United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 85-CHM-12
June 1985
Air
Chromium Screening
Study Test Report

Harbison-Walker
Refractories
Baltimore,
Maryland

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             EMISSION TEST REPORT
         HARBISON-WALKER REFRACTORIES
             BALTIMORE, MARYLAND
                  ESED 85/02

                 EMB 85CHM-12



                 Prepared by

       Entropy Environmentalists, Inc.
            Post Office Box 12291
Research Triangle Park, North Carolina  27709
           Contract No.  68-02-3852
     Work Assignments No. 18, 21, and 23
                  PN:  3023
               EPA Task Manager
               Dennis Holzschuh
    U. S. ENVIRONMENTAL PROTECTION AGENCY
         EMISSION MEASUREMENT BRANCH
 EMISSION STANDARDS AND ENGINEERING DIVISION
RESEARCH TRIANGLE PARK, NORTH CAROLINA  27711
                November 1985

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                                    CONTENTS
Figures                                                                    iv

Tables                                                                      v

1.0  INTRODUCTION                                                          1-1

2.0  PROCESS OPERATION                                                     2-1

     2.1  Process Description                                              2-1
     2.2  Air Pollution Control System                                     2-4
     2.3  Process Conditions During Testing                                2-4

3.0  SUMMARY OF RESULTS                                                    3-1

     3.1  Particulate Matter, Hexavalent Chroniun and Total Chromium       3-3
          3.1.1  Rotary Dryer Exhaust                                      3-4
          3.1.2  Fabric Filter Outlet                                      3-7
          3.1.3  Tunnel Kiln Stack                                         3-9
     3.2  Particle Size Distribution                                       3-10
     3.3  Emissions in Units of Process Rate and Control Equipment
            Collection Efficiency                                          3-12
     3.4  Sunmary of Analytical Results for Hexavalent and Total Chromium  3-14
     3.5  Visible Emissions Observation Data                               3-16

4.0  SAMPLING LOCATIONS AND TEST METHODS                                   4-1

     4.1  Rotary Dryer Exhaust (Sampling Location A)                       4-1
     4.2  Fabric Filter Outlet (Sampling Location B)                       4-5
     4.3  Fabric Filter Dust Hopper (Sampling Location C)                  4-7
     4.4  Tunnel Kiln Stack  (Sampling Location D)                          4-7
     4.5  Rotary Dryer Feed  (Sampling Location E)                          4-9
     4.6  Velocity and Gas Temperature                                     4-9
   .  4.7  Molecular Weight                                                 4-9
     4.8  Particulate Matter                                               4-10
     4.9  Particle Size Distribution                                       4-10
     4.10 Hexavalent Chromiun Content                                      4-11
     4.11 Total Chrcraiun Content                                           4-11

5.0  QUALITY ASSURANCE                                                     5-1
                                         ii

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                              CONTENTS (Continued)
APPENDICES
     A   TEST RESULTS AND EXAMPLE CALCULATIONS                             A-1
         Particulate, Hexavalent Chromium and Total Chromiun               A-3
         Example Particulate Test Calculations                             A-9
         Particle Size for Total Particulate, Hexavalent Chromiun          A-32
           and Total Chromiun
         Hexavalent Chromiun Particle Size Analytical Data                 A-58
         Total Chrccniun Particle Size Analytical Data                      A-60
         Total Chromium Analysis Calculation                               A-62
         Explanation of Total Chromium Analysis Calculation Table          A-64

     B   FIELD AND ANALYTICAL DATA                                         B-1
         Particulate Matter                                                B-3
         Particle Size Distribution                                        B-30
         Total Particulate Analysis                                        B-45
         Particle Size Distribution Analysis                               B-55
         Hexavalent Chromiun Analysis                                      B-62
         Total Chromium Analysis                                           B-67

     C  VISIBLE EMISSION OBSERVATION DATA                                  C-1

     D   SAMPLING AND ANALYTICAL PROCEDURES                                D-1
         Determination of Total Particulate Emissions                      D-3
         Determination of Hexavalent Chromium Emissions                    D-8
         Determination of Total Chromium Content                           D-15
         Determination of Particle Size Distribution                       D-22
         Grab Samples                                                      D-29

     E   CALIBRATION AND QUALITY ASSURANCE DATA                            E-1

     F   MRI PROCESS DATA                                                  F-1
         Process and Emission Capture Efficiency Observations of Rotary
           Dryer Baghouse During Testing                                   F-3
         Process Observation of the No. 1 Tunnel Kiln During Testing       F-7

     G   TEST PARTICIPANTS AND OBSERVERS                                   G-1
                                  ill

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                                    FIGURES




Number                                                                   Page




2-1  Flow Diagram for the Manufacture of Chromiun  Refractories             2-2




4-1  Process Air Flow Schematic of Rotary Dryer and Tunnel Kiln            4-2




4-2  Rotary Dryer Exhaust Duct (Sampling Location  A)                      4-4




4-3  Fabric Filter Outlet Stack (Sampling Location B)                      4-6




4-4  Tunnel Kiln Stack (Sampling Location D)                               4-8
                                       IV

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                                     TABLES

Number                                                                    Page

2.1  Final Operating Parameters for the Rotary Dryer and Tunnel
       Kiln No. 1                                                          2-6

3.1  Testing Schedule for Harbison-Walker                                  3-2

3.2  Sumnary of Flue Gas Conditions                                        3-5

3.3  Sunmary of Participate, Hexavalent Chromiun,  and Total
       Chromium Emissions                                                  3-6

3.4  Smmary of Particle Size Distribution                                 3-11

3.5  Summary of Emission Rates in Units of Process Rate and Efficiency     3-13

3.6  Sunmary of Analytical Results for Hexavalent and Total Chromiun       3-15

3.7  Sunmary of Analytical Results for Hexavalent and Total Chromiun
       Quality Assurance Samples                                           3-17

3.8  Sunmary of Visible Emissions Data for Fabric Filter for
       Harbison-Walker                                                     3-18

4.1  Sampling Plan for Harbison-Walker                                     4-3

5.1  Particle Size Blank Filter and Reactivity Filter Analysis             5-2

5.2  Audit Report Chromiun Analysis                                        5-4

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                               1.0  INTRODUCTION


    During the week of June 24, 1985, Entropy Environmentalists, Inc. conducted

an emission measurement program at Harbison-Walker Refractories plant located

in Baltimore, Maryland.  The purpose of this program was to provide data for a

screening study to determine the quantity and form of chromiun emissions

associated with the manufacture of refractories.

    Comprehensive testing was conducted on a rotary dryer controlled by a

cyclone and a fabric filter and an uncontrolled tunnel kiln.

    The rotary dryer and the tunnel kiln at this plant were selected for source

testing for the following reasons:

    •   The rotary dryer and tunnel kiln are typical process equipment for
        the refractories industry.  Both the chromite ore processed and the
        chromiun refractory bricks produced at this plant are typical for the
        industry.  Thus, uncontrolled emissions measured at this plant are
        expected to be representative of those at other plants in the
        industry.

    •   The rotary dryer is operated and used to dry chromiun-containing raw
        materials at least 8 to 12 hours per day.  Dryers at other plants are
        operated far less often.

    •   The fabric filter used to control the dryer and the degree of control
        achieved are typical of those at other plants in the industry.  Thus,
        the controlled emissions measured at this plant are expected to be
        representative of those at other plants in the industry.

    •   None of the tunnel kilns used in the industry are controlled.


    Participate concentrations and mass emission rates were measured at the

rotary dryer exhaust duct, fabric filter outlet, and tunnel kiln stack using

U. S. Environmental Protection Agency (EPA) Reference Method 5.*  Total chrcmiun
*40 CFR 60, Appendix A, Reference Method 5, July  1,  1981.

                                      1-1

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concentrations and hexavalent chromium concentrations  were measured at the  same




locations by further analysis of the Method 5  samples  using the alternate




sample preparation and analytical procedures as  described in Appendix  D.  Flue




gas flow rates,  temperature, moisture content,  and composition [oxygen (02),




carbon dioxide (002), and carbon monoxide (CO)]  were measured in conjunction with




the particulate tests.  In addition, the particle size distribution of




particulate matter emissions at the rotary dryer exhaust, the fabric filter




outlet, and tunnel kiln stack was determined along with hexavalent and total




chromium distribution by particle size.




     Representative samples of the dust collected by the fabric filter were




collected during the particulate tests for determination of the hexavalent  and




total chromiun content of the material entering  the fabric filter.




     Mr. Michael Maul [Midwest Research Institute (MRI)]  monitored process




operation throughout the test period.  Mr. Dennis Holzschuh (EPA Task  Manager)




of the Emission Measurement Branch (EMB) observed the  test program. Mr. A.  H.




Clark, Assistant Plant Manager - Engineering and Pat McDermott, Engineering,




served as the plant contacts and Mr. Ralph Crawford, Manager of Engineering,




served as the corporate contact for Harbison-Walker.




     This report is organized into several sections addressing various aspects




of the testing program.  Immediately following this introduction is the "Process




Operation"  section which includes a description  of the process and control




device tested.  Following this is the "Summary of Results"  section which




presents table summaries of the test data and discusses these results.  The next




section, "Sampling Locations and Test Methods"  describes and illustrates the




sampling locations for emissions testing and grab sampling and then explains the




sampling strategies used.  The final section,  "Quality Assurance,"  notes the
                                      1-2

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procedures used to ensure the integrity of the sampling program.  The




Appendices present the complete Test Results and Example Calculations




(Appendix A); Field and Analytical Data (Appendix B); Visible Emissions




Observation Data (Appendix C); Sampling and Analytical Procedures (Appendix D);




Calibration Data (Appendix E); MRI Process Data (Appendix F); and Test




Participants and Observers (Appendix G).
                                      1-3

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                          2.0  PROCESS OPERATION

2.1  PROCESS DESCRIPTION
      Harbison-Walker Refractories is a diversified refractories producer
with several plants throughout the country.   The Baltimore,  Maryland,
plant produces basic refractory brick and unformed refractories (specialty
refractories).  Magnesite-chromium refractory brick is the predominant
basic refractory brick produced at the plant.   The Baltimore plant is
listed by the U.S.  Bureau of Mines as one of the major users of chromium
in the refractory industry.   This plant is among the larger suppliers  of
chromium-containing refractories.  The chromite ore content in the
magnesite-chromium refractory brick ranges between 0 and 80 percent.
The process equipment used to produce basic brick at the Baltimore plant
is typical of that used in the industry.
      Figure 2-1 is a flow diagram for the manufacture of refractories
that contain chromium at the plant.   Chromite ore, which is imported,  is
stored outdoors in stockpiles adjacent to stockpiles of magnesite ore.
Magnesite-chromium brick that are rejected for sale (called "bats") are
also typically stored outdoors until  they are reprocessed.  A front-end
loader is used to transfer magnesite ore and the bats to a vibrating
grizzly,  which feeds into a gyrating crusher.   The crushed bats are
transported by belt conveyor to the rotary dryer that was tested, which
is used to dry raw materials containing chromium.   The crushed magnesite
ore is transported by belt conveyor to a rotary dryer used to dry only
magnesite ore.  The chromite ore, which does not require crushing, is
placed directly into a hopper next to the chromium rotary dryer by a
front-end loader.
      The chromium rotary dryer is approximately 6 feet (ft) in diameter
and 60 ft in length.  The burner is located at the discharge end of the
dryer and is fired by natural gas, although No. 2 fuel oil can be used.
The dryer operates at temperatures between 500° and 600°F and has a
rated production capacity of 25 tons/h.  The actual production rate is
about 14  to 20 tons/h, however, because of limitations in kiln production
rate.   Moisture content of the chromite ore is approximately 2 percent
prior to  drying and less than 0.5 percent after drying.
                                  2-1

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  PRESS
   I
  J     1
                 \
                             ROTARY DRYER
                             (CHROMIUM)
                             ROTARY DRYER
                             (MAGNESITE)
                   \
  PACKAGING AND
  SHIPPING
                         MIXEU
                                 TUNNEL KILN
                                                   STORAGE AND HOLDING BINS
fiATCM
RAILCAR
            SCREENS/    BALL HILL/
            AIR         DRY PANS
            SEPARATOR


             PACKAGING AND
             SHIPPING
Figure 2-1.   Flow diagram  for  the manufacture of chromium refractories.

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      The hot, dried materials, which are typically 350° to 400°F in
temperature at the dryer discharge end, are sent through a rotary cooler
located next to the rotary dryer.  The rotary cooler consists of a
horizontal, cyclindrical steel shell measuring approximately 6 ft in
diameter and 40 ft in length.  Cooling is achieved by the countercurrent
flow of ambient air into the cooler, which reduces the temperature of
the dried materials to 150°F.  The rotary cooler is used only during
summer months to hasten cooling so that binding agents added later in
the production process will not evaporate.
      After drying, the chromite ore and the other raw materials are
ground to specified sizes.   The different size raw materials are weighed
out in various proportions and mixed with a liquid binder and other
minor additives.   The resultant mixture is then fed to a mechanical
brick press where various refractory shapes are produced.  Any scrap
from the presses is recycled to the grinding, screening, and mixing
stages of the process.
      Although some of the pressed brick are dried, packaged, and shipped
without further processing, most of the pressed brick are placed on a
refractory-protected railcar and sent through either tunnel kiln No.  1
or No.  2 where they are fired at high temperatures.  Each kiln measures
approximately 320 ft in length, 12 ft in height, and 10 ft in width.
The kilns are equipped with 18 burners mounted along the middle section
of both sidewalls and are fired by natural gas.
      Each kiln has three zones, a preheating zone at the entrance of
the kiln, a firing zone in the middle section of the kiln, and a cooling
zone.   The hot combustion gases are drawn countercurrent to the flow of
brick through the firing and preheating zones by an induced draft fan.
The kiln exhaust gases, which total approximately 46,000 acfm at 660°F,
are ducted out through a stack.  The kiln firing temperature zone is
typically kept at 3200°F.   The entrances to the tunnel kilns are double
sealed with sliding doors to prevent air from being drawn in and disrupting
the countercurrent airflow.   Approximately 48 hours are required for the
brick to travel the entire length of a kiln.   Brick exiting the kilns
are cooled and subsequently packaged and shipped.
                                  2-3

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2.2  AIR POLLUTION CONTROL SYSTEM
      Emission points in the production process are controlled by baghouses
for raw material recovery and for air pollution control.   The chromite
ore dryer is equipped with a single compartment, negative-pressure
baghouse preceded by a cyclone.   The baghouse is located above the
rotary dryer and .inside the building that houses the dryer.   The baghouse
contains 456 woven glass bags that each measure 5 inches in  diameter and
9 ft in length, resulting in a cloth area of 5,372 square feet.   The
baghouse is designed to handle 9,000 acfm of gas at an air-to-cloth
ratio of 2.5:1 and a pressure drop of 6 inches w.c.   The bags are cleaned
once every 2 hours using vibration created by sonic horns.   Prior to
entering the baghouse, the temperature of the heated gas stream is about
350°F.   The baghouse exhaust is  discharged at a temperature  of about
140°F through a rectangular stack that extends from the baghouse outlet
up through the roof of the building.  Tests were conducted at both inlet
and outlet to the chromite ore dryer.
      The rotary cooler is controlled by a negative-pressure, continuous-
cleaning pulse jet baghouse.  The baghouse has 1 compartment with 144
polyester felt bags.  The bags measure 6 inches in diameter  and 8.3 feet
in length.   The total cloth area is 1,887 square feet.  The  baghouse is
designed to handle 10,000 acfm of gas at an air-to-cloth ratio of 5:1.
The stack dimensions are the same as those of the rotary dryer baghouse
stack.   The cooler baghouse was  not tested.
      Neither tunnel kiln is equipped with a control device.   Combustion
gases and any entrained particulate matter are emitted directly to the
atmosphere through a stack at an exhaust gas temperature of  between 700°
and 800°F.   Tests were conducted at the exhaust stack of the No. 1 kiln.
2.3  PROCESS CONDITIONS DURING TESTING
      The rotary dryer, the rotary dryer baghouse, and the No. 1 tunnel
kiln were monitored to ensure normal operation throughout the test.  The
dryer process parameters monitored included type of chromium product
dried,  percent Cr203 in the product, production rates, and operating
procedures.  The kiln process parameters monitored included type of
chromium product dried, percent Cr203 in the product, production rates,
                                  2-4

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operating procedures, draft pressure, temperatures in the firing zone,
exhaust gas temperatures, and fuel flow to the kiln.   Observations of
fugitive emissions escaping the dryer were made about every 15 minutes
of operation, and estimates of emission capture efficiency were recorded.
In addition, system wide pressure drop for the baghouse was monitored,
as were visible emissions from the baghouse stack.
      Table 1 lists the material throughput and characteristics for the
dryer and No. 1 tunnel kiln during testing.  Process parameters and
observations recorded during the test program are presented in Appendix F
Processes were operated within normal limits throughout the tests.
Observations of the dryer operation during testing were made about every
15 minutes.   No gauges were available to monitor the dryer firing tempera-
ture.  The flame temperature is adjusted based on operator judgment.
Because of the steady-state nature of the tunnel kiln, plant personnel
only record the firing zone temperature every 2 hours, the draft pressure
and exhaust temperature once every 4 hours, and the fuel flow once
each shift.
      During the first test on Tuesday, June 25, three different chromite
ores were processed by the dryer.  For the last 20 minutes of the run
during which the second chromite ore was being processed, the dryer
flame was turned off because there was sufficient heat in the dryer to
dry the remaining material adequately.  This flame shutdown is considered
normal operation by the plant and was done during each test run.  Twenty
minutes into the run during which the third chromite ore was being
processed, the chain on the rotary dryer slipped.   The dryer was shut
down, and the test was discontinued for the day.  The baghouse was not
cleaned during this test run.
      On Wednesday, June 26, the second test covered processing of one
type of chromite ore.   Testing continued during the cleaning of the
baghouse.   Visible emissions ranging between 0 and 35 percent opacity
were noted during cleaning and immediately after the baghouse came back
on-line.
      The third test on June 26 consisted entirely of recycled bats.
Because the brick typically contains less moisture than the ore, the
intensity of the burner flame was decreased from that used for ore
                                  2-5

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            TABLE 2-1.   FINAL OPERATING  PARAMETERS  FOR  THE  ROTARY
                        DRYER AND TUNNEL KILN  NO. 1
Test
run No.

1
1
2
3
4
4
1
2
3
Chromite Process
product weight, tons

Hammond-10
T-chrome
BC-3
Nu-60 bats
T-chrome
Hammond-10
0.65 Nu-60b
0.35 HW31-73
0.70 Nu-60
0.30 other brick
0.70 Nu-60
0.30 other brick
Rotary dryer
35.00
3.56
27.90
37.20
12.30
21.35
Tunnel kiln No.
7.35
8.59
8.03
Percent
Cr203

32
56.5
46.3
14.5
56.5
32.0
1
14.5
10. 0C
14.5
10.0
14.5,
10. Ob
Cr203
throughput

11.20
2.01
12.92
5.39
6.95
6.83
0.95
1.13
1.06
 Process weight during inlet testing only.   Process  weight during  outlet
 testing is similar since inlet and outlet testing were  done  as  close
.together as possible.
 Type of chromite product averaged over test run.
CApproximate average of Cr203 in the variety of chromite products.
                                    2-6

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drying.  More fugitive emissions escaped the dryer from the feed exit
during some of this test than during the tests for chromite ore processing.
Plant personnel indicated that a partial blockage in the ductwork leading
to the baghouse might be decreasing the airflow, rendering the baghouse
less effective for emission capture at the point of material transfer.
The crushed brick had more fine lightweight material than the chromite
ores and apparently overburdened the capture system at this point on
occasion.  Testing was not stopped because it was estimated that 98 percent
of rotary dryer emissions were still being captured by the baghouse
despite the increased fugitive emissions.   Two-thirds of the way through
the third test, the conveyor belt transporting the recycled brick to the
dryer jammed.  The dryer flame was turned down to low, and the rotation
of the drum stopped for about 5 minutes.  Testing was stopped temporarily
until the operation was back to normal.  Testing continued through the
cleaning cycle of the baghouse.   Visible emissions ranging between 0 and
5 percent opacity were noted during cleaning and immediately after the
baghouse came back on-line.
      The fourth dryer test on June 26 was done during the processing of
two different chromite ores.  The second chromite ore processed needed a
higher temperature flame to ensure sufficient drying.  The dryer was
stopped rotating for about 3 minutes during testing because of a
bottleneck downstream in the production process.  Because the burner was
firing and chromite ore was in the dryer,  testing was continued during
the short time the dryer was not rotating.  The baghouse was not cleaned
during this test run.
      The rotary dryer baghouse and tunnel kiln operated continuously
without interruption throughout the testing.
                                  2-7

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                            3.0  SUMMARY OF RESULTS








    Paniculate matter and particle size distribution tests  were conducted at




the rotary dryer exhaust (uncontrolled rotary dryer emissions),  the fabric




filter outlet (controlled emissions from rotary dryer and fugitive dust from




materials handling), and the tunnel kiln outlet (uncontrolled tunnel kiln




emissions).  The fugitive dust from the five material handling pick up points




entered the duct to the fabric filter downstream of the rotary dryer exhaust




sampling location and was not quantified.  The testing schedule  for




Harbison-Walker is shown in Table 3.1.




    In brief, the uncontrolled emissions from the rotary dryer averaged 28.9




pounds per hour of particulate, 0.0003 pounds per hour of hexavalent chromium




and 3.5 pounds per hour of total chromium.   The controlled emissions fron the




fabric filter controlling the rotary dryer and five fugitive dust material




transfer points averaged 5.3 pounds per hour of particulate, 0.0002 pounds per




hour of hexavalent chromium, and 0.64 pounds per hour of total chromiun.   The




overall collection efficiency of the fabric filter was greater than 80 percent




by weight for particulate emissions, greater than 35 percent by  weight for




hexavalent chromiun, and greater than 80 percent by weight for total chromium.




The collection efficiency values for both hexavalent chromiun and total




chromiun are not accurate representations of the actual collection efficiencies




since more than half the emissions exiting the fabric filter are materials




collected prior to the testing and held in the filter cake.   For this test




program, the material on the bags of the fabric filter which was collected




prior to testing was higher in hexavalent chromium concentration, thereby




making the hexavalent chromiun collection efficiency appear lower.







                                      3-1

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                                         TABLE 3.1.  TESTING SCHEDULE  FOR  HARBISON-WALKER
I
to
Date
(1985)
6/25
6/26
6/27
6/28
Sample Type
Particul ate
Particle size
Particul ate
Participate
Particul ate
Particle size
Particle size
Particle size
Particul ate
Particul ate
Particle size
Particle size
Particle size
Particul ate
Particle size
Rotary Dryer Exhaust
Run
No.
1
SI
3
5
7
S5
S9
Sll


Test Time
24 h clock
0815-1053
1117-1137
0813-1016
1124-1423
1623-1852
1019-1026
1508-1523
1856-1911


Fabric Fil ter Outlet
Run
No.
2
S4
4
6
8
S6
S8
S10


Test Time
24 h clock
0820-1110
0836-1101
0810-1033
1107-1432
1514-1829
0823-1006
1125-1418
1519-1807
-

Tunnel Kiln Stack
Run
No.


9
10
S12
S13
S14
11
S15
Test Time
24 h clock


1050-1401
1525-1833
0949-1150
1254-1654
1733-1933
0732-1050
0716-0916

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    The uncontrolled emissions from the tunnel kiln averaged 3.3 pounds per




hour of particulate matter, 0.009 pounds per hour of hexavalent chromium, and




0.14 pounds per hour of total chromium.



    The particle size distribution tests for the rotary dryer showed that about




24 percent of the uncontrolled particulate matter emissions were less than




10 ym and 52 percent of the controlled emissions were less than 10 ym in




diameter.  Further analysis of the combined particulate samples showed that




about 64 percent of the hexavalent chromium emissions were less than 10 ym and




75 percent of the controlled hexavalent chromium emissions were less than




10 ym.  The particle size distribution tests for the tunnel kiln showed that




84 percent, 84 percent, and 93 percent of the emissions by weight were less




than 10 ym for the uncontrolled emissions of particulate, hexavalent chromium




and total chromium, respectively.




    In the following sections, the results addressed above and additional




results are presented and discussed in detail according to the emission type




and sampling location.  The computer printouts of the emission calculations can




be found in Appendix A.  The original field data sheets and the analytical data




are located in Appendix B.







3.1  PARTICULATE MATTER, HEXAVALENT CHROMIUM, AND TOTAL CHROMIUM




    Particulate matter tests (EPA Method 5) along with the determination of the




associated flue gas flow rates were conducted at the rotary dryer exhaust,




fabric filter outlet, and tunnel kiln outlet.  The particulate matter samples




were initally analyzed using gravimetric techniques to determine the mass of




particulate matter.  Then the samples were further analyzed for hexavalent and




total chromiun.  Complete descriptions of each sampling location and the




sampling and analytical procedures used are given in Chapter 4.
                                      3-3

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3.1.1  Rotary Dryer Exhaust




    The emission measurements made at the rotary dryer exhaust represent the




uncontrolled emissions from the rotary dryer.




    Flue Gas Conditions and Isokinetic Sampling Rate - A sunmary of the flue




gas conditions at the rotary dryer exhaust is presented in Table 3.2.   The




volumetric flow rate for the four runs averaged 6,800 actual cubic meters per




hour (238,000 actual cubic feet per hour) with a flue gas temperature of




151°C (304°F), and a moisture content of 12.6 percent and composition of




16.2 percent oxygen, and 2.7 percent carbon dioxide.  The volunetric flow rate




at standard conditions averaged 4,100 dry standard cubic meters per hour




(145,000 dry standard cubic feet per hour).  Standard conditions are 20°C




(68°F), 760 mm Hg (29.92 in. Hg) and dry.




    The isokinetic sampling rate was within the allowable range for all runs.




    Particulate Emissions - The particulate emissions from the rotary dryer




(see Table 3.3) were variable.  The variability is believed to be the normal




variability related to the process operations.  The particulate emissions




averaged 3170 milligrams per dry standard cubic meter (1.39 grains per dry




standard cubic foot) and 13.1 kilograms per hour (28.9 pounds per hour).




    Hexavalent Chromixro Emissions - The hexavalent chromiun emissions were




variable when compared to the corresponding particulate run and averaged 9, 11,




20, and 6 micrograms of hexavalent chromium per gram of particulate matter




emissions.  The hexavalent chromiun emissions averaged 0.033 milligrams per dry




standard cubic meter (15 x 10~  grains per dry standard cubic foot) and




0.00014 kilograms per hour  (0.00032 pounds per hour).  The emission results




were in the quanifiable range, therefore, the variability is probably due to




the variability in the process and materials processed.
                                       3-4

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                                                               TABLE 3.2.  SUMWRY OF FLUE GAS CONDITIONS
i
Ln
Run
No.
Date
(1985)
Test Time
24 h clock
Volumetric Flow Rate
Actual8
acmh
x 106
acfh
x 106
Standard
dscmh
x 106
dscfh
x 106
Stack
Temperature
°C
°f
Moisture
%
°2
co2
CO
%
Isok 1 net Ic
%
                                                                        Rotary Dryer Exhaust
1
3
5
7
6/25
6/26
6/26
6/26
Average
0815-1053
0813-1016
1124-1423
1623-1852

0.0067
0.0070
0.0063
0.0070
0.0068
0.237
0.248
0.223
0.246
0.238
0.0036
0.0038
0.0049
0.0041
0.0041
0.127
0.135
0.171
0.146
0.145
176
188
84
156
151
349
371
184
313
304
18.2
13.7
5.6
12.8
12.6
15.8
14.6
19.6
15.0
16.2
3.2
3.4
0.8
3.4
2.7
0.0
0.0
0.0
0.0
0.0
109.9
100.3
92.5
100.2

                                                                        Fabric FlIter Outlet
2
4
6
8
6/25
6/26
6/26
6/26
Average
0820-1 110
0810-1033
1 107-1432
1514-1829

0.0156
0.0146
0.0153
0.0157
0.0153C
0.550
0.514
0.540
0.556
0.540C
0.0126
0.0117
0.0137
0.0135
0.0129C
0.446
0.412
0.484
0.476
0.454C
71
72
49
58
62C
160
161
121
136
144C
5.6
5.7
1.5
3.5
4.lc
19.2
18.0
19.9
19.7
19.2C
1.3
0.9
0.5
0.7
0.85C
0.0
0.0
0.0
0.0
0.0
95.3
97.5
80.7
96.4

                                                                               Tunnel Kiln Stack
9
10
11
6/27
6/27
6/28
Average
1050-1401
1525-1833
0732-1050

0.0982
0.0975
0.0989
0.0982
3.47
3.44
3.49
3.47
0.0394
0.0389
0.0404
0.0396
1.39
1.38
1.43
1.40
416
416
409
414
781
781
768
777
5.5
5.9
4.8
5.4
16.5
16.7
17.0
16.7
2.3
2.3
2.5
2.4
0.0
0.0
0.0
0.0
93.1
102.4
93.0

                  Volumetric flow rate In actual  meters  per  hour  (acmh)  and  actual cubic  feet per hour  (acfh) at stack conditions.
                  Volumetric flow rate In dry  standard cubic meters per  hour  (dsmh)  and dry standard cubic feet per hour  (dscfh).
                  These values show that the ambient  dilution air  was  approximately  twice the Inlet flue gas.

-------
                                           TABLE 3.3.  SUMM/RY OF P/ftTICULATE,  HEXAVALENT CWOMIUM, AND TOTAL CWOMIUM EMISSIONS
Run
No.
Date
(1985)
Parti cul ate
Concentration
mg/dscm
gr/dscf
Mass Emissions
kg/h
Ib/h
Hexavalent Chromium
Concentration
mg/dscm
gr/dscf
x 10~3
Mass Emissions
kg/h
Ib/h
Total Chromium
Concentration
mg/dscm
gr/dscf
Mass Emissions
kg/h
Ib/h
                                                                      Rotary Dryer Exhaust
1
3
5
7
6/25
6/26
6/26
6/26
Average
2)91
2675
2804
5027
3170
0.957
1.169
1.225
2.197
1.387
7.87
10.22
13.61
20.74
13.11
17.35
22.52
30.00
45.73
28.9
0.0196
0.0298
0.0554
0.0288
0.0334
0.00858
0.01304
0.02421
0.01260
0.01461
0.000071
0.000114
0. 000269
0.000119
0.000143
0.000156
0.000251
0. 000593
0.000262
0.000316
366
551
258
424
400
0.160
0.241
0.113
0.185
0.175
1.31
2.10
1.25
1.75
1.60
2.90
4.64
2.76
3.85
3.54
U)
I
en
                                                                       Fabric Fl Iter Outlet
2
4
6
8
6/25
6/26
6/26
6/26
Average
163.6
241.9
186.7
157. 1
187a
0.0715
0.1057
0.0816
0.0686
0.0818a
2.064
2.826
2.556
2.115
2.39
4.551
6.230
5.636
4.664
5.27
0.00460
0. 00642
0.00644
0.00717
0.006163
0.00201
0.00281
0.00281
0.00313
0.00269a
0. 000058
0. 000075
0. 000088
0.000097
0.000080
0.000128
0.000165
0.000194
0.000213
0.000175
21.9
29.0
17.7
22.6
22. 8a
0.0096
0.0127
0.0077
0. 0099
0.010a
0.276
0.339
0.242
0.304
0.29
0.609
0.747
0.533
0.670
0.64
                                                                                Tunnel  Kl In Stack
9
10
1 1
6/27
6/27
6/28
Average
46.94
42.70
24.37
38.0
0. 0205
0.0187
0. 01 06
0.0166
1.848
1.663
0.984
1.50
4.073
3.666
2.170
3.30
0.1034
0. 1 1 79
0. 0903
0. 1039
0.0452
0.0515
0.0395
0.0454
0.00407
0.00459
0. 00365
0.00410
0.00897
0.01012
0. 00804
0. 00904
1.09
2.36
1.48
1.64
0.00048
0.00103
0.00065
0.00072
0.043
0.092
0.060
0.065
0.095
0.203
0. 132
0.143
      The pollutant concentrations have been biased low by a factor of approximately three due to the fact that the dilution air was about

      twice the amount of the Inlet flue gas.

-------
    Total Chromiun Emissions - The total chromiun emissions for each test run




(see Table 3.3) were variable when compared to the corresponding particulate





results, and averaged 17, 21, 9, and 8 percent by weight total chromiun.  As




for the hexavalent chromiun emissions, the variability is probably due to the




variability in the process.  The total chromium emissions averaged 400




milligrams per dry standard cubic meter (0.175 grains per dry standard cubic




foot) and 1.60 kilograms per hour (3.54 pounds per hour).









3.1.2  Fabric Filter Outlet




    The fabric filter outlet emissions represent the controlled emissions from




(1) the rotary dryer and (2) five material handling pick up points (fugitive




dust).  Following the inlet sampling location were the insersections of an




emergency bypass stack with damper and the five ducts used to control fugitive




emissions from the material handling points.  The volume of ambient air




entering the system from the ducts and the damper was almost double the volume




of flue gas fron the rotary dryer.  This resulted in a measured outlet




volumetric flow (at standard conditions) of approximately three times that of




the measured inlet flow.  This did not cause any problems in sampling; the net




result is, however,  pollutant concentrations that are biased low by a factor




of three, a volumetric flow rate biased high by a factor of three, and a true




value for the mass emission rate.




    Flue Gas Conditions and Isokinetic Sampling Rate - A summary of flue gas




conditions at the fabric filter outlet is presented in Table 3.2.  The




volumetric flow rate (which includes the dilution air) was very consistent for




all runs and averaged 15,300 actual cubic meters per hour (540,000 actual cubic




feet per hour) with a flue gas temperature of 62°C (144°F) and a moisture




content of 4.1 percent and composition of 19.2 percent oxygen and 0.85 percent
                                       3-7

-------
carbon dioxide.  The volunetric flow rate (including dilution air)  at standard




conditions averaged 12,900 dry standard cubic meters per hour (454,000 dry




standard cubic feet per hour).  Standard conditions are 20°C (68°F),  760 mm Hg




(29.92 in. Hg) and dry.




    The isokinetic sampling rate was well within the allowable range for three




of the four sample runs.  The other run (at 81 percent) was less than 90




percent of the isokinetic sampling rate.  This would have very little effect on




the total results since the flue gas parameter values for this run were close




to the averages of the other runs.




    Participate Emissions - The particulate emissions from the fabric filter




were fairly consistent (see Table 3.3) and averaged 187 milligrams per dry




standard cubic meter (0.082 grains per dry standard cubic foot)  uncorrected for




dilution air and 586 milligrams per dry standard cubic meter (0.26 grains per




dry standard cubic foot) corrected for dilution air.  The emission rate




corresponding to both the uncorrected and corrected concentrations was 2.4




kilograms per hour (5.3 pounds per hour).




    Hexavalent Chrominu Emissions - The hexavalent chromiun concentrations in




the particulate catch were much higher at the fabric filter outlet than at the




rotary dryer exhaust and averaged 28, 27, 34, and 46 micrograms  of hexavalent




chromiun per gram of particulate matter for Runs 2, 4, 6, and 8, respectively.




This higher concentration is a result of the fact that the material previously




collected on the bags which was released during the testing was  several times




greater in chromiun concentration than the uncontrolled emissions.  The




hexavalent chromiun emissions averaged 0.006 milligrams per dry standard cubic




meter (2.7 x 10~  grains per dry standard cubic foot) and 0.00008 kilograms




per hour (0.00018 pounds per hour).
                                       3-8

-------
    Total Chromium Emissions - The total  chromiun  emissions  for  each  test  run




(see Table 3.3) were fairly consistent when compared  to  the  corresponding




particulate results and averaged 13,  12,  9,  and  14 percent by weight  total




chromiun.  The total chromiun emissions averaged 22.8 milligrams per  dry




standard cubic meter (0.01  grains per dry standard cubic foot) and 0.29




kilograms per hour (0.64 pounds per hour).









3.1.3  Tunnel Kiln Stack




    The tunnel kiln emissions represent the uncontrolled emisisons from the




tunnel kiln.  No air pollution control equipment is installed to collect these




emissions, therefore, these emissions are discharged  to  the  atmosphere.




    Flue Gas Conditions and Isokinetic Sampling  Rate  - A summary of the flue




gas conditions from the tunnel kiln is presented in Table 3.2.   These were very




consistent from run to run; the volunetric flow  rate  averaged 98,200  actual




cubic meters per hour (3,470,000 actual cubic feet per hour), with an average




flue gas temperature of 414°C (777°F), a  moisture  content of 5.4 percent,




and a gas composition of 16.7 percent oxygen and 2.4  percent carbon dioxide.




The volunetric flow rate at standard conditions  averaged 39,600  cubic meters




per hour (1,400,000 dry standard cubic feet per  hour).   Standard conditions are




20°C (68°F) , 760 mm Hg (29.92 in. Hg) , and dry.




    The isokinetic sampling rate was within the  allowable range  for all runs.




    Particulate Emissions - The particulate emissions from the tunnel kiln were




fairly consistent from run to run (see Table 3.3), and averaged  38 milligrams




per dry standard cubic meter (0.017  grains per dry standard  cubic foot) and 1.5




kilograms per hour (3.3 pounds per hour).




    Hexavalent Chromium Emissions - The hexavalent chromiun  concentration  in




the particulate catch was variable from run to run, averaging 2200, 2800, and




3700 micrograms of hexavalent chromium per gram  of particulate emissions.  The






                                       3-9

-------
hexavalent chrcmiun emissions averaged 0.10  milligrams per dry standard cubic




meter (0.045 x 10~  grains per dry standard cubic foot) and 0.004 kilograms per




hour (0.009 pounds per hour).




    Total Chromium Emissions - The total chrcmiun emissions for each test run




(see Table 3.3) were variable when compared to the corresponding particulate




results, and averaged 2.3, 5.5, and 6.1 percent by weight total chrcmiun.  The




total chromium emissions averaged 1.64 milligrams per dry standard cubic meter




(0.00072 grains  per dry standard cubic foot) and 0.065 kilograms per hour




(0.143 pounds per hour).








3.2  PARTICLE SIZE DISTRIBUTION




    Particle sizing runs were conducted at all locations tested for particulate




emissions.  The first of the four runs at each location was conducted at a




point of average velocity.  The other runs at the same location were conducted




at a point with a velocity similar to the first run.   This sampling procedure




was followed to ensure that the particle cut-size for all four runs would be




the same on corresponding impactor stages.




    The total mass of particulate matter collected on each stage was determined




using a gravimetric technique.  Stages were then combined in such a manner as




to obtain a quantifiable amount of hexavalent and total chromiun and determine




the particle size distribution of these chrcmiun species.  The particle size




distribution results are presented in Table 3.4 and the corresponding




calculations and graphs can be found in Appendix A.  The particle size




distribution for the uncontrolled rotary dryer emissions showed that




approximately 24 percent of the particulate, 64 percent of the hexavalent




chromiun, and 19 percent of the total chromium, by weight, were less than 10 ym




in diameter.  The controlled emissions from the rotary dryer and fugitive dust




sources showed that approximately 52 percent of the particulate, 75 percent of




the hexavalent chromiun, and 42 percent of total chromiun, by weight, were less




than 10 ym in diameter.                 3-10

-------
                                                    TABLE  3.4.   SUMM/R Y OF  P/WTICLE  SIZE DISTRIBUTION
OJ
i
Run
No.
Date
(1985)
Test Time
24 h clock
Part Icul ate
wt. less than size, %
1 y m | 5 ym
10 y m
Hexavalent Chromium
wt. less than size, %
1 ym | 5 ym
10 ym
Total Chromium
wt . less than si ze, %
liym
5 ym
10 ym
Rotary Dryer Exhaust
SI
S5
S9
S11
6/25
6/26
6/26
6/26
1117-1 137
1019-1026
1508-1523
1856-191 1
Average
0.6
3
0.5
0.8
1.2
9
18
14
12
13
17
30
30
20
24




3.5*




39*




64*




0.8*




9*




19*
                                                                         Fabric F!Iter Outlet
S4
S6
SB
SIO
6/25
6/26
6/26
6/26
0836-1 101
0823-1006
1125-1418
1519-1807
Average
3.5
5.5
0.5
3.5
3.2
33
39
19
33
31
54
63
39
52
52




8*




52*




75*




1.7*




23*




42*
                                                                           Tunnel  Kl I n Stack
S12
S13
S14
S15
6/27
6/27
6/27
6/28
0949-1 150
1254-1654
1733-1933
0716-0916
Average
72
71
72
70
71
79
78
80
74
78
87
85
85
81
84




71*




81*




84*




84*




91*




93*
                  'Values calculated  from  composites  of  all  runs.

-------
    The particle size distributions for the tunnel kiln emissions  are also

presented in Table 3.4 and show that the majority of the particulate,

hexavalent and total chromium emissions were less than 1 vm in diameter.

    The particle size distribution samples contained a smaller amount of

hexavalent and total chromium than the particulate samples  and were therefore

subject to a higher degree of analytical error.   The results are,  however,

believed to be representative and show a hexavalent chromium particle size

dependency toward the smaller particle sizes;  results from  two of  the three

locations sampled showed that the majority of  the hexavalent chromiun was

present in the particles less than 5 ym in diameter, which  is to be expected.


3.3  EMISSIONS IN UNITS OF PROCESS RATE AND CONTROL EQUIPMENT COLLECTION
       EFFICIENCY

    The emission rates in units of the process rate are expressed  in terms  of

grams of pollutant emissions per tons of chrcmite product processed and are

presented in Table 3.5

    To determine the collection efficiency of  the fabric filter, the un-

controlled and controlled emissions measured were used; no  actual  measurements

were made on the mass removal rates from the collector.

    Emissions from the rotary dryer are actually controlled by both a cyclone

and a fabric filter; fugitive emissions from the material transfer pick up

points are also controlled by the same fabric filter.  However, during the  test

program, the open bottom cyclone showed no collected material.  When the  rotary

dryer exhaust emissions were to calculate collection efficiency, that of  the

fabric filter (see Table 3.5) averaged about 80  percent by  weight  for particu-

late matter, 35 percent by weight for hexavalent chromiun,  and 80  percent by

weight for total chromiun.  The actual efficiency would be  somewhat higher

depending upon the amount of the unquantified fugitive particulate emissions.

                                      3-12

-------
TABLE 3.5.  SUMNVRY OF EMISS ION RATES IN UNITS OF PROCESS RATE AND EFFICIENCY
Run
No.
Process Rate
tons/h
Uncontrolled Emissions
part Icul ate
g/ton
hexavalent
chromium
g/ton x IO"3
total
chromium
g/ton
Controlled Emissions
partlcul ate
g/ton
hexavalent
chromium
g/ton x IO"3
total
chromium
g/ton
Collection Efficiency
partlcul ate
%
hexavalent
chromium
%
total
chromium
%
                     Rotary Dryer Fabric Filter  (+ Cyclone)
1,2
3,4
5,6
7,8
19.28
13.95
21.26
16.83
Average
408
732
641
1232
753
3.68
8.18
12.65
7.08
7.90
68.0
151
58.8
104
95.5
107
203
120
126
139
3.00
5.38
4.15
5.76
4.57
14.3
24.3
11.4
18. 1
17.0
>73.8
>72.3
>81.3
>89.8
>79.3
>18.5
>34.2
>67.2
>18.6
>34.6
>79.0
>83.9
>80.6
>82.6
>81.5
U)
I Tunnel Kl In
\->
U)
9
10
1 1
3.68
4.30
4.02
Average
502
388
246
379
1108
1068
910
1029
11.7
21.4
14.9
16.0

N/A



N/A



N/A



N/A



N/A



N/A



-------
    As previously noted, an accurate collection efficiency cannot be determined




for hexavalent chromium and total chromium for a fabric filter if the materials




typically collected are variable with respect to concentration of these




pollutants.  Based on other studies, it appears that about 50 to 80 percent of




the emissions from the fabric filter consist of materials previously collected




on the bags.  The collection efficiency for hexavalent chromium is apparently




lower due to the fact that material previously collected by the fabric filter




was much higher in hexavalent chroniun content.  The concentration of




uncontrolled hexavalent chromium emissions averaged about 11 yg of Cr   per




gram of particulate.  The material collected by the fabric filter and then




discharged through the hoppers averaged 76 yg of Cr   per gram of




particulate.  The emissions controlled by the fabric filter averaged 34 yg of



  +6
Cr   per gram of particulate.








3.4  SUMMARY OF ANALYTICAL RESULTS FOR HEXAVALENT AND TOTAL CHROMIUM




    The summary of analytical results for hexavalent chromium and total




chromiun for all samples collected is presented in Table 3.6.  The analytical




data sheets are contained in Appendix B.  The results shown in Table 3.6 for




hexavalent and total chromiun are the results obtained by the EPA tentative




method for "Determination of Hexavalent Chromiun Emissions frcm Stationary




Sources"  and the "EPA Protocol for Emissions Sampling for Both Hexavalent and




Total Chromiun" (see Appendix D).  When, for total chromiun analysis, the table




indicates that the sample "residue" was analyzed, then the values presented for




total chromiun content are a sun of (1) the hexavalent chromiun in the sample




filtrate from the extraction of the sample and (2) the chromiun in the residue




from the extraction as measured by Neutron Activation Analysis.  When the table




indicates that the "total" sample was analyzed, then the values presented for
                                        3-14

-------
TABLE 3.6.   SUMM/RY OF  ANALYTICAL RESULTS FCR  HEXAVALENT AND TOTAL CHROMIUM
Run
No.
Samp 1 e
Type
Samp 1 e
No.
Analyzed
Amount of
Sample
Analyzed
Hexavalent Chromium
Results
ii g
Concentration
ug/g
Amount of
Sampl e
Anal yzed
Total Chromium
Results
mg
Concentration
mg/g
Rotary Dryer Exhaust
1
1
3
5
7
51,5,9,11
SI, 5, 9,11
SI, 5, 9, 11
Part leu late Front Half
Impl nger Contents
Participate Front Half
Part Icul ate Front Half
Partlculate Front Half
Particle Size, Large
Particle SI ze. Medium
Partlc le SI ze, Smal 1
C-296
C-307
C-297
C-298
C-299
C-326
C-327
C-328
2989.1 mg
Total
3540.9 mg
3806.8 mg
7181 .6 mg
678.4 mg
257.9 mg
105.4 mg
26.8
< 0.2
39.5
75.2
41.2
3.8
5.0
3.7
8.97
negl Iglble
11.2
19.8
5.74
5.60
19.4
35.1
Residue
175 ml
Residue
Residue
Residue
Residue
Residue
Residue
499
0
729
350
605
103
19.4
9. 12
166.9
0
205.9
91.9
84.2
151.8
75.2
86.5
                                Fabric Fl Iter Outlet
2
2
4
6
8
54,6,8,10
54,6,8, 10
54,6,8,10
Partlculate Front Half
Impl nger Contents
Partlculate Front Half
Partlcul ate Front Hal f
Partlculate Front Hal f
Particle SIza, Large
Partlc le SI za. Medium
Particle SI ze, Smal 1
C-300
C-31I
C-301
C-302
C-303
C-329
C-330
C-331
598.2 mg
Total
1009.4 mg
672.6 mg
438.1 mg
191 .6 mg
191 .0 mg
1 09 . 2 mg
16.8
< 0.2
26.8
23.2
20.0
4.2
7.0
8.1
28.1
neg 1 Iglble
26.6
34.5
45.7
21.9
36.6
74.2
Residue
175 ml
Residue
Residue
Residue
Residue
Residue
Residue
80
0
121
63.6
62.9
25.4
14.8
8.38
133.7
0
119.9
94.6
143.6
132.6
77.5
76.7
                                  Tunnel  Kl In Stack
9
9
10
1 1
S12, 13, 14, 15
512,13,14,15
512,13,14,15
Partlculate Front Half
Impl nger Contents
Partlculate Front Hal f
Partlculate Front Hal f
Particle Size, Large
Particle Size, Medium
Particle SI ze, Smal 1
C-304
C-315
C-305
C-306
C-332
C-333
C-334
54.5 mg
Total
53.9 mg
29.0 mg
19.4 mg
8.0 mg
75.2 mg
120
< 0.2
148.8
107.5
1.7
1.7
9.7
2202
negl Iglble
2761
3707
87.6
212
129
Residue
175 ml
Residue
Residue
Residue
Residue
Residue
1.27
0
2.98
1.76
0.27
0.49
4.31
23.3
0
55.3
60.7
13.9
61.3
57.3
                                    Grab Samples
1
2
3
4
1
2
3
Ore Feed
Ore Feed
Ore Feed
Ore Feed
Fabric Filter Hopper
Fabric Filter Hopper
Fabric Filter Hopper
C-319
C-320
C-321
C-322
C-323
C-324
C-325

—
—
—
—
—
—
—
—
—
—
—
—
—
4.4
1.8
19.2
1.4
75.3
87.0
65.7
1 12.8 g
103.3 g
1 19.6 g
115.9 g
139.9 g
119.2 g
116.1 g
33.9
35.8
14.0
47.0
20.5
18.8
18.0
300.5
346.6
117.1
405.5
146.5
157.7
155.0
                                    Blank Samples

Particle SI ze Fl Iters
Dlstl 1 led H20 Blank
C-336
C-318
~
1.0
<0.2
negl Iglble
Residue
100 ml
0
0

-------
total chromium content are from the direct analysis of the total sample for




total chromium by Neutron Activation Analysis.   A table showing the total




chromium calculations for each sample can be found at the end of Appendix A of




th is repo rt.




    The hexavalent chromiun concentration was somewhat variable for most




sampling locations.  The variability of results for the particle size




distribution tests emissions may reflect some analytical imprecision due to the




small amount of hexavalent chromium analyzed.  The other samples had a




sufficient quantity of participate, hexavalent chromium and total chrcmiun,  and




should therefore be representative of the sample analyzed.  Overall, the goals




of obtaining quantifiable emissions were obtained.




    Quality assurance audit samples were analyzed for both the hexavalent and




total chromium methods.  As shown in Table 3.7, no bias was present and the




results are considered acceptable.








3.5  VISIBLE EMISSIONS OBSERVATION DATA




    Visible emission observations were performed at the fabric filter stack




exit by the EMB Task Manager (see Table 3.8 and Appendix C).  Readings were




made for two or three 6 to 7 minute sets for Runs 2,  4, and 6.  Under normal




operating conditions the opacity at the fabric filter stack was observed to be




0 percent; however, during the manual cleaning cycles used between product




runs, the opacity levels increased to an average of 3 to 10 percent with a




maximun range of 30 percent.
                                      3-16

-------
                              TABLE 3.7.  SUMWRY OF ANALYTICAL RESULTS  FCR  HEXAVALENT AND TOTAL OflOMIUM QUALITY ASSIRANCE  SANPLES

Run
No.

Samp 1 e
Type

Sampl e
No.

True
Value
Hexavalent Chromium
Results
pg/ml
%
Dev.
Total Chromium
Resul ts
ug
%
Dev.
Qual Ity Assurance Samples
	
—
—
—
Qual Ity Assurance
Qual Ity Assurance
Qual Ity Assurance
Qual Ity Assurance
C-335
QA-19
QA-20
QA-21
50 yg/ml Cr*6
50 ug Cr
100 p g Cr
200 vi g Cr
50.8
	
	
	
+ 1.6
	
	
	
— —
52.30
97.22
200.1
	
+4.6
-2.8
+0.05
 I
I-1
-J

-------
TABLE 3.8.  SUMMARY OF VISIBLE EMISSIONS DATA FOR FABRIC FILTER
                        HARBISON-WALKER
Date
Time
Range
Avg. % Opacity
Average Over
All Sets
Run Nos. 1 and 2
6/25
0906-0913
1007-1014
0
0-15
0
5
2.50
Run Nos. 3 and 4
6/26
0847-0854
0952-0959
1024-1033
0
0
0-30
0
0
10.14
4.08
Run Nos. 5 and 6
6/26
1321-1328
1425-1434
1630-1640
0
0-5
0-10
0
0.9
3.2
1.60
                               3-18

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                   4.0  SAMPLING LOCATIONS AND TEST METHODS








     This section describes the sampling locations and test methods vised to




characterize emissions from the rotary dryer and tunnel kiln at Harbison-Walker




Refractories in Baltimore, Maryland.  A total of five sampling locations were




used in the emission testing program.  At three sampling locations, emissions




testing was conducted for particulate matter, total chromiun content, hexa-




valent chromiun content, and particle size distribution and chromium




distribution with respect to particle size.  At the fourth and fifth sampling




locations, grab samples of the dust collected by the fabric filter and the




rotary dryer ore feed were taken for hexavalent and total chromiun analysis.




The relative positions and the type of testing conducted at each location are




shown in the simplified process flow diagram (see Figure 4-1) and accompanying




Table 4.1.  The subsections which follow further describe each sampling




location and applicable test methods.









4.1  ROTARY DRYER EXHAUST (SAMPLING LOCATION A)




     Particulate matter, hexavalent chromiun, total chromiun, particle size




distribution, and chromiun distribution with respect to particle size




distribution were measured in the rotary dryer exhaust duct.  A schematic of




this sampling location is shown in Figure 4-2.   A 3.5 by 17 inch slot for




sampling was cut in one side of the 17-inch square, vertical duct.  This




sampling slot was located 67 inches {3,9 equivalent duct diameters) downstream




of a bend in the duct and 17 inches (1 equivalent duct diameter) upstream of




another bend in the duct to the fabric filter.
                                      4-1

-------
                             To atmosphere
      Sampling Location D
                               I. D. Fan
      Formed
    Refractory 	
      Brick
Tunnel
 Kiln
      Sampling Location B
      Sampling Location A
      Sampl ing
      Location E
    Ore Feed — •
                             To atmosphere
                                I. D. Fan
                              Fabric Filter
                                 cyclone
                             Sampling
                      	 Location C
              *•—^	Hopper Dust
                                                         Fugitives
                                                           from
                                                         Materials
                                                         Handling
                                                         (5 Ducts)
                                               Emergency Bypass Duct
                                          Damper
Rotary
 Dryer
Figure 4-1.   Process Air Flow Schematic of Rotary Dryer and Tunnel  Kiln.
                                    4-2

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                    TABLE 4.1.   SAMPLING PLAN FOR HARBISON-WALKER
Sample Type
Samp!ing
Locations
  Number
of Samples
  Methods
Particulate matter
Hexavalent chromium
Total chromium
Particle size distribution

Hexavalent and total  chromium
distribution by particle size
Hexavalent chromium, total
chromium
A, B, D


A, B, D




A, B, D


A, B, D

A, B, D





  C, E
4 at A & B
 3 at D

4 at A & B
 3 at D
4 at A & B
 3 at D
4 at A & D
 5 at B
3 grab at C
4 grab at E
EPA Method 5
EPA 5 using Tentative
EPA Method for Hexavalent
Chromium

EPA 5 using EPA Protocol
for Total Chromium

Impactor (Andersen)

Impactor using Tentative
EPA Method for Hexavalent
Chromium and EPA Protocol
for Total Chromium

Tentative EPA Method for
Hexavalent Chromium,
EPA Protocol for Total
Chromium
                                         4-3

-------
                       17"
                                   17*
                                      •4	
                                      • t	
                                I
                                I
                               T
                                I
c
B
A
                              SECTION F-F
TRAVERSE POINTS

 4  AXES
 4  POINTS/AXIS
 16  TOTAL POINTS
          TO
     FABRIC FILTER
                     EMERGENCY
                      EXHAUST
           r
               67"
                          " ->
                        t
    FROM
ROTARY DRYER
            SIDE ELEVATION
                                     DAMPER
                                     (CLOSED)
       EMERGENCY
       EXHAUST
                                                      t
                                                    A B  C  D
       •4-17"
          t
                   SLOT
                (3.5" x 17")
   FRONT ELEVATION
    FIGURE  4-2.   ROTARY DRYER EXHAUST  DUCT (SAMPLING  LOCATION A)
                               4-4

-------
    For the Method 5 testing (used for particulate matter, hexavalent chromium,




and total chromium determinations), a total of 16 points (4 axes, 4 points per




axis), as per Method 1, were sampled.  Each point was sampled for 7.5 minutes




for a total sampling time of 120 minutes per run (one exception was Run 5 where




a process upset resulted in several points not being sampled and a shorter




total sampling time of 105 minutes).




    The particle size testing (including hexavalent and total chromium




distribution by particle size),  was conducted at a single point.  Runs S1, S5,




S9, and S11 were 20, 7.:52, 15,  and 15 minutes in duration, respectively.









4.2  FABRIC FILTER OUTLET (SAMPLING LOCATION B)




    Particulate matter, hexavalent chromium, total chromium, particle size




distribution, and hexavalent and total chromium distribution with respect to




particle size were measured at the fabric filter outlet.  A schematic of this




sampling location is shown in Figure 4-3.  A 3.5 by 22 inch slot for sampling




was cut in the long side of the 19 by 22 inch rectangular, vertical duct.  This




slot was located 110 inches (5.4 equivalent duct diamteters) downstream of the




fabric filter I. D. fan and 100  inches (4.9 equivalent duct diameters) upstream




of the fabric filter stack exit.




    For the EPA Method 5 sampling  (used for particulate matter, hexavalent




chromium, and total chromium determinations), a total of 16 points  (4 axes,




4 points per axis), as per Method 1, were sampled.  For the first run each




point was sampled for 15 minutes, however, a process upset prevented sampling




all the points resulting in a total run time of 170 minutes.  In addition, the




heavy particulate catch from this run suggested a shorter sampling time, so for




the remaining runs each point was sampled for 7.5 minutes.  The total sampling
                                      4-5

-------
TRAVERSE  POINTS

  4  AXES
  4  POINTS/AXIS
 16  TOTAL  POINTS
9"
T 	 ^ 	 r
•
•
•
*
*
•
•
*
«
«
•
•
•
«
•
«
                            A    B   C    D
                             SECTION T-T
     SLOT (3.5" x 22")
                                 22">
                                  t
                               AB CD
                                       - 100'
                                       -110"
                                              ELEVATION VIEW
                            FROM I.D. FAN
    FIGURE 4-3. FABRIC  FILTER  OUTLET  STACK (SAMPLING  LOCATION B>
                             4-6

-------
times for these runs were 136, 121, and 120 minutes.  For the 136 minute run,




the EPA Task Manager requested that sampling continue beyond the 120 minute




mark.




    The particle size testing (including hexavalent and total chromium




distribution by particle size) was conducted at a single point.  Runs S4, S6,




SB, and S10 were 100 minutes in duration.




    Visible emissions observations of the effluent from the fabric filter stack




were conducted by the EMB Task Manager for several 6 (or 7) minute sets during




Runs 2,  4, and 6.









4.3  FABRIC FILTER DUST HOPPER (SAMPLING LOCATION C)




    Grab samples representative of the material collected by the fabric filter




were taken from the fabric filter hopper during each set of test runs.  Each




grab sample was a composite of material from each of the three hopper sections




of the filter and each was analyzed for hexavalent chromium and total chromium




content.









4.4  TUNNEL KILN STACK (SAMPLING LOCATION D)




    Particulate matter, hexavalent chromium, total chromium, particle size




distribution, and hexavalent and total chromium distribution with respect to




particle size were measured at the tunnel kiln stack.




    A schematic of this sampling location is shown in Figure 4-4.  Two sampling




ports were installed at a 90° angle in the 42 inch diameter vertical stack.




These ports were located 96 inches (2.3 duct diameters) downstream of the




induced draft fan and 380 inches (9.0 duct diameters) upstream of the stack




exit.
                                      4-7

-------
  TRAVERSE POINTS

   2 AXES
   12 POINTS/AXIS
   24 TOTAL POINTS
                                      42" DIA.
                      SECTION  X-X
                          42"
                           t
 A
•O-
                           t
                               - 380"
                              B
                                   '"I
                                 96"   X
                                      ELEVATION VIEW
                        FROM KILN
FIGURE  4-4.  TUNNEL  KILN STACK (SAMPLING LOCATION D)
                        4-8

-------
    For the Method 5 testing  (used for particulate matter, hexavalent chromium,




and total chromium determinations), a total of 24 points  (2 axes, 12 points per




axis), as per Method 1, were sampled.  Each point was sampled for 5 minutes for




a total sampling time of 120 minutes per run.




    The particle size testing  (including hexavalent and total chromium




distribution by particle size) was conducted at a single  point.  Runs S12, S14,




and S15 were 120 minutes in duration, Run S13 was 240 minutes in duration.








4.5  ROTARY DRYER FEED  (SAMPLING LOCATION E)




    Grab samples representative of the feed material  (ore) entering the rotary




dryer were taken frcm the feed belt as it went to the dryer.  Samples were




taken at the beginning, middle, and end  (if possible because of process




operations) of each particulate test series.  The samples from each test  series




were combined into a single sample which was analyzed for hexavalent chromium




and total chromim content.








4.6  VELOCITY AND GAS TEMPERATURE




    A type S pitot tube and an inclined draft gauge manometer or two differen-




tial pressure gauges in-paralled were used to measure the gas velocity pressure




(A?)-  Velocity pressures were measured at each sampling  point across the duct




to determine an average value according to the procedures outlined in Method 2




of the Federal Register.*  The temperature at each sampling point was measured




using a thermocouple and digital readout.








4.7  MOLECULAR WEIGHT




    Flue gas composition was  determined utilizing procedures described in




Method 3 of the Federal Register.*  A bag sample was collected during each




particulate test run.  The bag contents were analyzed using an Orsat Gas




Analyzer.
*40 CFR 60, Appendix A,  Reference Methods 2, 3, and 5, July  1,  1980.




                                      4-9

-------
4.8  PAKTICULATE MATTER




    Method 5, as described in the Federal Register,* was used to measure





particulate grain loading at locations A, B, and D.  All tests were conducted




isokinetically by traversing the cross-sectional area of the stack and




regulating the sample flow rate relative to the flue gas flow rate as measured




by the pitot tube attached to the sample probe.  A sampling train consisting of




a heated, glass-lined probe, a heated 87 mm (3.4 inches) diameter glass fiber




filter (Gelman A/E), and a series of Greenburg-Smith impingers was employed for




each test.  An acetone rinse of the nozzle, probe, and filter holder portions




of the sample train was made at the end of each test.  The acetone rinse and




the particulate caught on the filter media were dried at room temperature,




desiccated to a constant weight, and weighed on an analytical balance.  Total




filterable particulate matter was determined by adding these two values.  See




Appendix D for detailed sampling procedures.








4.9 PARTICLE SIZE DISTRIBUTION




    Particle size samples were obtained using Andersen Mark III Cascade




Impactors.  These in-stack, multistage cascade impactors have a total of eight




stages, followed by a back-up filter stage and particle size cut-offs ranging




nominally from 0.5 to 15 microns.  Substrates were 64 mm diameter glass fiber




filters.  A constant sampling rate was maintained through the test period.




Sampling rates were set for isokinetic sampling as long as the sampling rate




did not exceed the recommended flow rate for the impactor.  See Appendix D for




detailed sampling procedures.




    Four impactor runs each were conducted at the rotary dryer exhaust, the




fabric filter outlet and the tunnel kiln stack.  At the locations sampled, a
* 40 CFR 60, Appendix A, Reference Methods 2, 3, and 5, July 1, 1980.
                                     4-10

-------
single point was sampled.  With the exception of selection of the sampling




point locations, the procedures used followed those recommended in the




"Procedures Manual for Inhalable Particulate Sampler Operation"  developed for




EPA by the Southern Research Institute.*









4.10 HEXAVALENT CHROMIUM CONTENT




    Hexavalent chromiun content was determined utilizing procedures described




in the tentative EPA Method "Determination of Hexavalent Chromiun Emissions




from Stationary Sources" (see Appendix D).  The Method 5 filter catch collected




and weighed for each Method 5 run was taken and analyzed for hexavalent




chromiun content using this method.  If was also used to determine the




hexavalent chromiun content of representative portions of the fabric filter




hopper dust and rotary dryer ore feed samples.









4.11 TOTAL CHROMIUM CONTENT




    Total chromiun content was determined using procedures described in the




" EMB Prototcol for Sample Preparation and Emission Calculation of Field Samples




for Total Chromiun" in combination with Neutron Activation Analysis (NAA) (see




Appendix D).  Samples collected during Method 5 runs and first submitted to




analysis for hexavalent chromium were then analyzed for total chromiun using




this method.  The total chromiun content of the fabric filter hopper dust and




the rotary dryer ore feed samples were also determined using these procedures




using a representative portion of the sample.
•Prepared for EPA under Contract No. 68-02-3118, November 1979.
                                      4-11

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                             5.0  QUALITY ASSURANCE


     Because the end product of testing is to produce representative emission

results, quality assurance is one of the main facets of stack sampling.

Quality assurance guidelines provide the detailed procedures and actions

necessary for defining and producing acceptable data.  Two such documents were

used in this test program to ensure the collection of acceptable data and to

provide a definition of unacceptable data.  These documents are:  the EPA

Quality Assurance Handbook Volume III, EPA-600/4-77-OZ7 and Entropy's "Quality

Assurance Program Plan" which has been approved by the U. S. EPA, EMB.

     Relative to this test program, the following steps were taken to ensure

that the testing and analytical procedures produce quality data.


     «   Calibration of field sampling equipment.  (Appendix E describes
         calibration guidelines in more detail.)

     •   Checks of train configuration and on calculations.

     •   On-site quality assurance checks such as sampling train, pitot
         tube, and Orsat line leak checks, and quality assurance checks of
         all test equipment prior to use.

     •   Use of designated analytical equipment and sampling reagents.

     In addition to the pre- and post-test calibrations, a field audit was

performed on the meter boxes used for sampling.  Entropy used the procedures

described in the December 14, 1983 Federal Register (48FR55670). In addition,

the analytical balance used for filter weighing was audited with Class "S"

weights.

     As a check on the reliability of the method used to analyze the filters

for particle size tests, sets of filters that had been preweighed in the lab

were resubmitted for replicate analysis.  Table 5.1 summarizes these results.
                                      5-1

-------
TABLE 5.1.  PARTICLE SIZE BLANK FILTER AND REACTIVITY FILTER ANALYSIS
Sample type
Particle size
blank run filters
B472
A472
B473
A473
B474
A474
B475
A475
SF192
Particle size
reactivity run
filters
B525
A525
B526
A526
B527
A527
B528
A528
SF205
Original tare
weight, mg


166.68
145.49
166.12
146.85
164.70
147.69
164.46
148.40
275.34



164.18
146.00
164.06
147.62
163.31
146.17
165.68
145.91
274.34
Bl ank weight,
mg


166.69
145.53
166.22
146.85
164.71
147.70
164.49
148.42
275.34



164.18
146.02
164.09
147.66
163.32
146.17
165.68
145.92
274.30
Net weight,
mg


0.01
0.04
0.10
0.00
0.01
0.01
0.03
0.02
0.00



0.00
0.02
0.03
0.04
0.01
0.00
0.00
0.01
-0.04
                               5-2

-------
    Audit solutions prepared by the EPA were used to check the analytical




procedures of the laboratories conducting the hexavalent and total chrcmivm




analyses.  Table 5.2 presents the results of these analytical audits.  The




audit tests show that the analytical techniques were good.




    The sampling equipment, reagents, and analytical procedures for this test




series were in compliance with all necessary guidelines set forth for accurate




test results as described in Volune III of the Quality Assurance Handbook.
                                     5-3

-------
                   TABLE 5.2.  AUDIT REPORT CHROMIUM ANALYSIS
Plant:
                                                   Task No.:
Date samples received:
Sample analyzed by:
Reviewed by:
                                                   Date analyzed:
                                                   Date of review:
Sample
Number
C-335"
3/^/5
5/f'2&
QA-2/



yg/ml
Cr+b or Cr
SO Mq InJLC^
So ^ Cr
J J
/CO ^ Cs
2.QDP1 t
\/£S
N&5
X6S



Audit
Value
5^>-6
5"^.3O
17. ZZ.
2.00. \



Relative
error, %
+ I.G>
+ +.U
-j.e
^o.osr



                                        5-4

-------