EPA PROJECT REPORT NO. 74-KPM-20
                           MEAD CORPORATION

                           Chillicothe,  Ohio
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
            Office of Air and Waste Management
        Office of Air Quality Planning and Standards
              Emission Measurement Branch
   ,      Research Triangle Park. North Carolina

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KRAFT PULP MILL LIME KILN EMISSION TESTS
          THE MEAD CORPORATION
            CHILLICOTHE MILLS
            CHILLICOTHE, OHIO
          A REPORT PREPARED FOR
  U.S.  ENVIRONMENTAL PROTECTION AGENCY
        RESEARCH TRIANGLE PARK
        NORTH CAROLINA   27711
        EPA REPORT NO. 7*ป-KPM-20
         CONTRACT NO.  68-02-0239
               TASK NO.  10
              PREPARED BY:
  COTTRELL ENVIRONMENTAL SCIENCES, INC.
 A SUBSIDIARY OF RESEARCH-COTTRELL, INC
              P.O.  BOX 750
     BOUND BROOK, NEW JERSEY   08805
                                 G.J. GRIECO
                                 CES-13^-10

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                     TABLE OF CONTENTS






                                                        PAGE






INTRODUCTION                                             1




SUMMARY AND DISCUSSION OF RESULTS                        4




PROCESS DESCRIPTION AND OPERATION                        6




LOCATION OF SAMPLING POINTS                             10




SAMPLING AND ANALYTICAL PROCEDURES                      12






LIST OF FIGURES
FIGURE I:    STACK LAYOUT AND TEST PORT LOCATION         2




FIGURE II:   KRAFT PULPING PROCESS                       7




FIGURE III:  FLOW DIAGRAM OF THE LIME KILN               9




FIGURE IV:   LOCATION OF SAMPLING POINTS                11






LIST OF TABLES




TABLE I:   SUMMARY OF RESULTS                             5






APPENDICES




APPENDIX  A:  TEST DATA CALCULATIONS AND SUMMARY SHEETS




APPENDIX  B:  RAW DATA SHEETS




APPENDIX  C:  VELOCITY PROFILES




APPENDIX  D:  VISIBLE EMISSIONS REPORT




APPENDIX  E:  PROCESS DESCRIPTION AND OPERATION  (EPA)




APPENDIX  F:  TEST METHODS




APPENDIX  G:  TEST LOG




APPENDIX  H:  PROJECT PARTICIPANTS

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                            -1-

                       INTRODUCTION
A Cottrell Environmental Sciences, Inc.  test team performed
stack sampling tests at a kraft pulp mill  lime kiln owned
and operated by the Mead Corporation, Chillicothe Mills,
Chlllicothe, Ohio, during the period of August 4 through
August 12, 1974.

The process tested was a 200 tons/day CaO rotary kiln that
can operate on either #2 fuel oil  or natural gas.  The emis-
sions are controlled by a high energy venturi scrubber/
demisting tower and are emitted to the atmosphere through a
69" I.D., 73'  high smokestack (See Figure I).  An induced
draft fan is located between the kiln and the venturi scrub-
ber.  The lime kiln was operating  at approximately 60% of
design capacity (120 tons/day) during the test period; this
production rate is typical  of normal operation at this kiln.

The purpose of the test program is to obtain emission data
as part of the background data needed to establish new
source performance standards as authorized by the Clean Air
Act.  The United  States Environmental Protection Agency's
Emission Standards and Engineering Division of the Office of
Air Quality Planning and Standards selected this particular
lime kiln control  system because it is thought to represent
best available control technology.  Several other kraft pulp
mill lime kilns are also being tested by the EPA to obtain
additional emission data.

Particulate samples were extracted from the smokestack
approximately 60'  from ground level.  The nearest upstream
disturbance was the straightening  vanes (2.0 E.D.'s) and the
nearest downstream disturbance was the top of the smokestack
(2.3 E.D.'s).   Hence, forty  eight  (48) sampling points were
utilized In accordance with  EPA Method I.   The original in-
tention of this task was to  perform six (6) particulate
sampling runs in  accordance  with EPA Method 5 andtsix (6)
Orsat analyses (CO, C02, and 02) in accordance with EPA Method
3.  Three particulate tests  were to have been performed
while the kiln was fired with #2 fuel oil  and three tests
were to take place while firing natural  gas.  The particulate
samples were then  to be analyzed for particulate mass and
trace elements.  However, due to kiln operational problems
and test equipment malfunctions, only one valid particulate
test could be performed.

During the pretest visit (April 18, 1974)  a preliminary
velocity traverse  was performed to determine the variation
In the direction  of flow of  the gas stream across the stack
(See Appendix C).   This data indicates that the gas flow
was not parallel  to the stack.  The velocity traverse data
from the presurvey was not  used to calculate a stack gas
flow rate because  Cp was not known, the temperature was not
monitored at each  traverse  point,  and the traverse points
were equally spaced  instead  of at  the centroid of equal

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                                 -2-
          TEST
              —^

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                         FIGURE  I
           STACK LAYOUT AND  TEST  PORT LOCATION

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                            -3-
areas.   The velocity traverse was used to check for cy-
clonic  flow, and the relative variation In magnitude of
the velocity head across the stack was sufficient for this
purpose.

It was  decided that this "cyclonic" flow (due to the demist-
ing tower) could be alleviated by the installation of straigh-
tening  vanes.  The Mead Corporation requested that the vanes
be temporary (no modifications to the existing stack).  Temp-
orary vanes were designed and installed prior to testing
and marginal success was achieved.  The straightening vanes
were located 11.5' (2 E.D.'s) upstream from the test site
(See Figure  I and Appendix C).

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                            -4-
             SUMMARY AND DISCUSSION OF RESULTS
A summary of test results Is presented in Table I.   Appendix
A  of this report contains a computer printout, sample cal-
culations, a handwritten calculation form, a sample weight
"master sheet" and a laboratory analysis form.   All raw data
sheets may be found In Appendix B.

An unusually high particulate mass  concentration was measured
in the acetone blank (0.0132 gm/100 ml).  There is  no appar-
ent reason to believe that the sample was contaminated.  Rea-
gent grade acetone was utilized.
                                                      i
Appendix C contains velocity and  volumetric flow rate data.
It includes velocity profiles based on two preliminary vel-
ocity t raverses and one particulate sampling run from this
EPA test program.  Due to a kiln  operational problem (over-
flowing storage tanks), the only  test performed had to be
terminated after 217 minutes.  Two  minutes had  elapsed while
sampling from the 44th point (point B20) when the test team
was notified of an Impending shutdown.  The kiln was operating
on natural gas.  The isoklnetic rate for this run was 92.83%.

Appendix D contains a paper prepared by Scott Environmental
Technology, Inc., entitled "Test  Visible Emissions  of a
Kraft Pulp Mill Lime Kiln."  This report concerns the results
of visibly determined smoke opacity data corresponding to
periods of particulate testing.  The aforementioned run I
was designated Test 2 in this visible emissions report (see
Page 3, Figures 3a and 3b of the  report).

The probe used during run I was glass lined; however, there
was a 2" stainless steel connection at the ball joint end of
the probe that was in contact with  the sampled  gas.

The test program was terminated on  August 11, 1974  due to
recurring equipment malfunctions.  One meter box developed a,
serious pump motor-shaft problem; the spare meter box was
broken beyond  (field) repair in shipping.  The  probe heater
was not operating properly.  The  broken filter  holder glass-
ware was the result of an oversized stainless steel ball
joint located on the glass lined  sampling probe.  When test-
Ing was terminated all of the "front half" portions of the
filter holders were broken (about six were originally ship-
ped to the job site).

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                              -5-
                             TAJil-E 1
                        SUMMARY OF P.ESULTS
RunNun^ber ' ! /- AJ/^UAL
Date
Stack Flow Rate - SCFM * dry
* *
7, Wciter Vapor - % Vol. .
. % C02 - Vol % dry
% 02 - Vol % dry
% Excess air @ sampling point
S0_ Emissions - ppm dry
NO __ Emissions - ppra dr>'
A _ .
Particulntes. :..'•.•
Probe, Cyclone, & Filter Catch
gr/SCF* dry
gr/CF @ Stack Conditions
Ibs./hr.
Total Catch
gr /SCF*dry
gr /CF @ Stack Conditions
Ibs./hr.
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 * 70 F, 29.92 "Hg. .    .                        '    .
** The Saturated  Mo.fsture Content  from the Psychometric  Chart
   was used  to  determine Emission  Data Shown.

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                           -6-
             PROCESS DESCRIPTION AND OPERATION
The Mead Corporation Mill  at Chillicothe, Ohio produces 600
tons of kraft pulp per day.   All  the pulp is bleached and
converted into paper.   In  1964, the mill  converted from the
soda pulping process to the  kraft pulping process.
                    PROCESS DESCRIPTION
                       A.   GENERAL

The process for making kraft pulp from wood is shown in
Figure II.  The process wood is chipped into small pieces
and then cooked in eight batch digesters at elevated pres-
sure and temperature.  The cooking chemicals,  called white
liquor, are sodium hydroxide and sodium sulfiddein water
solution.  The white liquor chemically dissolves  lignin,
leaving wood cellulose (pulp) which is filtered from the
spent liquor and washed.  The pulp is then bleached, and
made into paper.

The balance of the pulping process is designed to recover
the cooking chemicals.  Spent cooking liquor and  the pulp
wash water are combined for treatment to recover  chemicals.
The combined stream, called weak black liquor, is concentrat-
ed in multiple-effect evaporators.  The black liquor receives
its final concentration in direct contact evaporators and  is
then fired to a recovery furnace.

Combustion of the organic matter in the black liquor provides
heat needed to generate process steam.  Inorganic chemicals
in the black liquor are recovered as a molten smelt at the
bottom of the furnace.  The smelt, consisting of  sodium car-
bonate and sodium sulfide, is dissolved in water  and trans-
ferred to a causticizing tank.  Lime added to this tank con-
verts sodium carbonate to sodium hydroxide, completing the
regeneration of white  liquor, which is then recycled to the
digesters.  The calcium carbonate mud that precipitates from
the causticizing tank,  is recycled to a kiln to regenerate
1 i me.
                      B.  LIME KILN

The lime kiln was designed  byTraylor Company to produce 200
tons of lime  (CaO) per day.  This  is equivalent to a pulp
production rate of about 800 tons  per day.  This rotary kiln
Is 300 feet long, with an inside diameter of 11 feet.   It  is
fired with either natural gas or No.
2 fuel  oil
The  feed to the kiln  is the calcium carbonate slurry  that
precipitates from the causticizing tanks.  The slurry  is
washed and then dried on a rotary vacuum drum, as shown  in
Figure III.  The dried cake is  removed from  the drum  on  a
knife edge and conveyed to the  kiln.   In the kiln,  the calcium
carbonate mud  is roasted and carbon dioxide  is driven  off,

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                                       -7-
JJ
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(No
1,1 n A n •_
HE LIQ
Oil + Na

UOR
2S)
^^ * • • rf

DICE fi T f • R
SYSI I:M

RECOVERY
FURNACE
SYSTEM
STAPK 1
— PULP 	 	 ;.•!!!.[> J — IMJIJ-
— )--n- ' 	 ••• .... WAIL
— • v r A v r- 1 r\ •" v \ ' i \ ' \ f- !' ., - ,_ป..ซป
i • L f\ r\ 1.1 :.. t ' '^ K L i IJ '•• > ' >'• "-"" "•"••
HFAVY MULTlPLi:
, F i" F F C T
*— BLACK— ; -'.' -,.ซ—
LIQUOR sYSlfr
AIR -
UJ
     SMELT
(NaoCO-3 + Na2S)
Cฃ
          WATER
    SMELT
  DISSOLVING
     TANK
                   GREEN  LIQUOR
     DIGESTER)
                    CAUSTICIZING
                        TANK
                        1ANK
                      II[
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                            -8-
leaving calcium oxide (lime)  as product.

The combustion gases from the kiln are cleaned in an adjust-
able throat venturl  scrubber  manufactured by Air Pollution
Industries.  The gases then pass through  a mist eliminator
and out a kO foot stack.   The scrubber water is recycled from
the mist eliminator  and blended with fresh water makeup.  A
portion of the recycled water is purged to prevent excessive
accumulation of solids, and recycled back to the mud washers.
                     PROCESS OPERATION
The purpose of the tests was to measure emission levels dur-
ing normal kiln operation.   Process conditions were carefully
observed, and testing was done only when the test facility
appeared to be operating normally.

During the tests, important process conditions were monitored
and recorded on data sheets.  Readings were taken about
every half-hour.   These records are in Appendix E.   As far
as known from the process information and conversations with
the operators, the kiln and scrubber operated normally during
the only test performed.  However,  the test was terminated
just prior to completion when the kiln was shutdown due to
the lime storage tanks being full.

The test was performed while the kiln was burning natural
gas at a rate of about 13,200 cubic feet per hour.   The kiln
was operating at about 65 percent of capacity, which is nor-
mal operation.  During the test, the venturi scrubber was
operating at a pressure drop of 21.0 inches of water.  The
water flow to the scrubber was ^70 gallons per minute.

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LIMESTONE
   MUD —
   AIR
   GAS  OR
   NO. 2. OIL
             LIME
           (PRODUCT)
           SAMPLING  PORTS -
                                              EXHAUST
                                         ."•""  GAS  "
FRESH
WATER'
                                                                       STACK
                                                                              \
                              DEMISTER
                  RECYCLE-
                                                                           •^ BLEED
  Figure I I I.  Flow Diagram of the Lime Kiln at the Mead Mill in Chillicothe, Ohio

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                           -10-

                LOCATION OF SAMPLING POINTS
Figure IV illustrates the location of the A8 test points
used during velocity traverses and particulate runs (EPA
Test Program).   The nearest upstream disturbance was straigh-
tening vanes (2.0 E.D.'s) and the nearest downstream distur-
bance was the top of the stack (2.3 E.D.'s).  A cyclonic de-
mister was located k.k E.D.'s downstream of the sampling loc-
ation, as shown in Figure I.

The straightening vanes were  the most restrictive factor in
determining the number of traverse points.   However, the re-
quirements of EPA Method I  were fulfilled in that k8 trav-
erse points were selected.

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                                            --11-
B

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                           -12-

            SAMPLING AND ANALYTICAL PROCEDURES
Appendix F contains a copy of pertinent sections from the
Federal Register, Volume 36, Number 2^7, December 23, 1971,
a schematic of the sampling train utilized, and a laboratory
analysis procedure.

The Federal Register outlines the methods to be used for
sample and velocity traverses for stationary sources (Method
1), the determination of stack gas velocity and volumetric
flow rate (Method II) and the determination of particulate
emissions from stationary sources (Method V).

The sample train schematic illustrates the remote filter box
modification of EPA Method V.  The "optional" cyclone located
in the heated area between the probe and filter was not used.
Prior to testing, 100 ml of distilled, deionized water was
placed in both impingers, one and two, and 200 grams of sil-
ica gel was placed In impinger four.  Due to the high % mois-
ture In the flue gas stream, it was necessary to remove some
of the water collected in the impingers and replace the sil-
ica gel part way through run I.

The fI berg lass filters were prepared using a slightly dif-
ferent method than is outlined in the laboratory analysis
procedure.  Each filter was dessicated for 2k hours, weighed
to +_ 0.0002 grams, and stored in a tin container prior and
after use.  A "front half" water wash was also included in
the cleanup procedure, the resulting sample weight being
added to the "front half" acetone wash catch.
            analyses were performed per EPA Method V part1
            in accordance with EPA Method III utilizing a
Fisher brand Orsat Analyzer with a 100 ml burett.
Three Orsat
i cu1 a te run
A different analytical  balance was used
testing, and so the filter weights were
blank v a 1 u e .
                                        before and after
                                        corrected for a
An organic extract was performed on the impinger water.
                                WRITTEN BY
                               APPROVED BY
GJG/nak
                                             x1 r\ /i  •
                                             l0?ฎ^!^. \^AJjfjR
                                             G"ary(TJA. Gr ieco
                                             Source Testing
                                             Superv i sor
                                             N.R. Troxel
                                             Manager, Source
                                             Testing Operations

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