down Draft Mode
                             T

                             10
                                        T

                                       15
20
25
30
35
                                 Burning  rate,  Ib/hr
                        FIGURE  12.   CO EMISSIONS FOR ONE STOVE,

                                    THREE MODES OF BURNING.
                                             56

-------
'•a
o
o
O
o
o
 M
 S
 O
 o
 o
 !-i
•a
 >•,
 o
 H
   100 -
75 -
50 '
     25
                                           LEGEND


                                     d = Up Draft Mode



                                     O= Side Draft Mode



                                     A= Down Draft Mode
                                                    A
                             10         15        20


                                  Burning rate, Ib/hr
                                                         25
30
35
                        FIGURE 13.  THC EMISSIONS FOR  ONE  STOVE,

                                    THREE MODES OF  BURNING.
                                            57

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Moisture Content

          The moisture in wood is dependent upon the type of wood and the
amount of time it has been dried (seasoned).  The water in the wood increases
the amount of heat required to raise the wood to its combustion point.  This
reduces the rate of pyrolysis until the moisture is released from the wood.
          For investigating the effects of moisture, oven dried Douglas Fir
brands were soaked in water for different periods of time to provide dif-
ferent moisture contents.  The three different moisture contents were
0, 14, and 28 percent on a wet basis.  All tests were run in the downdraft
mode of burning with a bed of hot fine coals on the grate, two to three
inches thick, at the start of the test.  There was also a test run using
oak soaked in water to increase moisture content from 21 to 31 percent,
and split pine logs oven dried to remove all free moisture (see Table 2).
          Table 7 shows the effects of the augmented moisture concent on
the emissions, with no distinct trends evident from these limited tests.

  Wood Size and  Shape

           The  size of wood has a large  effect  on  the rate of pyrolysis.   The
  smaller  pieces of wood result in: a shorter distance for the pyrolysis
  products to diffuse, a larger surface area to mass ratio, and a reduction in
  the  time required to heat the entire  piece of wood.  The heat  transfer  co-
  efficient is generally  twice as high  for with-the-grain  transfer  as  opposed
  to across the  grain transfer.  Therefore split wood will become heated and
  pyrolyze quicker than unsplit wood of the same size under the same conditions.
           The  effects of size and configuration were  investigated in tests
  burning  cured  oak in the downdraft  mode.   The  stove was  run at the same
  conditions  for each test, so the burning rates were  different,  dependent
  only on  the wood.  The  smallest wood  used  was  oak kindling  which  was four
  to six inches  long and had an equivalent diameter of  about  one inch.  It
  was  all  split,  there were no round  sticks  used.   The  other  three  configu-
  rations  had the same length (11 to 14 inches) with an  equivalent  diameter
  as indicated in Table 8.  The differences were; the split wood was
  triangular and was split from large round pieces  of oak without bark,  the

                                          58

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                  TABLE 7.  EFFECTS OF WOOD MOISTURE CONTENT
Burning Mode
Fuel Used
Moisture Content, % wet basis
Burning Rate, Ib/hr
Gas Composition as measured
CO, percent
THC, ppm
Down
Oak
21
11.3
0.3
900
Draft
Logs
31
9.8
0.1
1500
Down Draft
Fir Brands
0
14.0
0.3*
1100*
14
10.7
0.4
900
28
18.0
0.4
2000
Up Draft
Pine
0
20.7
3.9
9100
42
21.6
2.0
7100
CO, percent
THC, ppm
Emissions , lb/1000 lb wood
CO
THC
0.3
900

48
11
0.1
1500

39
34
0.3*
1100*

67
16
0.4
900

74
9
0.4
2000

49
16
3.9
9100

330
44
2.0
7100

120
25
*  Secondary air rate was changed several times during this test, but no
   evidence of secondary burning was observed on the continuous recording
   monitors.
                                        59

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                TABLE  8.  EFFECTS OF WOOD SIZE
                          AND SHAPE ON EMISSIONS
                          Fuel:  Air Dried Oak
Test Run Number           61         64         60       63

Wood Size,               vL        -vL-3/4      2.8.       4
equivalent                                    (4x4
diameter, inches                              triangular)

Shape                   split       split     sawed     rounds

Burning rate,  Ib/hr     19.1        11.3      18.4       12.8

Gas Composition
as measured
  CO, percent            1.0         0.3       0.5        0.1
  THC, ppm              1600         900      1000        600

Emissions
lb/1000 Ib wood
  CO                     110           48        61         19
  THC                     10           11          7           7
                                 60

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4x4 wood was triangular and was sawed from 4 x 4's cut diagonally, the
rounds were round oak logs, the bark was left on.  All tests burned about
the same amount of wood (14 to 16 pounds).
          Table 8 shows the emission data.   As expected, the split kindling
resulted in the highest emissions, the larger round pieces had lowest
emissions.  These data are shown in Figure 14, together with the same
emission data from test 58 burning dry fir brands.

Wood Type

          The differences in ultimate analyses of wood on a dry basis
(carbon, hydrogen and oxygen) are within one to two percent for the majority
of all wood species.  The more important differences between woods arise
from moisture, density, and heating value.   The inherent difference between
soft wood and hard wood is the amount of resins that are contained in soft
woods, which increases their heating value on a weight basis.
          In two popular stove configurations, updraft and sidedraft, burning
of green  pine resulted in slightly lower emissions than the dried oak 4x4
fuel.  The one test conducted with the same pine fuel after being oven dried,
to nil moisture content resulted in emissions only slightly higher than the
oak 4x4 fuel.  The relatively lower emissions for the green pine presumably
result from the delayed pyrolysis associated with the moisture content,
whereas the dried pine pyrolyzed at a higher rate resulting in the increased
emissions.  Table 9 summarizes these comparisons.
          Charcoal was burned in the down draft mode to demonstrate the
effects of a wood based fuel with very low volatile matter (Test Run 76).
As expected,  the emissions for both total hydrocarbons and carbon monoxide
were  the  lowest of all test runs as shown in Table 1.

POLYCYCLIC AROMATIC HYDROCARBON EMISSIONS

          The  emissions of PAHs from the three burning modes in the naturally
drafted radiant  stoves are shown  in Table  10.  The  differences between  the
three burning  modes while  burning oak was not great.  The emissions for down-
                                         61

-------
   140 .
   120 .
•a

g  100 J
O
O
O
W
B
O
•H
w
eo
•H

W
    80 .
60
    40
    20 .
                             LEGEND

                            Oak, Round  ,
                            Oak, Split
                            Oak, 4x4
                            Oak Kindling
                            Fir Brands
             10   20    30    40    50   60    70   80

               Surface Area Wood/Volume Wood, I/ft
                                                      90   100
        FIGURE 14.   EFFECT OF WOOD SIZE ON CO EMISSION FACTORS.
                                 62

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                 TABLE 9.  EMISSIONS FROM BURNING
                           GREEN PINE
Burning mode

Fuel Used
  Updraft,  with grate
 Oak
4x4
Burning rate, Ib/hr  20.9

Gas Composition,
as Measured
  CO, percent         2.7
  THC, ppm           5900

Emissions,
lb/1000 Ib wood
  CO                  270
  THC                  34
Green
Pine

21.6
           2.0
          7100
           120
            25
Dried
Pine

20.7
           3.9
          9100
           330
            44
                      Side Draft
 Oak
4x4

18.7
           2.5
          6200
           190
             28
Green
Pine

18.4
           0.5
          1800
            40
             9
                                   63

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draft burning (50 lb/10  Ib wood) was about 3 times the emissions of updraft
burning with a grate (18 lb/10  Ib wood).  The side draft burning was
intermediate, in PAH emissions, with wet pine producing a slightly higher
factor than dry oak.  This difference is reversed for the emissions for
Benzo(a)pyrene (BaP), a very toxic constituent of the total PAH mixture.
The BaP emissions measured for updraft burning (1.4 lb/10  Ib wood) were
higher than that from sidedraft burning, and much higher than from down-
draft burning (0.38 lb/10  Ib wood).  The sidedraft mode was intermediate
again, with wet oak and dry pine producing 1.2 and 0.52 lb/10  Ib wood burned,
respectively.
          When burning split oak logs in the high turbulence burner, appre-
ciably lower emissions were observed than with either of the more conventional
stove designs.  Details of the measurements, techniques, and experimental
observations of PAH emissions are presented in more detail in Appendix C.

COMMERCIAL HIGH TURBULENCE BURNER

          The commerical stick burner was made to burn very efficiently by
utilizing a high turbulence level and other techniques as noted earlier (see
page  23).  It was operated as prescribed by the manufacturer burning stick
wood.  When the burner was fired with 4 very large split logs, one jammed in
the hopper and remained partially unburned.  When fired with the recommended
size  of split logs, operation was reliable with low emissions.  When fired
with  smaller sizes of split logs the emissions increased only slightly.
Table 10 shows the measured emissions when the burner was run until the
blower was automatically turned off.  When operating properly the emissions
are appreciably less than from the two  typical radiant stoves.  Even when
burning brands to deliberately maximize early hydrocarbon emissions or
when  faulty  fuel performance was encountered, the THC emissions were not
 as high as from the more conventional radiant stoves.  The low CO emissions,
when  properly burning the more appropriate split oak logs, is also much
 lower than from the radiant heaters.
          These data demonstrate how appreciable reductions  in emissions  can
 be obtained with the application of several combustion modification  techniques.
 Unfortunately, many of these techniques are not applicable  to  the naturally
 drafted radiant stoves, without  extensive  system redesign.

                                         64

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                                TABLE  10.  EMISSIONS FROM HIGH TURBULENCE BURNER





High Turbulence Burner


Fuel
Burned
Burning Rate, Ib/hr
Excess Air, %
Gas Composition
as Measured,
CO, %
THC, ppm
Emissions,
lb/1000 Ib wood,
CO
THC
PAH
Stack Inlet Temperatures,
°F
(°C)
Large
Split
Oak
Logs
22.1*
220


0.6
2000


97
18
ND

247
(119)
Split
Oak
Logs
**
24.1
920


0.1
200


25
5
0.011

343
(173)

Small Split
Oak Logs
( 4" edges)
21.9
110


0.3
300


30
2
ND

331
(166)

Dry
Fir
Brands
20.9
120


1.6
1900


222
16
ND

285
(141)
Comparable
Updraft
Stove With
Grate
Dry Oak
4x4
16.5
40


3.6
7100


280
32
0.018

950
(510)

Comparable
Side Draft
Stove
Dry Oak
4x4
18.7
42


2.5
6200


190
28
0.035

703
(393)
** =
ND
This run terminated with 31% of fuel unburned.  One log jammed in the
hopper and did not fall into the burning region.

Sizes of split logs recommended by manufacturer.

Not determined.

-------
                              REFERENCES
 (1)  Hartman, D. L. Proceedings  of  the DOE Residue and Waste Fuels
     Utilization Program Contractor Review Meeting.  U.S. Depart-
     ment of Energy, December  1979.

 (2)  Shelton, J.,  and A. B.  Shapiro.  The Woodburners Encyclopedia.
     Vermont Crossroads Press, 1976.

 (3)  Badger, G. M., J. K.  Donnelly, and T. M.  Spotswood.  Some Reactions
     of  Branched-Chain Carboxylic Acids.  Aust. J. Chem., 19:1023-1033, 1965.

 (4)  Badger, G. M.  Mode of  Formation of Carcinogens in  Human Environ-
     ment.  Nat. Cancer Inst.  Monogr., 9:1-16, 1962.

 (5)  Hoffman, D.,  and E. L.  Wynder.  Chemical  analysis and Carcinogenic
     Bioassays of  Organic  Particulate Pollutants.  In:   Air Pollution,
     Vol. II, 2nd  Ed., Chapter 20,  A. C. Stern, Ed.  Academic Press,
     New York, 1968.  pp.  187-247.

 (6)  Bauer, S. H.  Comments.   In:   Tenth Symposium on Combustion.
     Combustion Institute, Pittsburgh, Pennsylvania,  p.  511.

 (7)  Burton, H. R., and D. Burdick.  Thermal Decomposition of Tobacco.
     I.  Thermogravimetric Analysis.  Tob. Sci.,  11:180-185, 1967.

 (8)  Tibbitts, T.  W.  Ignition Temperature of  Tobacco.   Method of Deter-
     mination and  Relation to  Leaf  Burn.  Tob.  Sci., 6:170-173,  1962.
      (Pub.  in Tobacco 155(19):30-33, 1962).

 (9)  Grimmer, G.,  A. Glaser, and G. Wilhelm.   The Effect of Temperature
     and Flow Rate of Air  and  Nitrogen Atmospheres on  the Formation of
     Benzo[a]pyrene and Benzo[e]pyrene from Pyrolysis  of Tobacco.   Beitr.
     Tabakforsch., 3(6):415-421, 1966.   (In German).

(10)  Robb,  E. W.,  W. R. Johnson, J. J. Westbrook, and  R. B.  Seligman.
     Model  Pyrolysis.  Study of  Cellulose.  Beitr. Tabakforsch., 3(9):
     597-604, 1966.

(11)  Nekomm, S., J. Bonnet.  On  the Combustion of Organic Material and
     Origin-of Carcinogenic  Substances in Tobacco Smoke and in Food.
     Oncologia, 13:266-278,  1960.

(12)  Pyriki, C. Bull. Inf. CORESTA, No.  1:11,  1960.

                                   66

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(13)   Edmonds,  M.  D.,  M.  T.  Core,  A.  Bavley,  and R.  F.  Schwenker.
      Applications of  Differential Thermal Analysis  and Thermogravi-
      metric Analysis  of  Tobacco.   Tob.  Sci., 9:48-53,  1965.

(14)   Scholtzhauer,  W. S.,  I.  Schmeltz,  and L.  C. Hickey.   Tob. Sci.,
      11:31, 1967.

(15)   Kato,  K., F. Sakai, and  T.  Nakahata.  Thermal  Decomposition of
      Tobacco Lignin.   Nippon  Senbai Kosha Chuo Kenkyusho Kenkyu Hokoku,
      107:171-175, 1965.

(16)   Holmes, F. H.,  and  C.  J.  G.  Shaw.   The Pyrolysis of Cellulose and
      the Action of Flame-Retardants.   I.   Significance and Analysis of
      the Tar.   J. Appl.  Chem., 11:210-216, 1961.

(17)   Schwenker, R.  F., Jr., and  L.  R.  Beck.   Study  of the Pyrolytic De-
      composition of Cellulose by Gas-Chromatography.   J.  Polymer Sci.,
      Part C:Polymer Symposia,  No. 2,  331-340,  1963.

(18)   Woodstove Directory,  Energy Communications Press, Inc., 1980.

(19)   Fuchs, N. A.  The Mechanics of Aerosols.   MacMillan Co., New York,
      1964.

(20)   Butcher,  S.  S.,  and E. M. Sorenson.   A study of  Wood Stove Particu-
      late Emissions.   J. Air  Pollut.  Control Assoc.,  29(7):724-728, 1979.

The additional references listed below provide definitive information about
the characterization,  measurement, and significance  of wood stove emissions.

 (1)   DeAngelis, D. G., D.  S.  Ruffin,  and R.  B. Resnik.  Preliminary
      Characterization of Emissions from Wood-Fired  Residential Combustion
      Equipment.  EPA-600/7-80-040,  U.S. Environmental Protection Agency,
      Research Triangle Park,  North Carolina, March  1980.

 (2)   DeAngelis, D. G., D.  S.  Ruffin,  J. A. Peters,  and R. B. Resnik.
      Source Assessment:   Residential Combustion of  Wood.   EPA-600/2-80-042b,
      U.S. Environmental  Protection Agency, Research Triangle Park,
      North Carolina,  March 1980.   99 pp.

 (3)   Hall,  R.  E., and D. G. DeAngelis.   EPA's Research Program for Control-
      ling Residential Wood Combustion Emissions, J. Air Pollut. Control
      Assoc., 30(8):862-867, 1980.

 (4)   Cooper, J. A.  Environmental Impact of Residential Wood Combustion
      Emissions and Its Implications.   J.  Air Pollut.  Control Assoc.,
      30(8):855-861, 1980.
                                  67

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                              APPENDIX A
                    EMISSION MEASUREMENT PROGRAMS

          In the course of this project  a  search has been conducted to
identify programs in this country in which actual measurements of stove
emissions have been or are being made, wherein some correlation is possible
with store design and operating conditions.  The programs are few, and
there has been no consistency in the experimental techniques used for
          •  Stove installation
          •  Stove operation
          •  Sampling of emissions
          •  Analysis of collected samples
          •  Interpretation of the results
          The programs have used different fuels burned in different stoves
with different firing techniques, all of which have generally been adequately
described.
          Major problems exists in the characterization of the chimney and
draft systems used which have significant effects on both stove operation
and ultimate emissions, and emission sampling systems used which arbitrarily
separate gaseous from particulate emissions depending on the temperatures
of the point of particulate capture and retention.  Although the measurements
and observations of emissions have been related to stove parameters, these
other factors can materially affect the emissions as measured.

Monsanto Research Corp.

          This organization has conducted the most extensive analysis  of
emissions from residential wood burning equipment.   The tests were  conducted
early in 1979 at Auburn University.  The University  staff operated  the stoves
and measured  the efficiencies, and Monsanto staff conducted  the measurement
and analysis program.  Two similar stoves and a  fireplace were operated
burning both pine and oak cardwood, using both seasoned and  green wood.   In
addition to the normal combustion gasses (02> C02, SOX, NOX, and CO),  the
emission measurements included particulate matter, condensable organics,
volatile organics, aldehydes, major organic species,  and  polycyclic organic
species.  The tests were all operated at relatively  high  burning  rates,  and
did not demonstrate the effects of burning rate  on emissions.
                                     68

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          The effects of wood type and moisture content were shown to be
generally low, with green pine producing particulate and organic emissions
slightly higher than the other three woods burned.  Many POM species were
identified in the stack emissions (particulates and gases samples combined)
and bioassays  of these specimens were found to be both mutagenic and
 cytotoxic.
          This program was managed by D. G. DeAngelis of Monsanto under
EPA IERL/RTP sponsorship.

California Air Resources Board
          This agency has conducted tests in 1977 on two free-standing
stoves in both residential and laboratory test installations.   Fuels used
were oak, pine, and coal, and relatively high burning rates were maintained
with frequent additions of wood.  Particulate emissions were determined
using EPA method 5.  Bag samples were used for total hydrocarbon and other
gaseous determinations at another location using gas chromotography.
          These tests were conducted by Peter Kosel of the Stationary Source
Control Division of the Air Resources Board.

Bowdoin College,  Main

          This experimental program has focused on particulate emissions at
low  burning rates.  All emitted particulate matter was collected on
a filter after the flue gas has been cooled and diluted with large quantaties
of fresh air.  No gas composition or excess air measurements have been made.
The implications of the particulate collection system is that all organic
emissions condensible at ambient conditions will be collected as particles.
Approximately half of the particulate matter collected has been benzene
extractable.  Nearly half of this extractable material is neutral with
regards to acid-base extraction procedures, and this fraction would presumably
contain the polycyclic emissions.
          This study has shown  that the particulate emission factor varies
proportionally with the weight  of the initial fuel charge and with  the
reciprocal of actual burning rate.
          This program has been led by Professor S. S. Butcher, and the
results published  in the APCA journal.  Support has been received from the
State of Maine.
                                       69

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Canadian Combustian Research Laboratory

          This laboratory has  conducted  emissions  analyses  and  efficiency
tests on wood stoves of different  generic  designs.   Continuous  measurements
are made of CO, C02, 02, NOX,  and  total  hydrocarbons.   Split  cordwood
has been burned at relatively  low  rates  (< 50,000  Btu/hr) while overall
thermal efficiencies have been determined  by  the stack  gas  (indirect)
method.
          The results  to date  indicate that overall  efficiencies fall  off
at  the higher burning  rates, even  though the  emissions  of CO  and THC per
pound of wood burned decreases  and the  combustion efficiency increases.
Their comparison  of generically different  stoves shows  a general increase
in  emissions of CO and THC  (Ib/lb  fuel burned)  as  the burning rate  is
reduced.  Large variations  in  emissions  between different designs of up
draft stoves were observed.
          This study is led by ACS Hayden and R. W.  Braaten far the
Department  of Energy,  Mines and Resources, Ottawa, Canada.

 Del Green Associates,  Woodburn, OR

          This company has just started a program for Region X U.S.  EPA
 concerned with wood stove utilization in their area.  The multi-task
 program includes  a  source sampling task to (1) determine effects of wood
 moisture content  on emissions, (2) develop simplified testing procedure,
 and (3)  develop reasonable standards for stove emissions using  6 stoves
 in their program.  Another task includes indoor air pollution measurements
 in a few residences  heated by wood burning within the living space.
          This  program is being led by Norman Edmisten with cooperation
 from OMNI Environmental.
                                         70

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Auburn University - Auburn Alabama

          The Mechanical Engineering Department of Auburn has conducted
research on residential wood burning equipment for several years.  This work
has focussed on the measurement and characterization of stove performance,
and the safety of wood stove operation including creosote problems.  They
have developed extensive facilities and capabilities for measuring stove
efficiency and heat output rate.  Their emission measurements are normally
limited to 02, C02 and CO as manually determined from grab samples by Orsat.
          Auburn's program for improving the efficiency, safety, and utility
of woodburning units has been sponsored by DOE and has been led by Professors
Glennon Maples, David Dyes and Timothy Maxwell.  They have also been active
in developing wood stove evaluation techniques in conjunction with the ASHRAE
and the Fireplace Institute, and conduct the Fireplace Institute's ex-
perimental evaluation program.

Argonne National Laboratory, DOE

          This laboratory has an ultimate objective to develop emission factors
for residential wood stoves.  Their experimental program includes an in-
vestigation of stove design characteristics that affect emissions, and the
development of techniques and instrumentation to measure and characterize
these emissions.
          Their experimental program involves three stoves in a laboratory
facility with on-line CO and C02 measurements.  Stack samples are obtained
with cold traps, and analysis of POMS is with GC/MS.
          Their preliminary measurements have focused on low burning rates
 (air inlets 10 to 25% open). With above-bed temperatures below 400°F, no
polycyclic species have been detected.  More recently traces of naphthalenes
have been observed.
          John Harkness is leading this program at Argonne as an in-house
study for DOE.  No publications describing emissions have been issued to
date.
                                        71

-------
Tennessee Valley Authority

          This agency initiated an experimental evaluation of several
wood stoves proposed for customer use in regions of their utility district.
The program was initiated with the measurement of efficiency by the indirect
method, and emissions using on-line instrumentation.  The stoves were fired
with kiln-dried fir brands, using the UL batch burning procedure in which
a test consists of burning a  fresh charge of brands to 95% completion on a
weight basis.  Three rates of burning were maintained for each stove in
separate runs.
          After a destructive fire occurred at the TVA facility in Chattanooga,
Sattelle conducted additional tests for TVA at Battelle's Columbus Laboratories.
These continued tests were modified to include the burning of air-dried
oak in larger triangular pieces, simulating typical residential split cordwood.
The results of some of these tests have been used in support of this EPA
program at Battelle.
          The TVA program has been actively managed for the Solar Applications
Branch of TVA by Dr. Jerry Harper.  No publication of  these studies has been
made to date.

Virginia Polytechnic Institute
          This university has an active program related to control of emissions
from wood stoves,  Their three phases include:
          (1) Data aquisition facility development
              Their facility includes on  line  continuous measurement
              of 02, C02, CO, NOX, and stack gas flow  measurement.
              They plan  to incorporate a  hot FID  instrument for total hydrocarbons,
          (2) Catalyst bed afterburner
              This development is focussed on  a bed  type unit  for stack
              installation rather than within  the  stove.
          (3) Staged combustion studies
              This effort  is to determine experimentally what  conditions
              are necessary  and  sufficient to assure secondary combustion
              without  auxiliary fuel.  This  phase  is focusing  on gas
              composition, temperatures,  and mixing rates.

                                         72

-------
          This program has not resulted in any published results, although
catalysis tests have been run.
          Dr.  Dennis Jaasma is conducting this program primarily supported
by University funding although a limited industrial grant has been received.
They are seeking support for continuation of the program.

National Bureau of Standards
          The center for Fire Research, NBS, in conducting a study of "Gaseous
and Liquid Combustions Products from Wood Burning Devices".  The objective is
to provide data and techniques to support combustion modification efforts.
The emphasis is to be placed on detailed physical and chemical characterizaion
of the emission products as affected by time during a burn cycle, type of wood,
moisture content, and excess air.  Both within firebox phenomena and within
chimney effects are of concern.
          This study is to be led by Dr. Richard Gann, NBS, on funding
provided by DOE.  No published data has been generated by this program.

Thermocore, Inc. Lancaster, Pa.

          This company has attempted to improve stove thermal efficiency
(including combustion efficiency) by means of altered air supply, focussing
on preheating of the air, and alternative paths for air entry into the stove.
Their experimental program included extensive temperature measurements with
thermocouple recordings maintained throughout batch type test runs.  Their
emission measurements were limited to Orsat analyses made at several times
during the burning of a large charge of wood.  No combustibles were measured
by Orsat, and hydrocarbon emissions were estimated by visual plume
observations.
          Yale Eastman managed this program under the sponsorship of the
Philadelphia office of the DOE.  Their report has been submitted to DOE,  but
not released in any form for publication.
                                       73

-------
New York University of Plattsburgh

          This program of stove development has focussed on overall
efficiency and particulate emissions as affected by stove design, operating
procedures, and controls development (thermostatic).  The emission measure-
ments have been limited to particulates as measured by collection on a
cooled but not temperature-controlled filter from stack gasses withdrawn
through a probe.  The velocities of specimen withdrawal and stack flow are
measured by hot wire anemometers, with sampling velocities greatly exceeding
stack velocities.  Particulate collections have been made using one minute
sampling periods at 10 minute intervals through out run periods of several
hours.  Stove operation has generally been at very low burning rates, i.e.,
stove exit temperatures 140 to 500°F.
          This program has been conducted by Professor Stockton Barnett with
personal and internal funding, and outside support is being sought.  No
results have been formally published.

Vermont Environmental Control Agency

           This agency has been conducting a field measurement program of
the ambient environment in an area where residential heating is extensively
supplied by wood stoves.  The community has no large industrial sources, and
an extensive inventory has been conducted to determine the true extent of
wood burning for residential heating.  The principal emphasis is on the
determination of the contribution of wood burning to the total particulate
loading, as determined by analysis of the particulates caught on hi-volume
samplers placed around the community.  Microscopic observations of the
particulates are being made to determine their source or origin.  Some
emission measurements have been made at residences using a Rader High Volume
Sampler and an EPA Method 5 sampler.  The organic materials penetrating  the
Method 5 filter have been measured by extraction from the back half impingers,
but these materials have not been analyzed to determine their specie composition.
           Cedric Sanborn is conducting this program with state agency  support.
                                         74

-------
Institute of Man and Resources.

           This organization has conducted a field demonstration program
of ten different residential furnaces.   The emission measurements in-
cluded CO,  NOX, S02,  and particulates,  with short time emissions measured
under all operating modes of each unit.   The particulate measuring system
consisted of diluting and filtering the entire flue gas stream in the manner
used by Butcher.  The particulate samplers operated at temperatures below
100 C, and sampled for periods up to 10 minutes.   The filter catch was ex-
tracted with benzene and dried to determine the condensable organic content
which varied from 13 to 51 percent of the total particulate matters
collected.
           The emission test program was conducted for the institute by
Atlantic Analytical Services Ltd.,  Saint John,  N.B.  and led by Alex Graham.
The overall program received support from both provincial and federal
Canadian funds, and is coordinated by Rob Brandon.
                                        75

-------
                                  APPENDIX B
                        EXAMPLES OF RECORDED TEST DATA

     Attached are several typical plots of gas composition measurements through-
out test runs.   The high concentrations of organics,  as indicated by the total
hydrocarbon (THC) measurements, are usually accompanied by high CO concentrations
as in the up draft and side draft burning modes (Figures B-l and B-2).   These
result primarily from the rapid early pyrolysis of the wood after being placed
in the stove.  The high rate of pyrolysis gas generation, exceeding the local
availability of oxygen for complete burning, lasted about one quarter  hour in
the side draft mode of burning, and for nearly an hour in the up draft mode with
airflow through the grate.  The latter stages of burning in these two  tests
consisted primarily of burning the residual char with sufficient local air
supply, thus resulting in lower emissions of organics as indicated by  THC
measurements.
     These effects were not observed in the down draft mode, Figure B-3, as the
new charge of wood was not as rapidly heated by combustion products in the test
shown here, even though a similar charge of wood was placed in the pre-heated
stove.  The high turbulence burner, Figure B-4, also demonstrated this lack of
early pyrolysis, because the wood moved progressively from the cooled upper chamber
down into the active primary burning area as burning progressed.  The small peak
in organic emissions at approximately 0.5 hours into the high turbulence mode test
was presumably due to an erratic motion of wood into or within the primary
burning area.  In these two types of burning, the composition of the fuel actually
burning did not change appreciably during the test.
     Figure B-5 shows the weight loss record during the side draft burning.  It is
evident that the weight loss rate was higher during the early stages of burning
and generally reduced throughout the test.  The rate of heat released, however,
did not fall off proportionally, as the early weight loss was associated with
relatively low heating value pyrolysis products, whereas  the later burning  rates
were associated with fuel which was primarily char with  a higher heating value.

                                           76

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             6/10/80 RITEWAY OAK LOGS  RUN 77
   25.000 r
   20.000 -
 I
Z
O  15.000 -
                                              Q  C02

                                              e   eo
Z
O
u
   10.000
    5.000
    o.ooo
   25.000 r
                                                          -i 20.000
    0.000
        0.000      .313      .625     .938    1.250     1.563    1.875

                           TIME  (HOURS)
                                                             0.000
           FIGURE  B-l. COMPOSITION OF GAS  FROM UP

                        DRAFT  BURNING WITH  A GRATE
                        Burning  split oak logs

                        Burning  rate 14.4 Ib/hr (6.5 Kg/hr).
                                      77

-------
             6/17/80 DEFIANT  (SIDE  DRAFT)  OAK RUN 87
o
o
   25.000 r
   20.000 -
   15.000 -
   10.000 -
    5.000
    o.ooo
                                              o   coa
                                              o   cc
   25.000 r
-I  10.000
                                                             8.000
                                                             6.000
                                                                   X
                                                                   o
                                                              4.000 i
                                                                   a.
                                                                   o_
                                                              2.000
                                                              0.000
        0.000      .250     .500     .750     1-000    1.250    1.500
                           TIME  (HOURS)

         FIGURE  B-2. COMPOSITION OF  GAS FROM SIDE
                      DRAFT  BURNING
                      Burning split oak logs
                      Burning rate 16.6 Ib/hr  (7.5 Kg/hr).
                                   78

-------
             5/15/80 DEFIANT  (DOWN DRAFT)  ROUND OAK  LOGS  N.D-63
o
o
   25.000 r
   20.000 -
   15.000 -
   10.000
    5-000
    0.000
   25.000 r
    o.ooo I	1	1	1	1	1	1    i
                                                            50.000
                                                            40.000
                                                            30.000
                                                                   o
                                                                   X
                                                            20.000
                                                                   0_
                                                                   a.
                                                             10.000
         0.000      .250     .500     .750    1.000     1.250     1.500*
                           TIME  (HOURS)

         FIGURE  B-3. COMPOSITION OF GAS FROM DOWN
                      DRAFT  BURNING
                      Burning  small split  oak cordwood
                      Burning  rate 19.1 Ib/hr (8.7 Kg/hr).
                                                             0.000
                                       79

-------
              6/18/80 DUMONT  OAK  LOGS   RUN  91
 i
z
<
o:
z
o
o
   25.000 r
   20.000
   15.000
   10.000
    5.000
    o.ooo o
                                                o   002

                                                o   co
                  -S	B-
                      LfTj	L~   I —
 I
z
<
o:
 z
 o
 o
    25.000  r
    20.000
    15.000
    10.000
     5.000
     o.ooo
                                                    OXTQEH


                                                    TOT.HC
                                -e -1-
                                                                50.000
                                                                40.000
                                                                30.000
      o
      I

20.000 *7
      z
      0_
      0.
                                                                10.000
         0.000      .313     .625     .938     1.250     1.563    1.875

                             TIME  (HOURS)



          FIGURE  B-4. COMPOSITION OF GAS  FROM HIGH

                       TURBULENCE  BURNING

                       Burning  split oak  logs

                       Burning  rate 24.1  Ib/hr  (11 Kg/hr)  .
                                                                 o.ooo
                                      80

-------
               6/17/80  DEFIANT  (SIDE  DRAFT)  OAK  RUN  87
   25.000 r
   20.000
    15.000
u_
o

CO   10.000
CD
     5.000
     0.000
                                                     Q
                                                         WEIGHT
               J	I
I	I	I
J	I     I     I	I
         0.000      .250
.500      .750      1.000     1.250     1-5

  TIME  (HOURS)
                FIGURE B-5. WEIGHT LOSS DURING SIDE DRAFT BURNING

                         Burning split oak logs

                         Burning rate: 16.6 Ib/hr (7.5 Kg/hr).
                                    81

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                                 APPENDIX C

                      POLYCYCLIC AROMATIC HYDROCARBON
                         MEASUREMENTS IN FLUE GAS

          Particulate emissions and polycyclic aromatic hydrocarbons (PAH)
samples were collected using a Modified Method 5 sampling apparatus.  Both
the location and configuration of the sampling system were described pre-
viously in the experimental section (Section 6).  This apparatus allowed the
collection of particulate emissions using filtration followed by collection
of gas phase PAH by adsorption on XAD-2 resin.  Operation of the sorbent
                                                                  *
sampler and the extraction procedure have been described elsewhere.    The
analysis of PAH compounds is complicated by the structural similarity of many
members of this class of compounds.  Several compounds exhibit positional
isomers,  e.g.,  benzo(a)pyrene and benzo(e)pyrene, which coelute on most
chromatographic systems.   Such isomeric groups often show drastic differences
among their members in physiological behavior.  For instance, benzo(a)pyrene
is known to be a potent animal carcinogen while benzo(e)pyrene is only weakly
active.  In order to resolve these isomeric groups, high resolution, gas
capillary column chromatography coupled to quadrupole mass spectrometry was
chosen to separate PAH compounds from these complex mixtures.  Single ion
monitoring was used to quantify PAHs.   Single ion monitoring improved the
sensitivity of mass spectral measurements along with providing electronic
isolation of fragment or parent ions characteristic of the compound of
interest.  An additional parameter was used to verify compound identity,  the
gas chromato graphic retention time.  From the elution of a set of PAH standards
*  Neher, M. B., Jones,  P. W.,  and Perry,  P. J.  Performance Evaluation
   of a Solid Sorbent Hydrocarbon Sampler, Research Report EPRI EP-959,
   Electric Power Research Institute, January, 1979.
                                     82

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of known purity,  a retention time window was determined and quantification
was performed only on those compounds eluting at the proper time.  Chromato-
graphic and mass spectrometer stability were verified by analysis of the
reference standards at the beginning and end of each run of samples.  In
addition, standards were run in triplicate at five concentration levels to
establish the linearity and precision of the analytical curve.  The capillary
column used for this analysis exhibited a very high chromatographic efficiency
as shown by the chromatogram for a test mixture of 21 PAH standards in
Figure C-l.  The extracts from both filter and resin catches proved to contain
a complex mixture of organic species as shown in the GC/FID trace of the
particulate associated PAH from a radiant wood stove burning seasoned oak
brands and operating in the up draft mode (see Figure C-2).
          The specific compounds quantified are listed in Table C-l.  It
should be noted that several isomeric groups were measured together, e.g.,
methylanthracenes.  Since PAH species often exhibit a simple mass spectral
fragmentation pattern consisting of the parent ion, this single ion can be
searched at retention times corresponding to known members of the compound
class and area responses grouped together for quantification.
          The measured levels of individual PAH offer a very interesting
comparison of the effect of burn mode on distribution of PAH formed during
combustion (see Table C-2).  PAH production during combustion of wood is an
especially interesting phenomena since neither lignin nor cellulose contain
PAH  compounds in the raw fuel.  The data of Table C-2 show total PAH in
milligrams emitted during combustion of a weighed charge of wood.  A portion
of the  flue gas was sampled at the flue gas outlet and the measured PAH
concentration was multiplied by a factor representing the total flue gas
effluent.  Thus, Table C-2 gives the total PAH emissions discharged by the
test stoves.
           Examining the data in Table C-2, several effects are noticed.  The
lower molecular weight PAH are found predominantly in the gas phase while the
larger  molecules tend to be associated with particulate matter.  During
sampling,  the nozzle and filter holder were thermostatically controlled to
remain  at  or above 250°F (121°C), but the flue gas entering the sampler was
regularly higher than this temperature.  Thus the absolute distribution of
PAH  between gas and particulate samples is a function of sampling conditions.

                                     83

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                             FIGURE C-l.  GAS CHROMATOGRAM OF PAH STANDARD MIXTURE.

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00
                    FIGURE  C-2.  GAS CHROMATOGRAM OF PARTICULATE ASSOCIATED ORGANIC COMPOUNDS
                                FROM SEASONED OAK COMBUSTION.

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     TABLE C-l.   POLYNUCLEAR AROMATIC SPECIES  QUANTIFIED
          Compounds  in Order of Gas  Chromatographic
                       Elution on SE-52
                         Naphthalene
                        Acenaphthene
                       Acenaphthylene
                           Fluorene
                        Phenanthrene
                         Anthracene             /•  v
          Methylanthracenes/Methylphenanthrenes
                        Fluoranthene
                           Pyrene
             Methylpyrenes/Methylfluoranthenes
                     Benzo(a)anthracene
                          Chrysene  ,, ,
                     Methylchrysenes
                 Dimethylbenzo(a)anthracene
                    Benzofluoranthenes(b)
                       Benzo(a)pyrene
                       Benzo(e)pyrene
                          Perylene
                   Indeno(1,2,3-cd)pyrene
                    Benzo(g,h,i)perylene
                          Coronene
                     Dib enzo(a,h)pyrene
(a)   Summation of all isomers identified in  sample  excluding
     internal standard:  9-methylanthracene.

(b)   Summation of all isomers identified in  sample.
                              86

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TABLE C-2.  TOTAL PAH (rog) EMITTED IN WOOD STOVE EMISSIONS
Burn Mode
Fuel
Species Measured
Naphthalene
Acenapthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Methylanthracenes/
Me thy Iphenanthrenes
Fluoranthene
Pyrene
Methylpyrenes/Methyl-
fluoranthenes
Benzo (a) anthracene
Chyrsene
Methylchyrsenes
Dimethylbenzo (a) anthracene
Benzof luoranthenes
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno (1 , 2 , 3-cd) pyrene
Benzo (g,h,i)perylene
Coronene
Dibenzo (a ,h) pyrene
Total
Total Emission
Side Draft
Oak-Seasoned
Particulate Gaseous
1.2
0.12
0.06
0.08
0.24
0.09
0.07

2.6
2.8
0.79

5.9
5.6
0.56
0.29
14
3.5
5.0
0.51
15
22
10
4.2
95
358
45
58
26
19
62
18
3.2

18
8.6
0.53

1.0
1.1
0.14
-
0.96
0.24
0.27
0.10
0.29
0.20
0.11
-
263

Side Draft
Pine-Green
Particulate Gaseous
0.22
0.27
0.06
0.12
2.2
0.35
0.13

2.9
3.1
0.63

3.0
3.2
0.54
0.28
21
7.1
13
1.8
38
30
16
9.3
154
502
80
89
7.3
26
100
19
7.4

11
6.1
0.82

0.22
0.21
0.12
-
0.15
0.08
0.08
0.09
_
-
-
-
348

Up Draft Down Draft
Oak-Seasoned Oak-Seasoned
Particulate Gaseous Particulate Gaseous
0.16
0.10
0,04
0.07
0.35
0.09
0.07

0.30
0.28
0.16

0.39
0.37
0,16
0.09
1.3
0,42
6.3
0.14
1.3
1.2
0.51
0.39
14
If
11
18
6.4
8.2
20
4.6
1.4

9.1
6.8
1.9

13
8.2
1.0
0.25
17
3.8
6.5
0.68
3.9
3.2
0.55
0.23
146
.0
0.07
0.12
0.05
0.09
0.17
0.08
-

0.12
0.07
-

0.16
0.11
_
„
0.11
0.07
0.07
0.09
0.17
0.13
0.17
0.12
2.0
3
52
51
4.8
3.4
96
11
2.0

68
38
2.6

6.1
8.5
0.26
0.13
3.7
0.48
0.20
0.09
0.15
0.09

_
349
51
High Turbulence
Oak-Seasoned
Particulate Gaseous
0.36
0.60
0.27
0.46
0.99
0.43
0.33

0.73
0.46
0.30

0.96
0.73

—
0.93
0.50
0.50
0.50
1.1
0.83
0.86

12
1
62
31
1.9
2.4
40
2,2
0.99

15
9.6
1.5

1.8
1.9
0.60

0.86
0.43
0.40
0.46
0.80
0.50
0.63

175
87

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In normal home operations, the cooling of flue gas on leaving the stove
distribution system will cause an association and condensation of PAH with
the discharged particulate matter.  Thus stove emissions measured after
discharge to the ambient air would be expected to have increased particulate-
associated PAH concentrations.
          As a general trend, observed in many combustion generated PAH
samples,  the amounts of high molecular weight PAHs are generally lower than
the amounts of low molecular weight compounds.   Phenanthrene was found to be
a predominant species,  a situation analogous  to high phenanthrene concentra-
tions found in coal combustion products.   Benzo(a)pyrene and benzo(a)pyrene
were produced in equivalent amounts except in the case of the up drafted
stove burning seasoned  oak,  a situation where the benzo(a)pyrene content was
appreciably higher.
          The measured  gas  concentration  and  emissions of the PAHs are shown
in Table  C-3.   The operating  conditions of  the  stoves  were shown in Table 2
of the report.   Comparing stove burning modes,  it  is observed that PAH
production was  similar  for  different modes, with up draft producing slightly
less total PAH than  side or down draft.   Green  pine generated slightly higher
levels of PAH than seasoned oak when the  two  fuels were  burned in the same
stove. The most  significant reduction  in total PAH was  observed in the high
turbulence furnace which evidently produced a highly efficient burn condition
and greatly reduced  PAH emissions.
          Benzo(a)pyrene average concentrations and emissions were separately
determined because of the special interest  in this specie and its relatively
high level of toxicity.  The side draft mode  produced  slightly lower emissions
of this specie when burning oak than the  up draft  burning mode.   The
down draft and high turbulence burning  modes, however, resulted in signifi-
cantly lower average emissions than the more  conventional side draft and up
draft modes.  These benzo(a)pyrene  average emissions were lower by one to two
orders of magnitude.
          A recent study of PAH emissions from residential wood combustion
                    *
was reported by EPA.   Data from  that  program can be directly compared with
*  DeAngelis, D.G.,  Ruffin,  D.S.,  Reznik,  R.B., and Milliken, J.O.,
   Preliminary Characterization of Emissions from Wood-Fired Residential
   Combustion Equipment, EPA-600/7-80-040, March, 1980, pg 60.
                                      88

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              TABLE C-3.   COMPARISON OF STOVE OPERATING PARAMETERS
                          AND EMISSION FACTORS FOR PAH COMPOUNDS
Burn
Mode
Fuel
Side
Draft
Oak(a)
Side
Draft
Pine(b)
Up
Draft
Oak(a)
Down
Draft
Oak(a)
Turbu-
lence
Oak
-------
data from this study (see Table C-4) since test stoves were operated with
similar fuels and similar operating parameters.  In Table C-4, specific
compounds and compound classes which were measured in both studies are
compared as parts-per-million (W/W) of discharge based on the weight of
fuel burned.
          The data from these two  studies show similar patterns for production
of PAH although the earlier  report found generally higher levels of total PAH.
Both studies  found that the  lower  molecular weight PAH were produced in
larger amounts than larger molecules and both studies showed that anthracene
and phenanthrene  are a  large fraction of the  PAH produced.   This finding
suggests that benzene may be produced in significant  amounts during
residential wood  combustion  and future  studies  of  wood combustion products
should include this important  suspect carcinogen in measurements.
          The apparent  difference  in  levels of  PAH measured  in the two
studies can possibly be explained  by  differences in stove operating parameters
or possibly by the difference  between the packed column gas  chromatographic
technique used in the earlier  report  compared to the  glass capillary method
used in this  study.  The packed column  can make  integration  of peak areas
difficult due to  coelution and peak overlap.  Since these two  studies were
not conducted identically, the observed  differences in PAH emissions are well
within the variability  of this type of  emission  measurement, and the vari-
ability in operating parameters for the  stoves tested.   Operating  parameters
are expected  to be the  major contributing factor to observed differences in
PAH content,  but  consideration should be given to  the  lack of  multiple tests
required to establish the precision of  reported  data.
                                      90

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                   TABLE C-4.   COMPARISON  OF REPORTED  PAH  EMISSIONS  (rag/kg or  lb/10   Ib  Wood  Fuel)
        Stove

        Fuel
Baffled  Non-Baffled*3)  Non-Baffled(a)  Side Draft(b)  Side Draft(b)  Up Drafc(b)  Down Draft(b>  High Turbulence^)

  Oak(c)        Oak(c)         Pine(d)         Oak(e)        Pine
-------
                               TECHNICAL REPORT DATA
                        (Pleat read lauructions on the reverse before completing)
.REPORT NO.
EPA-600/7-81-091
                          2.
                                                     3. RECIPIENT'S ACCESSION NO.
.TITLE AND SUBTITLE
Control of Emissions from Residential Wood Burning
by Combustion Modification
                                       5. REPORT DATE
                                        May 1981
                                       6. PERFORMING ORGANIZATION CODE
.AUTHORIS)
                                       8. PERFORMING ORGANIZATION REPORT NO.
J.M.Allen and W.M.Cooke
. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle, Columbus Laboratories
505 King Avenue
 olumbus, Ohio 43201
                                       10. PROGRAM ELEMENT NO.

                                        C9BN1B
                                       11. CONTRACT/GRANT NO.

                                        68-02-2686, Task 114
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
                                       13. TYPE OF REPORT AND PERIOD COVERED
                                        Task Final; 6/79-11/80
                                       14. SPONSORING AGENCY CODE
                                         EPA/600/13
s.SUPPLEMENTARY NOTES iERL_RTp project officer is Robert E. Hall,  Mail Drop 65, 919/
541-2477.
6. ABSTRACT
         The report describes an exploratory study of factors contributing to atmos-
pheric emissions from residential wood-fired combustion equipment. Three commer-
cial appliances were operated with both normal and modified designs, providing dif-
ierent burning modes: updraft with a grate, updraft with a hearth, crossdraft, down-
draft, and a high-turbulence mode utilizing a forced-draft blower. Fuels were nat-
urally dried commercial oak cordwood, commercial green pine cordwood, oven-dried
fir brands,, and naturally dried oak cut into reproducible  triangles. Continuous mea-
surements of stack gases included O2, CO2, CO, NO, SO2, and total hydrocarbons
(FID) as an indication of the total organic species in the stack gases  during batch
:ype operation. Several combustion modification techniques were  identified which
lave an appreciable effect on emission factors and, therefore, can be developed and
applied to reduce emissions in consumer  use. The more  promising design modifica-
tions include: prevention of heating the inventory of wood within the stove but not yet
actively burning, focusing the air supply into the primary burning area with high tur-
bulence,  and increasing the temperatures in the secondary burning regions of the
appliances.
                            KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                           b.lDENTIFIERS/OPEN ENDED TERMS
                        c. COSATi Field/Croup
Pollution
Residential
 Buildings
 Combustion
Stoves
Wood
Flue Gases
Dust
Sampling
Carbon Monoxide
Nitrogen Oxides
Aromatic Polycyclic Hydro-
 carbons     	
Pollution Control
Stationary Sources
Combustion Modification
Wood Stoves
Particulate
13 B

13M
21B
ISA
11L
11G
14B
07B


07C
118. DISTRIBUTION STATEMENT
 Release to Public
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                                          Unclassified
                                                    21. NO. OF PAGES
                                                       101
                           20. SECURITY CLASS (This page)
                            Unclassified
                        22. PRICE
EPA Form 2220-1 U-73)
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