United States      Industrial Environmental Research  EPA-600/7-79-156
Environmental Protection  Laboratory          July 1979
Agency        Research Triangle Park NC 27711
Process Measurement
Procedures:
Emissions

Interagency
Energy/Environment
R&D Program Report

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                 RESEARCH REPORTING SERIES


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

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental  Studies

    6. Scientific and Technical Assessment Reports  (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports

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

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

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                                         EPA-600/7-79-156

                                                   July 1979
Process Measurement Procedures
                          Emissions
                          by

                  R. Maddalone and N. Garner

              TRW Defense and Space Systems Group
                      One Space Park
                 Redondo Beach, California 90278
                   Contract No. 68-02-2165
                       Task No. 202
                  Program Element No. INE624
                EPA Project Officer: Robert M. Statnick

             Industrial Environmental Research Laboratory
               Office of Energy, Minerals, and Industry
                Research Triangle Park, NC 27711
                       Prepared for

            U.S. ENVIRONMENTAL PROTECTION AGENCY
                Office of Research and Development
                    Washington, DC 20460

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                             ACKNOWLEDGMENT

       The work was originally conducted under the FPA Project  Officer
Dr. R. M. Statnick, Environmental  Research Center, Research  Triangle  Park,
North Carolina.  The current EPA project officer is fir.  Frank  Briden.
Dr. C. A. Flegal was the Program Manager and the Task Order  Manager was
Dr. R. F. Maddalone.  The laboratory tests during the development  of  these
procedures were done by Mr.  Morton L.  Kraft, Mr. David R.  Moore and
Mr. Maynard D. Cole.  We wish to thank Mr. Steve Newton  of the  TVA and
Mr. Ray Grote of the EPA for their review of the document.   The overall
review and support, during the field test program, from  Mr.  Richard G.
Rhudy of EPRI, and fir.  Steven Newton and fir. John Lawton of  the TVA
has been greatly appreciated.

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                                 CONTENTS                                page
ACKNOWLEDGEMENT. .	ii
TABLES & FIGURES	IV

   1.    INTRODUCTION  	    1
   2.    EQUIPMENT AND MATERIALS	   3
        2.1   Sampling Materials  	  3
        2.2   Reagents and Apparatus  for H?SO.  	  5
   3.    REQUIREMENTS  	  9
        3.1  System Design 	  9
        3.2  Sampling	     9
        3.3  Handling of Glassware	12
        3.4  Calibration and Maintenance 	   12
        3.5  Cleanliness	12
        3.6  Safety	12
   4.    PROCEDURE	13
        4.1  Probe Manufacture 	   13
        4.2  Filter Holder Fabrication	17
        4.3  Site Equipment Set-Up  and Operation	19
        4.4  Analysis Procedures  	   22
   5.    DATA MONITORING PROCEDURES	29
        5.1  Acid Base Titration	29
        5.2  Data Monitoring by Statistical Quality Control  	  30
   6.    MAINTENANCE SCHEDULES 	  32
   7.    TROUBLESHOOTING AND REPAIR  PROCEDURES  	  35
   8.    REFERENCES	40

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                                   TABLES
                                                                    Page
 1.  Critical Checkpoints for Controlled Condensation H?SO.
     Sampling System	    14
 2.  General Maintenance Schedule 	    33
 3.  Troubleshooting and Repair 	    36
                                 FIGURES
 1.   Vycor Sampling Liner 	     4
 2.   Controlled Condensation Coil (CCC) 	     6
 3.   Controlled Condensation System Set-Up	    10
 4.   Expected Coefficient of Variance (CV) of the HpSCL Measurement
     Based on the Number of Samples Taken	    11
 5.   Controlled Condensation System Probe Design	    16
 6.   Quartz Filter Holder 	    18
 7.   Controlled Condensation Field Data Sheet 	    21
 8.   Controlled Condensation Coil Rinsing Apparatus 	    23
 9.   Laboratory Data Sheet	    25
10.   Statistical Quality Control  Chart for Contamination
     Measurements 	    31
                                     IV

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                            1.   INTRODUCTION

     This manual has been prepared for the Industrial  and Environmental
Research Laboratory of the Environmental  Protection Agency,  Research Tri-
angle Park, North Carolina, as part of Task 13 of Contract No.  68-02-2165.
     The technical  objective of this task was  to develop a stack sampling
procedure for the measurement of the mass emission rate of sulfur trioxide
(H?SO. vapor) within a precision of ±10 percent, but not to  exceed a pre-
cision of ±20 percent.  The method chosen on the basis of previous expe-
rience (Task 02 of this program) was the Controlled Condensation System
(CCS).
     The Controlled Condensation System (CCS)  is designed to measure the
vapor phase concentration of SOo as H^SO. in controlled or uncontrolled
flue gas streams.  This method is specifically designed to operate at tem-
peratures up to 250°C (500°F)  with 3000 ppm S09, 8-16 percent H90, and up
        3
to 9 g/m  (4 gr/cf) of particulate matter.
     By using a modified Graham condenser,  the gas is cooled to the acid
dew point at which the SO- (hLSO. vapor)  condenses.   The temperature of
the gas is kept above the water dew point to prevent an interference from
SOp while a heated quartz filter system removes particulate  matter.   The
condensed acid is then titrated with 0.02 N NaOH using Bromophenol Blue  as
the indicator.
     The CCS was evaluated under simulated  stack conditions  in  the labora-
tory.  This test program had three phases:
        •  Test the efficiency of the CCS under varying concentrations
           and mixtures of HgSO^ S02, 02,  H20, and C02 with and without
           fly ash present on  the filter.
        •  Evaluate the CCS versus the EPA  H^SO. methods.
        •  Test the CCS inlet  and outlet  of an ESP at  a coal-fired utility.

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As a result of this test program these facts were learned about CCS:

   t  The average laboratory coefficient of variance was  ±6 percent.

   t  Fly ash at the level of 0.3 g on the surface of the filter
      can reduce the amount of 1^04 recovered by 12 percent when a
      10 ppm gas stream of ^804 is passed through the system.
                                     .              o
   •  Extensive field evaluation under high (11 g/m ) mass loading
      and high S02 (4000 ppm) concentrations showed that  as little
      as 0.1 ppm of H2S04 can be detected.

   •  The coefficient of variance for the percentage removal  of
      H2S04 by wet scrubbers at a coal-fired utility was  found  to
      be ±18 percent.  This value compares well with the  ±11  percent
      for the estimated field accuracy.

   •  Oxidation of SO? at the recommended filter holder temperatures,
      4000 ppm SOp and 8 percent 02 did  not occur.  When  fly ash from
      a coal-fired utility was placed on the filter, it did not have
      a catalytic effect under those conditions.

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                        2.   EQUIPMENT AND MATERIALS
     The following sections list the materials required to fabricate
duplicate CCS's.
2.1  SAMPLING MATERIALS
2.1.1  Probe Construction Materials.  (Note:  These materials are for a
91 cm (3-foot) probe.  Longer probes can be made by increasing the dimen-
sions presented).
     •  Three Vycor tubes 1.3 cm (0.5 in.)  OD x 91 cm (36 in.) with a
        18/9 female ball-and-socket joint placed on one end (special
        order, A. H. Thomas or Ace Glass, see Figure 1).
     •  Three glass insulated heating tapes - 1/2 inch x 72 inch; 288 watts
        (Fisher Sci. Co., No. 11-463-50C or equivalent).
     •  Three 33 inch x 1 inch OD x 0.065 inch wall 304 SS tubes used as
        probe sheaths.
     •  One dozen silicone rubber No.  6 stoppers (A. H. Thomas, No.  8747-
        E65).
     •  Glass tape (Scotch glass-fiber electrical  tape).
     •  Four Omega (Stanford, Conn.) shielded thermocouples (I/C),
        (TJ36-ICSS-18G-12) with 8-foot lead.
     •  Four Omega (Stanford, Conn.) unshielded thermocouples (I/C),
        (IRCO-032 with  8-foot lead).
     •  Six Omega male  connectors (ST-ICRO-M).
     •  Two six-foot heavy-duty (^ 20A) electrical cords.
     •  Four 1-1/2 inch hose clamps.
     •  Two square yards of asbestos cloth  (VWR, Atlanta,  Georgia,
        No.  10930-009).
     •  Three adaptors  for connecting  hoses (Ace Glass, No.  5216-23).
     •  Two Teflon Swagelok Unions (T-810-6).
2.1.2  Train Components
     •  Two pumps capable of pulling 1  cfm  of free air.
     •  Two bath controller-circulators (A.  H. Thomas,  No.  9840-B15  or
        equivalent).

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1.3 cm
 T
                         THERMOCOUPLE WELL
                                                                46 cm
                                            91 cm
18/9
THERMO-
COUPLE
WELL
                                       Figure  1.   Vycor  sampling liner.

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     •  Fifty feet of 1/2 inch x 1/4 inch rubber tubing (A.  H.  Thomas,
        No. 9544-R57).
     •  Controlled Condensation Coils (CCC) — Three Graham condensers are
        modified to hold an enclosed 60 mm medium frit (Figure  2).
     •  Two insulated chests capable of holding a two-gallon bucket.
     •  Three glass insulated heating tapes, 3/8 inch x 24 inch, 96 watts
        (A. H. Thomas, No. 5954-H22 or equivalent).
     t  Four autotransformers, variable, 10 amp.  (A.  H. Thomas, No. 9461-
        D10 or equivalent).
     •  One hundred Tissuequartz filters, 37 mm diameter (Pallflex  Corp.,
        Kennedy Drive, Putnam, Conn. 06260).
     §  Eight pinch clamps (A. H.  Thomas, No.  2841-21  or equivalent).
     •  Six Greenburg-Smith type impingers or equivalent.
     •  Sodium Carbonate, technical grade.
     t  Indicating silica gel (10  Ibs).
     •  Stopcock grease (Ace Glass Co., No. 8229-10).
     •  Two three-inch bushings with a 1-1/8 inch hole drilled  in the
        center.
     •  Two RdF digital temperature indicators-series-2000 with iron/con-
        stantan sensors.
     •  Two vacuum gauges (A. H. Thomas, No. 5654-B10).
     •  Two 0 to 100 ml/min flowmeters (Fisher Scientific Co.,  No.  11-164-
        50 or equivalent).
     •  Two Glass-Col  heating mantles for filter  system (Glass-Col, 711
        Hulman St., Terre Haute, Ind., special  order  to fit  filter  holder).
     t  Two quartz filter holders  (see Section  4.2  for design fabrication).
2.2  REAGENTS AND APPARATUS FOR H2S04 TITRATION
     t  Carbon dioxide-free distilled water -  Prepare  all  stock and standard
        solutions, and dilution water for standardization  procedure,  using
        distilled water which has  a pH of not  less  than 6.0.  If the  water
        has a lower pH, it should  be freshly boiled for 15 minutes  and
        cooled to room temperature.

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CTl
    THERMOCOUPLE
         WELL
     18/9
   3 CM-
         60 MM MEDIUM
            FRIT
                                                                                                18/9
                                     THERMOCOUPLE
                                         WELL
4.0 CM-
23.8 CM
-4 CM-
                                                                                                             GAS
                                                                                                             FLOW
                                   Figure 2.  Controlled  condensation coil (CCC).

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                              NOTE
 Deionized water may be substituted for distilled water provided
 that  it has a conductance of less than 2 micro-ohms/cm and a pH
 greater than 6.0.

 f  NaOH pellets — Reagent grade.

 •  Stock 1.0 N NaOH - Dissolve 40 g of reagent grade NaOH in 1 liter
   of COp free distilled water.  Store in a Pyrex glass container with
   a  tignt-fitting rubber stopper.

 •  0.0200 N NaOH - Dilute 20 ml of 1 N NaOH with OL free distilled
   water to 1 liter.  Store in a tightly rubber stoppered Pyrex glass
   bottle protected from atmospheric (XL by a soda lime tube.  For
   best results, prepare daily.  This solution will be standardized
   against potassium biphtalate (see Section 4.4.2).
t  Potassium biphthalate (KHCoH^O,) -Anhydrous, reagent grade.

t  0.0200 N potassium biphthalate (KHP) solution - Dissolve 4.085 g
   of dry (110°C for 1 hour) KHP into 1 liter of (XL free distilled
   water.

                              NOTE

The normality of the KHP solution equals (wt. KHP)/204.2.

•  Anhydrous ethyl  alcohol  — U.S. P. or equivalent.

§  Phenolphthalein indicator solution — Dissolve 0.05 g of reagent
   grade phenol phthalein in 50 ml ethyl alcohol  and dilute to 100 ml
   with C02 free water.

•  Bromophenol Blue indicator solution — Dissolve 0.1 g in 7.5 ml of
   0.02 N NaOH.  Dilute to 250 ml with C02-free  distilled water.

•  Ten milliliter micro-buret, Kimble 17132F (A.  H.  Thomas, No.
   1993-M-30 or equivalent).

•  Desiccator (A. H. Thomas, No.  3751-H10 with cover and plate to fit)

•  Drierite desiccant -5 Ibs. Drierite (A. H. Thomas, No. C288-T49).

§  Four Erlenmeyer flasks with 28/15 ball-and-socket joint, 125  ml
   (Ace Glass Co.,  Louisville, Ky., No. 6975 or  equivalent).

•  Four stoppers for 28/15  ball-and-socket joint  (Ace Glass Co.,
   No.  8263-08 or equivalent).

•  Four 50 ml  volumetric flasks.

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Dowex 50W-X8 cation exchange resin 20 to 50 mesh.

Barium perch]orate trihydrate.

0.01 f1 Ba(C10J2.3 H20 - Transfer approximately 3.9 g of reagent
grade barium perchlorate trihydrate into a one-liter reagent bottle.
Add enough D.I.  HpO to dissolve the salt and then dilute to the mark.

Sulfonazo III Solution, 0.1  percent W/V -Transfer 0.025 g of
Sulfonazo III into a 25-ml bottle, add water to dissolve the
indicator and fill to the mark.

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                             3.   REQUIREMENTS
3.1  SYSTEM DESIGN
      The SOo (HpSO. vapor) Controlled Condensation System (CCS) consists
of a heated Vycor probe, a modified Graham condenser (condensation coil),
impingers, a pump and a dry test meter (see Figure 3).
3.2  SAMPLING
      Since a gas  or a small aerosol is being sampled, no traverse will
be performed in the stack.  It can be shown (Reference  7) that the aver-
age degree of stratification in the duct is ±15 percent of the mean con-
centration.  Because of the large fluctuation in source emission rates
(±65 percent), elimination of the error due to stratification will not
significantly improve the sampling accuracy.  For these reasons, the
sample probe will be positioned at the center of the duct or stack.
      It is possible to predict the expected variance in the average H?SO.
value.  The sampling variance of an estimated average of I^SCL determined
from a sample of D days and H samples per day is given  by:
                             x     D     H
        9                                    9
where OQ  is the variance between days and o^  is the variance per sample
within a day.   Converting this equation to terms of the coefficient of
variation (CV) we have:
                                   cv2
From previous experience for a coal-fired utility,  the CVU  was  determined
                                                         rl
to be ±32.4 percent and CVn was determined to be ±57.9 percent.   Using  these
values, Figure 4 is generated from equation 2.   Thus,  if it is  desired  to
estimate the average H^SO, within  20 percent, a  sampling plan of  five days

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                                                                                        RUBBER VACUUM
                                                                                           HOSE
              ADAPTER FOR CONNECTING HOSE

                               TC WELL
STACK
                       ASBESTOS CLOTH
                         INSULATION
            GLASS-COL
            HEATING
            MANTLE
                                                                   RECIRCULATOR


                                                                   THERMOMETER
DRY TEST
METER
                                                                                                   THREE WAY
                                                                                                     VALVE
                                                                                            SILICA GEL
                           Figure 3.   Controlled Condensation System Set-up.

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 •"fr
o

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with five samples per day, or six days with two samples per day, or seven
days with one sample per day is required.
3.3  HANDLING OF GLASSWARE
     Because of the corrosive nature of SCL (HLSCL vapor), only Vycor and
Pyrex glassware are used.  Severe mechanical shocks are to be avoided,
especially when the probe is heated to 316°C (600°F).  Never place any
strain on glass ball joints.  Clean the ball joints of grease and dirt
after each run.
3.4  CALIBRATION AND MAINTENANCE
     After each run the probe, connecting lines, controlled condensation
coil, filter holder, and impinger system must be cleaned.   The probe and
connecting lines can be cleaned with a long-handle test tube brush and
backflushed with high pressure air.  If particulate matter adheres to the
inside of the probe, rinse with D.I. water followed by acetone (or
isopropyl alcohol).  The impinger system is flushed out and the proper
solvents are then replaced in the impinger bottles prior to the next run.
The filter holder is inspected and cleaned before the next run and the
filter pad is replaced.  See Sections 6.0 and 7.0 for the recommended
schedule of maintenance and troubleshooting activities.
3.5  CLEANLINESS
     Contamination of the condensation coil rinse solutions must be avoided
to prevent neutralization of the hLSO^.  Keep the rinse solutions in a
covered flask.
3.6  SAFETY
     OSHA safety requirements with regard to working environment and opera-
tor safety must be met at all times.  The reagents mentioned in the proce-
dure are not extremely toxic, but misuse of any chemicals can be harmful.
                                     12

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                              4.   PROCEDURE

     This section contains the necessary information to build, set-up, and
operate the CCS.  Table 1 is a checklist of critical items giving an over-
view of the procedure.  These critical items consist of:
        •  Recommended flowrates, temperatures and sampling times
        t  Reminders on laboratory and sampling techniques
        •  Specific equipment checks
     While this list is provided for review prior to the sampling run, its
best use is as an on-site checklist for the supervisor and quality assurance
personnel during the run.  During a test audit the supervisor or QA repre-
sentative should initial each item successfully completed, and the entire
list should be included with the documentation of that test run.  The oper-
ating personnel should also have copies of the checklist for reference dur-
ing the execution of the test run.  Copies can be posted in the laboratory
and sampling site for this purpose.
4.1  PROBE MANUFACTURE (Refer to Figure 5)
     The necessary equipment is listed in Section 2.1.1.  Follow correct
electrical safety procedures at all times.  Be sure that no sharp pieces of
metal abrade any of the electrical wires.
    a)  Cut the 304 SS one-inch tubing into 32-inch lengths.
    b)  Align the shielded thermocouple (TC) as shown in Figure 5.  Using
the glass tape, secure the shielded thermocouple to the Vycor probe.  Place
the unshielded thermocouple in the thermocouple well and secure with the
glass tape.  Continue down the probe, securing both thermocouple leads
simultaneously against the tube.
                                   NOTE
         Be careful  never to kink the thermocouple or thermocouple
         leads.
   cj  Take the 72-inch glass heating tape and fold it in half.
   d)  Beginning 5 inches from the probe tip,  wrap the probe with the glass
heating tape.   Make sure the heating tape is snugly up to the probe and
secured every  6 inches with a wrapping of glass tape.   Wrap the coils close

                                    13

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           TABLE  1.    CRITICAL  CHECKPOINTS FOR  CONTROLLED CONDENSATION
                         H2S04 SAMPLING  SYSTEM
                             Checkpoint
                                                                            Initials
                                                                    Supervisor  QA Inspector
Remarks
  I.   Laboratory Preparation

      -  Inspect and clean CCC.  Both filter holder  and CCC are
        cleaned with hot chromic acid solution and  D.I. FUO.

      -  Rinse with acetone and air dry CCC.

      -  Place Tissuequartz filter in filter housing.

      -  Check seal  between end of joint and filter.

      -  Do not use grease on joints.

      -  Inspect and clean all glass joints.

 II.   Site Setup

      -  Rinse the inside of probe prior to run.

      -  Rinse probe with acetone until  rinse solution is clear.

      -  Perform leak test.

      -  Leak rate must be less than 80 ml/min (0.003 cfni).

      -  Thermocouple leads  attached to  probe and  filter.

      -  CCC water bath held at 60°C (140°F) il°C.

      -  Leak test train.

      -  Probe temperature maintained at 316°C (600°F) !17°C.

      -  Gas temperature out of filter holder held at 288°C (550°F).

      -  Fresh solutions placed in impingers.

      -  Fresh absorbent replaced in final  impinger.

      -  Adjust flowrate in system to 8 1pm.

III.   Sampling Run

      -  Turn vacuum pump on just before inserting probe in the stack.

      -  Check seal  between probe and port to prevent any outside air
        from entering the stack.

      -  Run test for 1 hour or until coils are frosted to 1/2 or
        2/3 of their length.

      -  After run cap both ends of  the probe and  lay in horizontal
        position.

      -  Rinse the CCC coils into the modified Erlenmeyer flask with a
        maximum of 40 ml of D.I. H20.

      -  Has any of the solution lost (   ml estimated)?

      -  Handle hot glassware  carefully to prevent personnel  injury
        and damage to equipment.

      -  After probe has cooled, the probe  is rinsed with a maximum
        of 40 ml.  D.I. H20 into a  125 ml Erlenmeyer.
                                                                                          (continued)
                                                   14

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TABLE 1.  (continued)
Checkpoint
- Was any solution lost ( ml estimated)?
- Clean support equipment prior to next run.
- Save filter for titration.
IV. Laboratory Analysis
- Clean glassware prior to titration.
- Use Bromphenol Blue indicator.
- Is the NaOH buret protected with a CO,, absorbent tube?
- When was NaOH standardized last (Date )?
- Filter any solution that has suspended particulate.
- Use same number of indicator drops for each titration.
- Perform indicator blank on a volume of D.I. H20 equal to
sample aliquot used.
- Indicator blank added to HpSO. milli-equivalents found.
- Perform all analyses in triplicate.
V. Data Analysis Verification
- Obtain and titrate test samples from main laboratory.
Initials
Supervisor















QA Inspector















Remarks















         15

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                                                                                   PROBE T.C.
                                18/9
                                                                  SILICONE
                                                                  STOPPER


                                                              ASBESTOS
                                                              CLOTH WRAP
cr>
                         SILICONE
                         STOPPER
             VYCOR TUBE

       TEFLON UNION


        6 MM
HEATING TAPE
                             SHIELDED
                             T.C.
                                     GLASS HEATING
                                     TAPE LEAD
                        STACK
                        T.C.
  (?) STOPPERS SHOULD BE AWAY FROM HEATING TAPE

  (T) ASBESTOS COVER SHOWS SLIGHT OVERLAP
                                Figure  5.   Controlled condensation system probe design.

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enough so that the heating wire is completely used up 2 inches from the
ball joint.  Secure the end of the heating tape with a final wrap.
   e)  Bore a 9/16-inch hole into two No. 6 silicone rubber stoppers, then
cut a slit vertically down one side of the stopper into the 9/16-inch hole.
The slit will allow easy assembly.
   f)  Cut a piece of asbestos cloth approximately 30 inches long and wide
enough to wrap the probe and heating tape with a 1/2 turn overlap.  Tightly
wrap the probe and secure the asbestos cloth with glass tape.
   g)  Slide the 304 SS sheath over the Vycor probe.  Avoid scratching the
insulation on the electrical leads.  Position the sheath so that the end
near the tip extends one inch past the start of the heating tape.
   h)  Spread the stopper open, slip it over the tip of the probe, and
slide it into the 304 SS sheath.  The stopper is then wired to help hold
it in place.  Repeat this procedure for the other end, only use a hose
clamp to hold the back stopper in place.
   i)  Place the male quick connects on the end of the TC leads.   The red
TC lead goes to the negative terminal.
   j)  The probe should be tested in the laboratory to ensure that all
parts are in order.  Simply connect the heating wire to the Variac and
allow the probe to heat up.  Monitor the temperature to verify the TCs are
functioning.
                                   NOTE
         Whenever heating up the probe, start off with very low
         power inputs (^5 percent) until heating starts.
   k)  The  0.25-inch  nozzle and Teflon union  (Figure 5)  are attached  prior
to the test run.   The nozzle consists of a 0.5-inch diameter quartz tube
tapered to 0.25-inch  at one end and a 90° bend placed in the center of its
2.5-inch length.

4.2  FILTER HOLDER FABRICATION
     Figure 6 details the recommended design  for the quartz filter holder.
This  filter holder consists of a modified 40/50 standard taper quartz joint.
The modifications included adding a coarse quartz frit and an extension  tube

                                     17

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           18/9
           BALL
                                 SPRING
                                 ATTACHMENT
                                 HOOKS
TISSUE QUARTZ
FILTER
                                 18/9
                                SOCKET
00
                THERMOCOUPLE
                    WELL
                               STANDARD
                               TAPER QUARTZ
                               40/50
 SEAL
 EXTENTION
 TO STD.
 TAPER JOINT
EXTRA COARSE
QUARTZ FRIT
                                     Figure 6.  Quartz filter holder.

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to the male joint to act as a pressure seal when the Tissuequartz filter
pad is in place.  Ball-and-socket (18/9) joints are used to connect the
filter holder to the probe and controlled condensation coil.
                                   NOTE
         Be sure the extension tube seals on the Tissuequartz filter.
         If there is not a tight seal, carefully cut a washer out of
         a spare Tissuequartz filter to make a seal.  Do not use two
         filters.
4.3  SITE EQUIPMENT SETUP AND OPERATION
   a)   In the 3-inch port, insert a 3-inch plug with 1-inch hole.
   b)   Use a table or another suitable device to support the CCS (see
Figure 3).
   c)   Prior to use, be sure the controlled condensation coil (CCC) is
clean and dry.  Carry the CCC to the site with each end stoppered.   If any
condensation appears because of temperature changes, connect the CCC to the
water bath and start the circulation of the 60°C (140°F) water.   This  should
evaporate any premature condensate.
   d)   With the probe still out of the stack, assemble the train as shown
in Figure 3.  Be sure that each ball joint is completely clean and  free of
dust.   Because of the possibility that the greases will freeze at the tem-
peratures employed, it is not recommended that any grease be used.   Proper
care of the ground glass fittings will ensure that vacuum seals  are main-
tained.   Should any ground glass fitting not seal  vacuum-tight,  a small
amount of Apiezon H grease may be used for emergency repair.  As soon as
it is  possible, the joint in question should be returned to the  glass shop
for regrinding (see Tables 2 and 3 for further suggestions).
   e)   Connect the flowmeter to the vacuum pump exit.   Be sure that the
flowmeter is vertical.   Close off the end of the probe with a stopper, turn
on the vacuum pump and adjust the vacuum to read 380 torr (15 in. Hg).
   f)   Begin measuring the flowrate with the flowmeter.  If the  leak rate
is less  than 80 ml/min (0.003 cfm),  then the system is ready for use.   If a
leak rate greater than 80 ml/min is  found, the system should be  checked for
loose  joints and connections.  The pump should also be checked and  any worn
parts  replaced.  See Tables 2 and 3 for corrective action.

                                    19

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   g)  Once the vacuum test is completed, slowly turn the three-way valve

to the vent position and allow the air to bleed into the system.   This

must be done carefully to prevent a pressure surge from backing up the

impingers.  Remove the flowmeter from the system and unstopper the probe.

   h)  Begin heating the probe and the filter holder to 316°C (600°F) and

288°C (550°F), respectively.   The heating bath should already be at 60°C

(140°F).   Once the skin temperatures reach these values, the run can

commence.

                                   NOTE

         During the course of the run, the filter temperature will
         be controlled by the gas out temperature which should be
         288°C (550°F).

    i)  After  leak  testing, the  pump is  again  turned on  and  the  flowrate
 adjusted to 10 1pm (0.33 cfm)  using the dry test  meter  and  a  stopwatch.

 The  pump is turned off without  readjusting  the valve settings.

    j)  Pinch  the  hose  at the  end of the controlled  condensation  coil  and

 insert the heated  probe into  the duct with  the nozzle pointed downstream.

                                   NOTE

         The downstream orientation of the probe nozzle will reduce
         the gross amount of particulate collected in the probe and
         filter section.  Sulfuric acid aerosols should not be dis-
         criminated against because of their extremely small size,
         which allows them to follow the flow lines  into the nozzle.

    k)  Turn on the pump, release the pinched hose,  and obtain an initial

dry gas meter reading.   Throughout the run,  collect  the data required (see

Figure 7).

    1)  Sample for one hour or until 1/2 to  2/3 of the length of the coils

are frosted with HoSO..

                                   NOTE

         If the coil is operating properly,  the ^04 will  cover
         the inside of the coils as a thin gray-white film.   If
         large drops of a clear liquid form  and begin to block
         the coil, then moisture is being condensed.  Either the
         percentage moisture has exceeded 16 percent or the tem-
         perature of the water bath has dropped below 60°C.   Abort
         the run and check the water bath temperature with  an Hg
                                    20

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Sample Location_
Run #	
Run Date/Time_
Operator
Flowrate (cfm)
Ambient Pressure  (P)
                                    AEROSOL  SOs
                              (CONTROLLED CONDENSATION)
                                 FIELD DATA  SHEET
Reheater Air Flow Rate, acfm_
Inlet Gas Rate,  acfm
Sample Location  S02 (ppm]_
Boiler Load (mw)
Leak  Rate
Time (Min)


















AVG.
Temperature (°F)
Stack



















Probe



















Filter
Skin



















Out



















Recirc.
Water



















Exit
Coil



















Dry Gas
Meter
In



















Out



















Gas Meter
Reading,
cu. ft.



















          Figure 7.   Controlled  condensation field  data  sheet.
                                          21

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         thermometer and confirm the percentage moisture in the
         gas stream.  If the water bath is below 60°C, recalibrate
         the temperature bath control.   For every percent above
         16 percent h^O, adjust the CCC temperature 2°C upward.
         Clean and dry the CCC, and replace the reagents in the
         impingers prior to restarting  the run.
    m)  At the end of the sampling period, remove the probe from the duct
and slowly shut off the pump.  After the pressure drops, remove the CCC
from the system without removing the water bath hoses.  Carefully connect
the G/R coil (Figure 8) to the Erlenmeyer flask without spilling any con-
densate in the tube.  In 10 ml increments (up to 30 ml), use D.I. water to
rinse out the CCC.  Be careful to avoid introducing any dust or grease into
the rinse solution.  Take the rinse solution in the stoppered Erlenmeyer to
the laboratory, dilute to 50 ml with ^-free water prior to analysis.
                                   NOTE
         Multiple rinses are recommended to ensure a quantitative
         wash of the coil.
    n)  Rinse the probe with 30 to 40 ml of D.I. H^O after it has cooled.
Take this solution back to the laboratory, and filter it through a Whatman
number 1 filter into a 50 ml volumetric.  Dilute this solution to 50 ml
with COp-free water.
                                  CAUTION
            Wait until the filter has cooled before proceeding.
    o)  Remove the filter and any debris from the filter holder and place
it into a beaker.  Add 30 ml of D.I. H^O and swirl the beaker.  Filter the
solution through a Whatman number 1 filter into a 50 ml volumetric.  Repeat
with 10 ml portions of D.I. HLO until the volumetric is filled to the mark.
4.4  ANALYSIS PROCEDURES
     Two procedures can be used to determine the amount of H-SO* collected:
        1)  An acid/base titration using  Bromophenol  Blue  indicator  or
        2)  A sulfate titration using Sulfonazo III as the indicator.
     Since the end points for titrations are very color dependent, the end
point will probably vary slightly for each operator's sense of color.  To
                                    22

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                                                PIPET BULB
                                                 ADAPTER
                                              SOLUTION
                                            POSITIONING
                                               DRAIN
                                           STOPCOCK VALVE
                                             125 ML ERLENMEYER FLASK
 D.I.

 FROM COIL
Figure 8.   Controlled  condensation  coil rinsing apparatus.

                              23

-------
obtain the most accurate data, the following techniques should be employed

in all titrations:

        •  Always add the same number of drops of indicator.

        t  Have the same operator do the blank and sample.

        •  Always titrate to the same color intensity.

        •  Avoid parallax errors - keep eyes at the same level as
           the liquid meniscus and hold a white piece of paper
           behind it with a dark line horizontal  to the table top.

        •  Remove air bubbles from buret tip prior to use.

        •  Never store reagent in buret.  Always  rinse out  buret
           with a slight amount of titrant.

        •  Always record titrant type and volume  used.

Because of the simplicity and sensitivity of the  acid/base  titration,  it is

the recommended procedure.  The sulfate procedure is included in this  sec-

tion to act as a backup or total sulfate method if the need arises.   In

either case all the titrations should be done in  triplicate and the  results

recorded on the laboratory data sheet (Figure 9).

4.4.1  Sulfate Titration Using Sulfonazo III.  (References)

     1)  Hash the Dowex 50 W-X8 cation exchange resin with  10 percent
         V/V HC1 .  Fill a 1/2-inch I.D. ion exchange column to a
         3-inch bed depth and place glass wool pads at the  bottom
         and top of the bed.  Rinse the column with deionized water
         until the  elutant tests neutral with pH  paper.

     2)  Transfer 0.025g of chemically pure Sulfonazo III indicator
         [(NaS02)2  C10 H2 (OH)21 (N:NC§ H4S03H)2  to a 25 mi-bottle,
         add water  to dissolve the indicator, and fill  to the mark.

     3)  Transfer approximately 3.90 q of reagent grade barium per-
         chlorate trihydrate [BatClO.lL.SHpO] into a one-liter
         reagent bottle, add a small amount of distilled water to
         dissolve the salts, and then fill  to the mark.  Mix the
         contents of the bottle.
     4)  Standardize the Ba^lO.K by titrating sodium sulfate.  Dry
         the iJa9SO» in an oven for two hours at 125°C and allow to
         cool t& room temperature in a desiccator.  Weight out accu-
         rately in triplicate 12  to  16 mg of the Na2S04 from a weigh-
         ing bottle into 125 ml  Erlenmeyer flasks, dissolve  with  10 ml
         deionized water, add 10  ml  acetone and three drops  Sulfonazo
         III indicator solution,  and titrate with the barium perchlorate.

                                    24

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                                AEROSOL S03
                           (CONTROLLED CONDENSATION)
                           LABORATORY  DATA  SHEET
Run #
Sample  Location
Run Date/Time_

Analyst	
Date Lab Analysis Completed
            Variable
               Value
Aliquot Size (A)
Normality of titrant (N)
ml of titrant used to titrate G/R coil
rinses (v)
Blank (equivalent NaOH)
Net titration volume (V)
Absolute dry gas meter temperature (Tm)
Volume of gas sampled (Vm)
Meter Pressure (P )
ppm HpSO. (vol/vol)
(ml)
(eq./O
(ml)
(ml)
(ml)
Avg. (ml)
(ml)
(ml)
(°R)
(ft3)
(in. Hg)


Normality of acid used to titrate blank
(if used)
                    Figure 9.   Laboratory  data sheet.

                                     25

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     5)   Repeat this procedure in triplicate for the sample  and  blank
         (D.I.  H20):
                            M  =
                                  (142)  (V-va)
         Where:   M  =  Molarity  of  the  barium  perchlorate  solution,
                      moles/liter

                 W  =  Weight of sodium sulfate titrated,  mg

                 V  =  Average volume of barium perchlorate solution
                      required  for titration  of sodium sulfate,  ml

                 v3  =  Average volume of D.I.  water blank  titration.
                  a

     6)  Take a  10 ml  aliquot of the rinse solution and pass  it  through
         the ion exchange column at 3  ml/min.   Rinse the  column  with
         30 ml  deionized water  and collect the elutant and rinsings  in
         a 50-ml volumetric flask  and  dilute  to the mark  with deionized
         water.

     7)  After every tenth use  of  the  column,  regenerate  it with 100 ml
         of 10 percent W/V HC1  at  3 ml/min flowrate and rinse until  the
         elutant tests neutral  to  pH paper.   Rinse the column with  50 ml
         of D.I. water.

     8)  Add 10  ml acetone and  three drops of the Sulfonazo  III  indicator
         to a 10 ml  aliquot of  the ion exchange elutant.

     9)  Titrate with  0.01 M Ba(C104)2 using  a magnetic stirrer  and  back
         lighting.  The color will change from purple to  blue.   The  end
         point is the  point at  which an additional drop of titrant does
         not change the color of the solution.  The end point should not
         fade unless left standing for more than 5 to 10  minutes.   Record
         the volume of 0.01 M Ba(C10»)~ used to reach the end point  and
         calculate the average  titration volume.  Titrate a 10 ml  aliqout
         of D.I. water in the same fashion to obtain the  titration  blank.

4.4.2  Acid/Base Titration

     The preferred method of analysis  is the  acid/base titration using

Bromophenol Blue  indicator.  Carefully handle and store the samples  in  clean

glassware and analyze  them as soon as  possible.  Record all results  on the

laboratory data  sheet.
                                     26

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     Each acid/base indicator in this procedure will change color over a
different pH range.  For example:
        Indicator               pH Range               Color  Change
     Bromphenol Blue           3.0  to  4.6           yellow to blue
     Phenolphthalein           8.2  to  10.0          colorless to pink
     The point measured by the indicator is simply the point at which the
color change occurs.  The actual end point where exactly the right amount
of acid and base have reacted (equivalence point) can be close to or far
away from the indicator end point.   Thus Bromophenol Blue is chosen for the
NaOH/H2S04 titration, since the equivalence point occurs at about pH 3.
Phenolphthalein is used for the KHP/NaOH standardization titration because
the equivalence point is near pH 7.
     Even though the indicators have been selected to be as close as pos-
sible to the actual end point, a small difference still exists and is
called the indicator blank.  The indicator blank for phenolphthalein is
the amount of NaOH required to change a specific amount of water contain-
ing a known number of drops of phenolphthalein pink.  This value is sub-
tracted from the milliliters used to titrate the sample.
     The indicator blank from Bromophenol Blue is determined in the same
way (known volume and number of drops) except that a standard acid (H2$OJ
is used to backtitrate the indicator in distilled water to a  yellow color.
The number of milliequivalents used is added to the amount found titrating
the sample.
                                   NOTE
         Blanks can vary with sample size and number of drops
         of indicator;  therefore determine the indicator blank
         under the same conditions  in  which the sample is
         titrated.
     The procedures for standardization and sample analysis follow:
     1)   Pipet 10 ml  of the 0.0200  N KHP solution into a  125  ml  wide-
         mouth Erlenmeyer flask.
     2)   Add 3 drops of the Phenolphthalein indicator.   With  a swirling
         action of the  flask, titrate  with 0.02 N NaOH solution  until  the
         first pink color stays.  Record the volume and repeat from  (1)
         in  triplicate.   Repeat this procedure using D.I.  H^O (blank).

                                    27

-------
     3)  Average the volume used to titrate the KPH solution.   The
         true normality of the standard NaOH solution equals:
                           (0.0200)  (10 ml)
                     N =
                           (ml  titrant - ml  blank)

     4)  To titrate the H?SO, in the condensation coil, probe, and
         filter rinses, piper 10 ml  of one of these solutions into
         a 125-ml  Erlenmeyer flask.

     5)  Add 3 drops of the Bromophenol  Blue indicator to the solution
         and titrate to the blue end point with standard NaOH.  Trip-
         licate analyses should be performed as well  as an indicator
         blank during the blank test titration.  (See Paragraph 4.4.2).
         Remember this Bromophenol Blue  sample blank is added to the
         sample value.

4.4.3  Calculation of the H^SO. ppm (v/v) Concentration

     Using either the sulfate or acid base titration, the concentration  of
SO- as H?SO, in the flue gas stream can  be calculated.

     Note:  The formula is based on  a 50 ml  original  sample volume.

     1)  From the Field Data Sheet (Figure 7)  obtain the average dry
         test meter temperature, volume  of gas sampled and the pressure
         at the meter box.  Record these values on  the Laboratory Data
         Sheet.  (Figure 9).

     2)  Using the Laboratory Data Sheet, insert the correct numbers into
         the following formula
                                                        /NVT  \
         for acid/base titration:  ppm H2SO. = 1,201.9  1 ... p  I
                                                        \  m m/

         for sulfate titration:  ppm H?SO, = 12,019
         The result is ppm (v/v)  H2S04 at 70°F and 29-92  in Hg.

         Note:  This value can be 12 percent low due to fly ash  present
                on the filter (See Introduction).
                                    28

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                      5.  DATA MONITORING PROCEDURES

     The data monitoring procedures for the CCS are devoted mainly to the
acid-base titration performed in the laboratory and to the monitoring of
the H2S04 ppm values calculated.
5.1  ACID BASE TITRATION
     In order to check the accuracy of the titrations performed on the CCS
samples, an independent check of the NaOH solution and titration method is
required.  An unknown standard sample of f^SO, approximately 0.01 N should
be analyzed by the lab personnel every couple of weeks.  Analysis of the
sample should be in triplicate and reported to 3 places (O.X Y I).  Analy-
sis of this sample will  provide information on the precision of the CCS
titrations and accuracy of the results.
     The procedure follows:
     1)  Take a 10 ml aliquot of the unknown standard.
     2)  Titrate in triplicate with Bromophenol Blue to the blue
         end point and record the number of millilHers used.
     3)  Determine the normality of the solution from:
                                          Vfl
         where:  N. = Normality of the acid
                 V. = Volume acid aliquot taken (ml)
                 NB = Normality of the base
                 VB = Volume of the base used to titrate the sample (ml)

     The results of the determination should not differ by more than ±10
percent within the triplicate numbers nor should the  determined normality
be off by more than ±10 percent.
                                    29

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     If the values differ by more than 10 percent:
        •  Check the calculations and be sure the correct values
           have been used.
        •  Repeat the analysis.
        •  If the value is  still  off, restandardize the NaOH with KHP.
        •  Repeat the test.
5.2  DATA MONITORING BY STATISTICAL QUALITY CONTROL
     In many cases where inlet and outlet information in h^SO*  values are
measured, it was possible to monitor the SO., results by plotting the inlet
and outlet S03 values.   Since there is a direct correlation between outlet
and inlet concentrations, a  simple control  chart using regression analysis
can be used (Figure 10) to  evaluate the data.  The area between the 2 and
3a limits is the warning zone.  A point falling in this area indicates
that the measurement system  may be out of control.   The region  between  the
-2a and +2a limits should contain, in the long run, 95 percent  of all
future paired measurements.   The region between the -3o and the +3a limits
should, essentially, contain all  future paired measurements of  inlet and
outlet contamination.  A point falling outside of the 3o limits indicates
that the measurement system  is out of control.
     The a limits should be  based on a "large sample", say  >30, of paired
measurements.  If, for a particular environmental situation, the sample
size is less than 30, interim charts will be established using  tolerance
limits.  Thus, the warning  limits will be the (90,90) limits.   That is,
it is expected that 90 percent of the future observations will  lie within
such limits, 90 percent of  the time.  The rejection limits, or  the limits
that indicate that the system is out of control will be the (90,95) limits.
That is, it is expected that 95 percent of the future observations will be
within these limits 95 percent of the time.  At all times:
        t  Check with the power plant of the scrubber control room to find
           out if any mechanical  problems occurred during the run.
        •  Verify that all  the laboratory numbers are correct and
           repeat the analysis if solution is left over.
                                    30

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        re
        s-
        o>
        (J
        c.
        o
        d)
CO
                                                                                                  +30 limit


                                                                                                  +2
-------
                        6.  MAINTENANCE SCHEDULES

     Table 2 details the recommended maintenance schedule.   Following this
schedule is imperative to prevent breakdown and to maintain the high accu-
racy required in the program.
                                    32

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                                                     TABLE  2.   GENERAL MAINTENANCE  SCHEDULE
           Component
                                                          Maintenance  Schedule By:
           Run
          Week
                                       Month
      Calibration Procedure
        Probe nozzles
        Quartz probe
        Impingers
oo
GO
        Pump
        Swage!ok fittings
        CCS filter holder
        CCC
        NaOH solution
Inspect nozzle for  damage.

Brush nozzle before and
after run to remove inside
particulate.

Before and after each  run
brush and rinse with rea-
gent grade acetone  or
Freon then D.I. ^0 until
the rinse is clean.

Rinse out after each run
with D.I. water.

Inspect and clean seal
area and 0-rings.

Leak test before each  run.
Before each run check  leak
rate in pumping system.
Inspect fitting,  espe-
cially ferrule and seat
for wear and dirt.  Clean
or replace fitting as
required.

Inspect and clean after
each run.  Replace filter
after each run.
Inspect and clean  after
each run
                              Inspect vanes on diaphragm.
                              Inspect and clean motor
                              brushes.
Clean frit each week
in hot chromic acid
for 12 hours.   Rinse  to
neutral pH with D.I.  H20.

Clean coils and frit  each
week in hot chromic acid
for 12 hours.   Rinse  to
neutral pH with D.I.  H20.

Standardize the stock NaOH
with KHP weekly.
                                                            Measure nozzle  ID with micrometer.
                                                            N/A
                                                            N/A
Leak test at 380 torr  (15" Hg)
and verify that a leak rate of
<80 ml  (0.003  cfm) is maintained.

Total leak rate in system at
380 torr (15"  Hg) must be less
than 80 ml/min (0.003  cfm).

N/A
N/A
                                                                                                                      N/A
                                                                                                                                       (Continued)

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                                                                   TABLE  2.   (continued)
              Component
                                                             Maintenance Schedule By:
            Run
                                         Week
                                                                      Month
                                                                   Calibration Procedure
          Thermocouples
          Temperature
          Indicator
OJ
-p.
          Connecting
          lines
Inspect lines for wear and
kinks.
Clean readout of all  dust.
Clean tips of shielded TCs.

Clean connector prongs
with steel wool.
          Dry test meter
Blow out connecting lines
with air.

Visually inspect exterior
for wear.  Especially
inspect hose to fitting
connections.

Clean exterior.
Flush with water and dry
with clean plant air.
Calibrate thermocouples.
                               Have  electronics  shop
                               remove  the  back and clean
                               the inside  of  the unit.

                               Check indicated tempera-
                               ture  with calibrated
                               thermocouple.
                               Calibrate versus wet test
                               meter  every 3 months.
Calibrate TC at two points  (ice-
water and near boiling).  Compare
TC readings to mercury thermometer.
Replace TC if agreement is  not
within 3°C (6°F).

Perform thermocouple calibration
with readout unit  using indepen-
dently calibrated  thermocouple.

Check indicated temperature read-
ings with calibrated thermocouple.
                               N/A
                               Run wet and dry test meters in
                               series; note temperature and
                               pressure.  If dry test meter is
                               >3% off, send to factory for
                               recallbration.

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                7.    TROUBLESHOOTING AND REPAIR PROCEDURES

     Table 3 lists  possible problems that can be encountered with the
equipment used in the test program.  This list should be updated by the
field personnel  as  new problems are encountered and solved.
                                    35

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                                                      TABLE  3.   TROUBLESHOOTING  AND REPAIR
             Component
                                         General Remarks
                                                         Problem
                                               Repair Sequence
         S-Pitot Nozzles
         Probe Nozzles
CO
en
         Quartz Probes
         Impingers
Alignment of pitot tubes  is  critical.
The tubes must be facing  180° with
respect to each other and parallel
to gas flow in the duct.
A smooth circular edge is  required
for accurate sampling.  Alignment
of nozzle face must be perpendicular
to gas flow.
Avoid mechanical  shocks  especially
when probe is hot.   Before  cleaning
probe with liquids,  allow the  probe
to cool to air temperature.

Impingers, should be cleaned with soap
and water.  Deposits should not  be
allowed to build  up  inside  impinger.
All nozzles should reach to within
±1.3 cm (0.5") of the bottom of  the
impinger.   To ensure good seals,
keep the impinger seals  clean.
Misaligned nozzle
Damaged edge


Nozzle wear or damage



Misalignment



Normal wear and cleanliness




Normal wear and cleanliness
                                                                          Leakage  in  impinger system
Return S-Pitot tubes  to original 180°
alignment.

Align nozzles  to  be parallel to gas
flow.

Position face  of  nozzle to  be perpen-
dicular to gas flow.

File and buff  edge to smooth oval -
repeat alignment  checks.

Loosen Swagelok fitting and realign
(x-axis) nozzle face  to perpendicular
to gas flow.

Bend nozzle neck  (y-axis) so that
nozzle face is perpendicular to gas
flow.

Brush and rinse with  acetone after
each run (Note:  Test brush tc ensure
it is not dissolved by the  acetone).
Rinse out with D.I.  water  after each use.
Dry impinger to be used  for moisture
trap.

Clean sealing edges.
                                                                                 Check all Swagelok fittings.

                                                                                 Inspect  impinger seal area for dirt or
                                                                                 damage.  Clean area if dirt found.

                                                                                 Use  larger 0-ring.

                                                                                 If all other measures fail to locate leak,
                                                                                 pressurize and immerse in water to  find
                                                                                 leak.
                                                                                                                                             (continued)

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                                                                  TABLE 3.    (continued)
              Component
            General  Remarks
              Problem
          Repair  Sequence
          Thermocouples
          Temperature
          Indicator
GO
          Mantle or probe
          Connecting lines
          Pump
Thermocouple (TC)  leads and wire  are
fragile and require care in arranging
the equipment set-up to prevent kink-
ing and stripping  of leads.  Never
pull a TC apart by pulling on the
lead.  Verify that the polarity is
not reversed anywhere in the system.
Be sure that the same type of TC
wire and connectors are used in the
system (Iron-constantan or chromel-
alumel).  Do not bend casing of
shielded thermocuople.

Store in dust-free area.
Never exceed maximum temperature as
stated in the manufacturer's manual.
While these lines are either heavy
vacuum hose or steel-braided Teflon
lines, care should be taken to mini-
mize weight supported by the lines
and excessive mechanical abuse.
Care must be taken in shutting the
pump off after a run.  Rapid shut-
down without bleeding air into the
pumping system will cause the
impingers to back up toward the
filter.
Temperature- indicator fluctuat-
ing over wide range
Temperature readings fluctuat-
ing on one channel

No temperature readout or fluc-
tuating temperatures on all  the
channels with thermocouples
attached

No temperature rise with current
on
General maintenance
Leakage (oil-free)
Locate possible short  in TC wire or con-
nectors.   Once portion of wire with short
is located,  mark and have the wire
replaced.

Have readout checked by electrical
shop if no external short can be found.
Check thermocouple for short  in  lead or
connectors.

Return to electronic shop for repair.

Return to manufacturer if problem cannot
be found.

Check electrical  connections.

Check main power.

Check fuses and circuit breakers.

Verify thermocouple connected.

Replace any worn or corroded  parts.
Check all valve and hosing connections
leading to pump.

If the leakage has been isolated in  the
pump, disassemble pump and inspect vanes
for wear and replace if necessary.
                                                                                                                                              (continued)

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                                                                   TABLE  3.    (continued)
             Component
           General  Remarks
                                                         Problem
          Repair Sequence
         Pump
         (Continued)
                                           Leakage  (diaphragm)
         Swagelok fittings
Swagelok fittings are designed to  seal
with a minimum of tightening.   Exces-
sive torque applied to the fitting
will eventually cause leakage.
                                                                           Installation
OJ
CO
                                                                           Reinstallation
For leakage or low  flow  in  diaphragm
pumps check the diaphragm cover to ensure
it has not vibrated loose.

Remove face plate and  inspect diaphragm for
signs of wear or pinholes.  Check the dia-
phragm gasket for wear;  replace if
necessary.

Insert the tubing in the service.

Insert the tubing into the  Swagelok tube
fitting.  Make sure that the tubing rests
firmly on the shoulder of the fitting and
that the nut is finger-tight.

Due to the variation of  tubing diameters,
a common starting point  is  desirable.
Therefore, use a wrench  to  snug up the
nut until the tubing will not turn (by
hand) in the fitting.  'At this point,
scribe the nut and  body  at  the 6 o'clock
position of the fitting. Now while hold-
ing the fitting body steady with a backup
wrench, tighten the nut  one-and-one
quarter turns.  Watching the scribe mark,
make one complete revolution and continue
to the 9:00 o'clock position.

Tubing with preswaged  ferrules inserted
into the fitting until front ferrule
seats in fitting.  Tighten  nut by hand.
Rotate nut about one-quarter turn with
wrench (or to original one-and-one
quarter tight position), then snug
slightly with wrench.
                                                                                                                                             (continued)

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                                                                  TABLE 3.   (continued)
             Component
                                          General Remarks
                                                                                         Problem
                                                                                           Repair Sequence
         Dry Test Meter
          CCS  filter
oo
10
          ccc
These meters are very sensitive to
mechanical shock and should be handled
with care.  Corrosive gas from the
stack should never be passed through
the meter without prescrubbing.

The 6/R filter holder is made out of
quartz and especially when it is hot,
mechanical shocks will cause break-
age.  The filter holder is designed
to always be run with a filter on the
quartz frit.  Because of the high
temperatures employed, greasing the
joints is not recommended.
The coil is an especially delicate
piece of equipment.  Clear visibility
of the coils is necessary to  main-
tain the water jacket's cleanliness.
Incorrect volume  readings
No seal  to filter
                                                                           Gas leakage
                                                                           Plugged frit
Gas leakage
Check meter for blockage.

Check mechanical  linkage  for wear.

Recalibrate meter.

Check extension tube.   If it is  not mak-
ing a seal, have the glass blower  repair.
As a temporary repair, a  washer  out of
Tissuequartz can be used  to promote a
seal.

Check thermocouple well for pinhole leak.

Check alignment of ball-and-socket joints.
Try to maintain linearity.

Check seal at joints, clean joints, and
retest.

Check joints for thermal  warping.  Replace.

Soak in hot chromic acid cleaning  bath  for
12 hours.  Rinse with D.I. H20 till
neutral.

Check thermocouple well for pinhole  leak.

Check alignment of ball-and-socket joints.
Try to maintain linearity.

Check seal at joints, clean joint, and
retest.

Check joints for thermal  warping.  Replace.

Soak in hot chromic acid cleaning  bath  for
12 hours.  Rinse with D.I. H2<3 till
neutral.

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                          8.    REFERENCES



1.   Federal  Register,  Volume  41,  No. Ill, pages 23061-23063.

2.   Goksoyr, H.  and  K.  Ross,  J.  Inst.  Fuels, 35, 177 (1962).

3.   Lisle, F.S.  and  J.D.  Sensenbaugh,  Combustion, 1, 12 (1965).

A.   Nacovsky, W.,  Combustion, J,  35  (1967).

5.   Standard Methods for  the  Examination of Water and Wastewater,
     13th Ed., pages  52-56 (1971).

6.   Maddalone R.,  C. Zee, and A.  Grant,  "Procedure for Titrimetric
     Determination  of Sulfate  Using Sulfonazo III Indicator," TRW
     Systems, EPA Contract No. 68-02-1412, Task 6, February 14, 1975.

7.   E.F. Brooks  and  R.L.  Williams, "Technical Manual for Process
     Stream Volumetric  Flow Measurement and Gas Sample Extraction
     Methodology,"  TRW  System, EPA Contract 68-02-1412, Task 13,
     November 1975.
                                40

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                                TECHNICAL REPORT DATA
                          (Please read Instructions on the reverse before completing)
 1. REPORT NO.
 EPA-600/7-79-156
                           2.
                                                      3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
 Process Measurement Procedures: H2SO4 Emissions
                                5. REPORT DATE
                                July 1979
                                                      6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

 R. Maddalone and N. Garner
                                                      8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 TRW Defense and Space Systems Group
 One Space Park
 Redondo Beach, California 90278
                                                      10. PROGRAM ELEMENT NO.
                                INE624
                                11. CONTRACT/GRANT NO.

                                68-02-2165, Task 202
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC 27711
                                13. TYPE OF REPORT AND PERIOD COVERED
                                Task Final; 6/76 - 2/77
                                14. SPONSORING AGENCY CODE
                                 EPA/600/13
 15. SUPPLEMENTARY NOTES EPA project officer R.M.Statnick is no longer with IERL-RTP;
 for details, contact F.E.Briden, Mail Drop 62, 919/541-2557.
 16. ABSTRACT Tne report gives procedures to measure H2SO4 vapor or aerosols in con-
 trolled or uncontrolled flue gas streams. The method was designed to operate at
 temperatures up to 250 C with 3000 ppm SO2, 8-16% H2SO4,  and up to 9 g/cu m of
 particulate matter.  The basis of the method is the clean separation of particulate
 matter, H2SO4 vapor, and SO2.  A heated (>250 C) quartz filter system removes
 the particulate matter, but passes most of the H2SO4 vapor to a modified Graham
 condenser. There the gas is cooled to about 62 C to condense and collect the  H2SO4
 vapor while passing the SO2  and H2O vapor. The condensed acid is titrated with
 either NaOH using bromophenol blue indicator or Ba(ClO4)2 using Sulfonazo HI as
 the indicator. The laboratory coefficient of variance is + or  - 6% and the estimated
 field accuracy is + or - 11%. Flyash on the filter was shown to reduce the recovery
 of H2SO4 by 12% at the 10 ppm H2SO4 level.  Field experiments showed that as little
 as 0.1 ppm H2SO4 could be detected.
 7.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                                          b.IDENTIFIERS/OPEN ENDED TERMS
                                            c. COS AT I Field/Group
 Pollution
 Sulfuric Acid
 Vapors
 Aerosols
 Sulfur Dioxide
 Dust
Flue Gases
Pollution Control
Stationary Sources
Particulate
13B
07B
07D
                                            11G
2 IB
 3. DISTRIBUTION STATEMENT
 Release to Public
                                          19. SECURITY CLASS (ThisReport)
                                          Unclassified
                                                                   21. NO. OF PAGES
                                                  45
                   20. SECURITY CLASS (Thispage)
                    Unclassified
                                            22. PRICE
EPA Form 2220-1 (9-73)
                                       41

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